Negative photosensitive film, multilayer film, dry film, and negative photosensitive composition

Abstract

This negative photosensitive film comprises a tri- or higher-functional epoxy resin, a photoacid generator, and an adhesion enhancer having a functional group which is hydrolyzed to form a hydroxy group, and is characterized by having a moisture content of 0.1-1 mass%. A dry film (100) comprises a substrate film (110) and, laminated thereto in the following order, the negative photosensitive film (120) according to the present invention and a cover film (150). A multilayer film (130) comprises a substrate film (110) and, laminated thereto, the negative photosensitive film (120) according to the present invention. The present invention can provide: the negative photosensitive film (120) which has enhanced adhesion to substrates and is less apt to form inclusions therein; the multilayer film (130) and the dry film (100) in which the negative photosensitive film (120) has been laminated; and a negative photosensitive composition.

Description

Negative-type photosensitive film, laminated film, dry film, and negative-type photosensitive composition

[0001] The present invention relates to a negative-type photosensitive film, a laminated film, a dry film, and a negative-type photosensitive composition. This application claims priority under Japanese Patent Application No. 2024-195916, filed in Japan on November 8, 2024, the contents of which are incorporated herein by reference.

[0002] With the recent miniaturization and increased density of electronic devices, there is a growing demand for photosensitive dry films used in the manufacture of electronic components. For example, by adhering a photosensitive dry film to the surface of a semiconductor wafer, selectively exposing the dry film to radiation such as light or electron beams, developing it to form a pattern, and then pressing it against a transparent substrate (e.g., a glass substrate), the dry film can be used as a spacer between the semiconductor wafer and the transparent substrate. The photosensitive resin layer of the dry film must contain a photosensitive material and be able to be patterned by photolithography, as well as maintain its shape as a spacer. Furthermore, since it is pressed against a transparent substrate after exposure and development, it is required to have excellent developability, resolution, and adhesion between the patterned photosensitive resin layer and the transparent substrate.

[0003] Conventionally, negative-type photosensitive compositions used in photosensitive dry films have been proposed that contain a substrate component containing epoxy groups and a cationic polymerization initiator. As cationic polymerization initiators, fluorinated antimony-based cationic polymerization initiators with high sensitivity to light (e.g., SbF) have been proposed. ６ － Polymerization initiators having the anionic portion are widely used (see, for example, Patent Document 1).

[0004] Japanese Patent Publication No. 2005-55865

[0005] However, as the formation of increasingly finer patterns progresses, conventional photosensitive dry films require greater adhesion between the film and the substrate. In addition, as patterns become finer, the impact of defects such as foreign matter that occur in the pattern after development becomes greater, making it difficult to stably form patterns of the required fine dimensions.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a negative-type photosensitive film that can improve adhesion to a substrate and is less prone to generating foreign matter, as well as a laminated film, a dry film, and a negative-type photosensitive composition obtained by laminating the same.

[0007] To solve the above problems, the present invention employs the following configuration.

[0008] In other words, the first aspect of the present invention is a negative-type photosensitive film containing a polyfunctional epoxy resin with three or more functions, a photoacid generator, and an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis, wherein the moisture content is 0.1% by mass or more and 1% by mass or less.

[0009] A second aspect of the present invention is a laminated film in which a base film and a negative-type photosensitive film according to the first aspect are laminated together.

[0010] A third aspect of the present invention is a dry film in which a negative-type photosensitive film according to the first aspect and a cover film are laminated on a base film in that order.

[0011] A fourth aspect of the present invention is a negative-type photosensitive composition comprising a trifunctional or polyfunctional epoxy resin, a photoacid generator, an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis, and water, wherein the water content is 0.1 parts by mass or more and 1 part by mass or less per 100 parts by mass of the trifunctional or polyfunctional epoxy resin.

[0012] According to the present invention, it is possible to provide a negative-type photosensitive film that has improved adhesion to a substrate and is less prone to generating foreign matter, as well as a laminated film, a dry film, and a negative-type photosensitive composition obtained by laminating the same.

[0013] This is a cross-sectional view showing one embodiment of a dry film.

[0014] In this specification and within these claims, “aliphatic” is defined as a concept relative to aromatic, meaning a group, compound, etc., that does not possess aromaticity. Unless otherwise specified, “alkyl group” includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups. “Halogenated alkyl group” is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples of such halogen atoms include fluorine, chlorine, bromine, and iodine atoms. “Fluorinated alkyl group” or “fluorinated alkylene group” means a group in which some or all of the hydrogen atoms of the alkyl group or alkylene group are substituted with fluorine atoms. “Constituent unit” means a monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer). When it is stated that "may have substituents" or "may have substituents," this refers to the case where a hydrogen atom (-H) is substituted with a monovalent group, and the case where a methylene group (-CH) is substituted with a monovalent group. ２ This includes both cases where the negative (-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation irradiation.

[0015] "Constituent units derived from styrene" refers to constituent units formed by the cleavage of the ethylenic double bond of styrene. "Constituent units derived from styrene derivatives" refers to constituent units formed by the cleavage of the ethylenic double bond of styrene derivatives. "Styrene derivatives" is a concept that includes styrene in which the hydrogen atom at the α-position is substituted with other substituents such as alkyl groups and alkyl halides, as well as their derivatives. Examples of such derivatives include styrene in which the hydrogen atom of the hydroxyl group of styrene, whose α-position hydrogen atom may be substituted with a substituent, is substituted with an organic group; and styrene in which a substituent other than a hydroxyl group is bonded to the benzene ring of styrene, whose α-position hydrogen atom may be substituted with a substituent. Note that α-position (the carbon atom at the α-position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified. Substituents that substitute the hydrogen atom at the α-position of styrene are the same as those listed as α-position substituents in the α-substituted acrylic acid esters mentioned above.

[0016] The alkyl group as the α-substituent is preferably a linear or branched alkyl group, specifically an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc.). Furthermore, the halogenated alkyl group as the α-substituent is specifically a group in which some or all of the hydrogen atoms of the alkyl group as the α-substituent are replaced with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine being particularly preferred. Furthermore, the hydroxyalkyl group as the α-substituent is specifically a group in which some or all of the hydrogen atoms of the alkyl group as the α-substituent are replaced with hydroxyl groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, with 1 being the most preferred.

[0017] A dry film according to one aspect of the present invention is characterized by a negative-type photosensitive film constituting a photosensitive composition layer, and known techniques can be applied to components other than the photosensitive composition layer.

[0018] Figure 1 is a cross-sectional view in the thickness direction of the film showing one embodiment of a dry film. Note that in the drawing, components may be shown schematically for clarity, and the dimensional scale may be different for some components. In Figure 1, the dry film 100 is formed by laminating a negative-type photosensitive film 120 and a cover film 150 on a base film 110 in that order. Alternatively, the dry film 100 is formed by laminating a base film 110 and a negative-type photosensitive film 120 into a laminated film 130, with the cover film 150 laminated on the negative-type photosensitive film 120 side. The negative-type photosensitive film 120 employs a negative-type photosensitive film according to one aspect of the present invention. The dry film 100 is provided, for example, as a roll wound around a core.

[0019] (Negative-type photosensitive film) One embodiment of the negative-type photosensitive film contains a polyfunctional epoxy resin with three or more functions, a photoacid generator, and an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis. The moisture content of the negative-type photosensitive film of this embodiment is 0.1% by mass or more and 1% by mass or less, based on the total mass of the negative-type photosensitive film.

[0020] In the dry film 100 shown in Figure 1, since it is equipped with the negative-type photosensitive film 120 of this embodiment, the adhesion between the cured photosensitive composition layer (negative-type photosensitive film) and the substrate is good. In addition, in the dry film 100, since it is equipped with the negative-type photosensitive film 120 of this embodiment, foreign matter is less likely to be generated during pattern formation, the occurrence of defects is suppressed, and fine-dimensional patterns can be stably formed.

[0021] When the negative-type photosensitive film of this embodiment is used and selectively exposed, the photoacid generator decomposes in the exposed areas of the negative-type photosensitive film to generate acid. Due to the action of this acid, the epoxy groups in the epoxy resin undergo ring-opening polymerization, reducing the solubility of the epoxy resin in a developer containing an organic solvent (organic developer). On the other hand, the solubility of the epoxy resin in the organic developer does not change in the unexposed areas of the negative-type photosensitive film. Therefore, a difference in solubility in the organic developer occurs between the exposed and unexposed areas of the negative-type photosensitive film. Consequently, when the negative-type photosensitive film is developed with an organic developer, the unexposed areas are dissolved and removed, leaving the exposed areas as afterimages and forming a negative-type pattern.

[0022] <Moisture Content of Negative Photosensitive Film> The moisture content of the negative photosensitive film in this embodiment is preferably 0.1% by mass or more and 1% by mass or less, and more preferably 0.1% by mass or more and 0.9% by mass or less, relative to the total mass of the negative photosensitive film. If the moisture content of the negative photosensitive film is above the lower limit of the above range, for example, the adhesion between the cured photosensitive composition layer (negative photosensitive film) and the substrate can be improved. On the other hand, if it is below the upper limit of the above range, foreign matter is less likely to be generated during pattern formation.

[0023] From the viewpoint of adhesion to the substrate, the moisture content of the negative-type photosensitive film of this embodiment is preferably 0.15% by mass or more and 1% by mass or less, more preferably 0.18% by mass or more and 1% by mass or less, and even more preferably 0.50% by mass or more and 1% by mass or less, based on the total mass of the negative-type photosensitive film. From the viewpoint of minimizing the generation of foreign matter, the moisture content of the negative-type photosensitive film of this embodiment is preferably 0.10% by mass or more and 0.80% by mass or less, more preferably 0.10% by mass or more and 0.50% by mass or less, and even more preferably 0.10% by mass or more and 0.20% by mass or less, based on the total mass of the negative-type photosensitive film.

[0024] The water contained in the negative-type photosensitive film may be water that has been intentionally added or water that has been introduced unintentionally, that is, water contained in the measurement sample described later. Intentionally added water includes, for example, water that has been incorporated into the negative-type photosensitive composition for forming the negative-type photosensitive film. Water that has been introduced unintentionally includes, for example, water contained in components other than water (trifunctional or more polyfunctional epoxy resin, photoacid generator, adhesion enhancer, or other components) incorporated into the negative-type photosensitive composition for forming the negative-type photosensitive film, or water absorbed by the negative-type photosensitive film.

[0025] The moisture content of a negative-type photosensitive film can be adjusted by controlling the heating conditions (e.g., temperature, heating time) when forming the negative-type photosensitive film during the production of the laminated film. Alternatively, the moisture content of a negative-type photosensitive film can be adjusted by controlling the water content in the negative-type photosensitive composition used for forming the negative-type photosensitive film.

[0026] [Measurement of Moisture Content of Negative Photosensitive Film] The moisture content of negative photosensitive film was measured using the Karl Fischer electrocautery method (combination of electrocautery and moisture vaporizer) for each sample, with a heating temperature of 110°C and carrier gas: dry N2. ２ This value is measured under the specified conditions. The moisture content of a negative-type photosensitive film is expressed as the amount of moisture contained in the sample, as a percentage (mass%) of the total mass (100% mass%) of the sample.

[0027] The negative-type photosensitive film of this embodiment has a moisture content of 0.1% by mass or more and 1% by mass or less, and contains a trifunctional or polyfunctional epoxy resin, a photoacid generator, an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis, and other components as needed.

[0028] <Trifunctional or higher polyfunctional epoxy resin>In the present embodiment, the trifunctional or higher polyfunctional epoxy resin refers to an epoxy resin having three or more epoxy groups in one molecule. As the trifunctional or higher polyfunctional epoxy resin (hereinafter also referred to as the "(A1) component") contained in the negative photosensitive film of the present embodiment, those having sufficient epoxy groups to form a negative pattern by exposure are used.

[0029] As the (A1) component, a bisphenol novolak type epoxy resin is preferable. Examples of the bisphenol novolak type epoxy resin include a polyfunctional epoxy resin produced by the reaction of a bisphenol novolak resin and epichlorohydrin, or a polyfunctional epoxy resin obtained by novolakizing bisphenol glycidyl ether. Among them, due to good adhesion to the substrate and easy availability, etc., bisphenol A novolak type epoxy resin can be preferably used.

[0030] As the bisphenol novolak type epoxy resin, a resin represented by the following general formula (A1-1) is preferably mentioned.

[0031] [In formula (A1-1), R ｐ１ and R ｐ２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A plurality of R ｐ１ may be the same as or different from each other. A plurality of R ｐ２ may be the same as or different from each other. n １ is an integer of 1 to 5. R ＥＰ is an epoxy group-containing group. A plurality of R ＥＰ may be the same as or different from each other. ]

[0032] In the above formula (A1-1), R ｐ１ and R ｐ２The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups, while examples of cyclic alkyl groups include cyclobutyl and cyclopentyl groups. Among these, R ｐ１ , R ｐ２ As such, a hydrogen atom or a linear or branched alkyl group is preferred, a hydrogen atom or a linear alkyl group is more preferred, a hydrogen atom or a methyl group is even more preferred, a methyl group is particularly preferred, R ｐ１ , R ｐ２ It is most preferable that all of them are methyl groups. In formula (A1-1), multiple R ｐ１ These may be identical or different from one another. ｐ２ They may be identical or different from one another.

[0033] In the above formula (A1-1), n １ is an integer from 1 to 5, preferably 2 or 3, and more preferably 2.

[0034] In the above formula (A1-1), R ＥＰ R is an epoxy group-containing group. ＥＰThe epoxy group-containing group is not particularly limited and includes groups consisting solely of epoxy groups; groups consisting solely of alicyclic epoxy groups; and groups having an epoxy group or an alicyclic epoxy group and a divalent linking group. An alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically, a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that forms the basic skeleton of an alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. Examples of polycyclic alicyclic groups include norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, and tetracyclododecyl group. Furthermore, the hydrogen atoms of these alicyclic groups may be substituted with alkyl groups, alkoxy groups, hydroxyl groups, etc. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or alicyclic epoxy group is bonded via the divalent linking group bonded to the oxygen atom (-O-) in the formula.

[0035] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have substituents, a divalent linking group which contains a heteroatom, and so on.

[0036] Regarding divalent hydrocarbon groups which may have substituents: Such divalent hydrocarbon groups may be aliphatic hydrocarbon groups or aromatic hydrocarbon groups. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated. More specifically, examples of such aliphatic hydrocarbon groups include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups which contain a ring in their structure.

[0037] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically a methylene group [-CH] ２-], ethylene group [- (CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ Examples include -]. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6, even more preferably 2 to 4, and most preferably 2 or 3. A branched alkylene group is preferred as the branched aliphatic hydrocarbon group, specifically -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkyl methylene 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 - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH２ -ien-CH ２ CH (CH ３ )CH ２ CH ２ Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0038] Examples of aliphatic hydrocarbon groups containing a ring in the structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically examples include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0039] The aromatic hydrocarbon group in a divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This 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, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of aromatic hydrocarbon groups include: a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) in which one hydrogen atom is replaced by an alkylene group (e.g., a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0040] The divalent hydrocarbon group may have substituents. The linear or branched aliphatic hydrocarbon group, as the divalent hydrocarbon group, may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0041] The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in its structure, as a divalent hydrocarbon group, may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, etc. Preferably, the alkyl group as a substituent has 1 to 5 carbon atoms, and most preferably it is a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Preferably, the alkoxy group as a substituent has 1 to 5 carbon atoms, and preferably it is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, or tert-butoxy group, with methoxy and ethoxy groups being the most preferred. Examples of halogen atoms as a substituent include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. Examples of alkyl halides as a substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. Alicyclic hydrocarbon groups may have some of the carbon atoms constituting their ring structure substituted with substituents containing heteroatoms. Examples of such substituents containing heteroatoms include -O-, -C(=O)-O-, -S-, and -S(=O). ２ -, -S (=O) ２ -O- is preferred.

[0042] As a divalent hydrocarbon group, the aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. As the alkyl group substituent, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl groups, ethyl groups, propyl groups, n-butyl groups, and tert-butyl groups are most preferred. Examples of alkoxy groups, halogen atoms, and alkyl halides as substituents include those exemplified as substituents that substitute for hydrogen atoms in the alicyclic hydrocarbon group.

[0043] Regarding the divalent linking group containing a heteroatom: The heteroatom in the divalent linking group containing a heteroatom 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, a halogen atom, etc.

[0044] In the divalent linking group containing a heteroatom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)-(H may be substituted with a substituent such as an alkyl group, an acyl group, etc.); -S-, -S(=O) ２ -, -S(=O) ２ -O-, general formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ , -[Y ２１ -C(=O)-O] ｍ” -Y ２２ - or -Y ２１ -O-C(=O)-Y ２２ - represented by the group [wherein, Y ２１ and Y ２２ are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m'' is an integer of 1 to 3.], etc. are exemplified. When the divalent linking group containing the heteroatom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)-, the H thereof may be substituted with a substituent such as an alkyl group, an acyl group, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms. For the formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ -, -[Y ２１ -C(=O)-O] ｍ” -Y ２２ - or -Y ２１ -O-C(=O)-Y ２２ - in, Y２１ and Y ２２ These are, independently, divalent hydrocarbon groups which may have substituents. Examples of such divalent hydrocarbon groups include those similar to the "divalent hydrocarbon groups which may have substituents" mentioned in the above-mentioned description of divalent linking groups. ２１ Preferably, a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, a linear alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred. ２２ Preferably, the group is a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula - [Y ２１ -C (=O) -O] ｍ” -Y ２２ In the base represented by -, m'' is an integer from 1 to 3, preferably 1 or 2, and particularly preferably 1. That is, formula -[Y ２１ -C (=O) -O] ｍ” -Y ２２ As a base represented by -, see formula -Y ２１ -C(=O)-O-Y ２２ Groups represented by - are particularly preferred. Among them, the group represented by formula - (CH ２ ) ａ’ -C(=O)-O-(CH ２ ) ｂ’ A base represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0045] Among them, R ＥＰ A glycidyl group is preferred as the epoxy group-containing group in this product.

[0046] Alternatively, as component (A1), a novolac-type epoxy resin having a constituent unit represented by the following general formula (anv1) is also a suitable example.

[0047] [In the formula, R ＥＰ R is an epoxy group-containing group. ａ２２ and R ａ２３ These are, independently, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0048] In the above formula (anv1), R ａ２２ , R ａ２３ The alkyl group having 1 to 5 carbon atoms is R in formula (A1-1) above. ｐ１ , R ｐ２ This is similar to alkyl groups with 1 to 5 carbon atoms. ａ２２ , R ａ２３ The halogen atom is preferably a chlorine atom or a bromine atom. In the above formula (anv1), R ＥＰ R in formula (A1-1) is ＥＰ Similar to the above, a glycidyl group is preferred.

[0049] The following are specific examples of the constituent units represented by the above formula (anv1).

[0050]

[0051] Component (A1) may be a resin consisting only of the constituent unit (anv1), or it may be a resin having the constituent unit (anv1) and other constituent units. Examples of resins consisting only of the constituent unit (anv1) include cresol novolac type epoxy resins and phenol novolac type epoxy resins.

[0052] The following is a specific example of a resin consisting only of constituent units (anv1). n0 represents the number of repetitions of the constituent unit (anv1).

[0053]

[0054] In a resin having the aforementioned constituent unit (anv1) and other constituent units, examples of such other constituent units include the constituent units represented by the following general formulas (anv2) to (anv3), respectively.

[0055] [In the formula, R ａ２４ R is a hydrocarbon group which may have substituents. ａ２５ ~R ａ２６ , R ａ２８ ~R ａ３０ Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. ａ２７ This is an epoxy group-containing group, or a hydrocarbon group which may have substituents.

[0056] In the above formula (anv2), R ａ２４ This is a hydrocarbon group which may have substituents. Examples of hydrocarbon groups which may have substituents include linear or branched alkyl groups or cyclic hydrocarbon groups. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, n-pentyl groups, etc. Among these, methyl groups, ethyl groups, or n-butyl groups are preferred, and methyl groups or ethyl groups are more preferred.

[0057] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0058] R ａ２４When the group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0059] R ａ２４ When the cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This 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, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. ａ２４Specific examples of aromatic hydrocarbon groups in this context include: a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0060] In the above formulas (anv2) and (anv3), R ａ２５ ~R ａ２６ , R ａ２８ ~R ａ３０ Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. The alkyl group having 1 to 5 carbon atoms and the halogen atom are each R ａ２２ , R ａ２３ It is similar to that.

[0061] In the above formula (anv3), R ａ２７ R is an epoxy group-containing group or a hydrocarbon group which may have substituents. ａ２７ The epoxy group containing the R in formula (A1-1) is ＥＰ It is similar to R. ａ２７ The hydrocarbon group which may have substituents is R in formula (anv2). ａ２４ It is similar to that.

[0062] The following are specific examples of the constituent units represented by the above formulas (anv2) to (anv3).

[0063]

[0064] If component (A1) has other constituent units in addition to constituent unit (anv1), the proportion of each constituent unit in component (A1) is not particularly limited, but the total amount of constituent units having epoxy groups is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol% relative to the total amount of all constituent units of component (A1).

[0065] Alternatively, as component (A1), a trifunctional epoxy compound having three epoxy groups in the molecule is preferred. Examples of such trifunctional epoxy compounds include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, and trifunctional epoxy compounds represented by the following general formula (A1-2).

[0066] [In formula (A1-2), R ｐ３ , R ｐ４ and R ｐ５ Each of these is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ＥＰ This is an epoxy group-containing group. Multiple Rm ＥＰ They may be identical or different from one another.

[0067] In the above formula (A1-2), R ｐ３ , R ｐ４ and R ｐ５ The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups, while examples of cyclic alkyl groups include cyclobutyl and cyclopentyl groups. Among these, R ｐ３ , R ｐ４ and R ｐ５ Preferably, each of these is a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, even more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group in all cases.

[0068] In the above formula (A1-2), Rm ＥＰ is an epoxy group containing R in formula (A1-1) above. ＥＰ Similar to the above, a glycidyl group is preferred. Multiple Rm ＥＰ They may be identical or different from one another.

[0069] The following are specific examples of trifunctional epoxy compounds represented by the formula (A1-2).

[0070]

[0071] Among the trifunctional epoxy compounds, compounds having a structure in which the distance between the three epoxy groups within the molecule is large are preferred because intramolecular crosslinking reactions do not proceed easily. Tris(4-hydroxyphenyl)methane triglycidyl ether or the trifunctional epoxy compound represented by the above general formula (A1-2) is more preferred, the trifunctional epoxy compound represented by the above general formula (A1-2) is even more preferred, and the trifunctional epoxy compound represented by the above chemical formula (A1-2-1) is particularly preferred.

[0072] Alternatively, as component (A1), an epoxy compound that is liquid at 23°C (hereinafter also referred to as "component (A2)") may be used. The molecular weight of component (A2) is, for example, 300 or less, preferably 100 to 290, and more preferably 200 to 270.

[0073] Component (A2) is, for example, an aliphatic epoxy resin that is liquid at 23°C. Examples of aliphatic epoxy resins include compounds containing a substructure represented by the following general formula (A2-m1) (hereinafter also referred to as "component (m1)").

[0074] [In the formula, n ２ [This is an integer between 1 and 4.]

[0075] In formula (A2-m1), n ２ is an integer between 1 and 4, preferably between 1 and 3, and more preferably 2.

[0076] Component (m1) includes compounds in which multiple substructures represented by the general formula (A2-m1) are bonded via a divalent linking group or a single bond. Among these, compounds in which multiple substructures represented by the general formula (A2-m1) are bonded via a divalent linking group are preferred. The divalent linking group here is not particularly limited, but preferred examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. For divalent hydrocarbon groups which may have substituents and divalent linking groups which contain heteroatoms, R in formula (A1-1) above is used. ＥＰ Similar to the divalent hydrocarbon group and the divalent linking group containing a heteroatom described in (epoxy group-containing group), which may have substituents, among these, the divalent linking group containing a heteroatom is preferred, -Y ２１ The group represented by -C(=O)-O-, -C(=O)-O-Y ２１ A group represented by - is more preferable. Y ２１ Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0077] Furthermore, aliphatic epoxy resins also include compounds represented by the following general formula (A2-m2) (hereinafter also referred to as "(m2) component").

[0078] [In the formula, R ＥＰ This is an epoxy group-containing group. Multiple R ＥＰ They may be identical or different from one another.

[0079] In the formula (A2-m2), R ＥＰ is an epoxy group containing R in formula (A1-1) ＥＰ It is similar to that.

[0080] Furthermore, examples of component (A2) include epoxidized polybutadiene, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, inositol hexaglycidyl ether, etc.

[0081] In the negative-type photosensitive film of this embodiment, component (A1) may be used alone or in combination of two or more types. Among the above, a preferred component (A1) is solid at 23°C and has a softening point of, for example, 50°C or higher, which may be 55°C or higher, 60°C or higher and 80°C or lower, or 65°C or higher and 75°C or lower. The softening point of the epoxy resin is a value measured by the ring-and-sphere method.

[0082] The epoxy equivalent of component (A1) is preferably 180 g / eq. to 300 g / eq., more preferably 180 g / eq. to 280 g / eq., even more preferably 180 g / eq. to 240 g / eq., and particularly preferably 180 g / eq. to 230 g / eq. The epoxy equivalent of the epoxy resin can be measured by potentiometric titration as described in JIS K-7236. Examples of methods for measuring epoxy equivalent by potentiometric titration include the hydrochloric acid-dioxane method, the perchloric acid-tetraethylammonium bromide method, the perchloric acid-cetyltrimethylammonium bromide method, the hydrochloric acid-potassium iodide method, and the Dubertaki method using hydrobromic acid acetic acid solution.

[0083] Component (A1) is preferably at least one polyfunctional epoxy resin selected from the group consisting of bisphenol novolac type epoxy resin, novolac type epoxy resin, and trisphenol type epoxy resin; more preferably at least one polyfunctional epoxy resin selected from the group consisting of the resin represented by the general formula (A1-1), the novolac type epoxy resin having the constituent unit represented by the general formula (anv1), and the trifunctional epoxy compound represented by the general formula (A1-2); even more preferably at least one polyfunctional epoxy resin selected from the group consisting of bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and the trifunctional epoxy compound represented by the chemical formula (A1-2-1); and from the viewpoint of adhesion to the substrate, at least one polyfunctional epoxy resin selected from the group consisting of bisphenol A novolac type epoxy resin and cresol novolac type epoxy resin is particularly preferred.

[0084] The content of component (A1) in the negative-type photosensitive film of this embodiment is preferably 80% by mass or more, more preferably 80 to 95% by mass, even more preferably 85 to 95% by mass, and particularly preferably 90 to 95% by mass, based on the total mass of the negative-type photosensitive film.

[0085] (A1) Component may be a synthesized polyfunctional epoxy resin or a commercially available product. Examples of commercially available products for component (A1) include jER-152, jER-154, jER-157S70, jER-157S65 (all manufactured by Mitsubishi Chemical Corporation); EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON Examples include HP5000 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), YDCN-704 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), and TECHMORE VG3101L (manufactured by Printec Co., Ltd.).

[0086] <Photoacid Generator> The photoacid generator (hereinafter also referred to as "component (I)") contained in the negative-type photosensitive film of this embodiment is a compound that generates cations upon irradiation with active energy rays such as ultraviolet light, far ultraviolet light, excimer laser light such as KrF and ArF, X-rays, electron beams, etc., and these cations can act as polymerization initiators. Examples of component (I) include antimonate salts, borate salts, and other photocationic polymerization initiators (other photocationic polymerization initiators).

[0087] <<Antimonate Salts>> Suitable antimonate salts include, for example, compounds represented by the following general formula (I2-2).

[0088] [In the formula, R ｂ０６ R is a fluorinated alkyl group which may have substituents, or a fluorine atom. ｂ０６ They may be the same or different from each other. q is an integer greater than or equal to 1, and Q ｑ＋ This is a q-valent organic cation.

[0089] - In the anion part of formula (I2-2), R ｂ０６ R is a fluorinated alkyl group which may have substituents, or a fluorine atom. ｂ０６ They may be identical or different from one another. ｂ０６ The fluorinated alkyl group in is preferably one to ten carbon atoms, more preferably one to eight, and even more preferably one to five. Specifically, examples include alkyl groups having one to five carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms. Among these, R ｂ０６ Preferably, a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom is preferred, more preferably a perfluoroalkyl group or a fluorine atom having 1 to 5 carbon atoms, and a fluorine atom ([SbF ６ ] － ) is even more preferable.

[0090] - In the cation part of formula (I1), Q ｑ＋Suitable examples include sulfonium cations and iodonium cations, with organic cations represented by the following general formulas (ca-1) to (ca-5) being particularly preferred.

[0091] [In the formula, R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ Each of these independently represents an optionally substituted aryl group, heteroaryl group, alkyl group, or alkenyl group. ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ These atoms may bond to each other to form a ring with the sulfur atom in the formula. ２０８ ~R ２０９ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２１０ This may be an aryl group having a substituent, an alkyl group having a substituent, an alkenyl group having a substituent, or an -SO group having a substituent. ２ - Contains a cyclic group. L ２０１ This represents -C(=O)- or -C(=O)-O-. ２０１ Each of these independently represents an arylene group, an alkylene group, or an alkenylene group. x is either 1 or 2. W ２０１ This represents a (x+1) valence linking group.

[0092] R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. ２０１ ~R ２０７ , and R ２１１ ~R ２１２Examples of heteroaryl groups in this context include those in which some of the carbon atoms constituting the aryl group are substituted with heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Examples of such heteroaryl groups include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and examples of substituted heteroaryl groups include a group obtained by removing one hydrogen atom from 9H-thioxanthene-9-one. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkenyl group in is preferably one with 2 to 10 carbon atoms. ２０１ ~R ２０７ , and R ２１０ ~R ２１２ Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

[0093] [In the formula, R' ２０１ Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0094] In the above equations (ca-r-1) to (ca-r-10), R' ２０１ Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0095] A cyclic group which may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0096] R' ２０１ The aromatic hydrocarbon group in R' is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. ２０１ Specifically, examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R' ２０１ Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, anthracenyl groups, etc.), groups in which one of the hydrogen atoms of the aromatic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl groups, etc.), groups obtained by removing one hydrogen atom from a ring in which some of the hydrogen atoms constituting the aromatic ring are substituted with oxo groups, etc. (for example, anthraquinones, etc.), and groups obtained by removing one hydrogen atom from an aromatic heterocycle (for example, 9H-thioxanthene, 9H-thioxanthene-9-one, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0097] R' ２０１ The cyclic aliphatic hydrocarbon group in this context refers to an aliphatic hydrocarbon group that contains a ring in its structure. Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group from which one or more hydrogen atoms have been removed from a monocycloalkane. The preferred monocycloalkane has 3 to 6 carbon atoms, and specifically includes cyclopentane and cyclohexane. A preferred polycyclic alicyclic hydrocarbon group is a group from which one or more hydrogen atoms have been removed from a polycycloalkane, and the preferred polycycloalkane has 7 to 30 carbon atoms. Among these, polycycloalkanes having a cross-linked ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are more preferred; polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0098] Among them, R' ２０１ The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, with adamantyl and norbornyl groups being particularly preferred, and the adamantyl group being the most preferred.

[0099] The linear or branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically a methylene group [-CH]. ２ -], ethylene group [- (CH ２ )２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ Examples include -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 methylene 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 - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0100] A chain-like alkyl group which may have substituents: R' ２０１ The linear alkyl group may be linear or branched. Linear alkyl groups preferably have 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, and docosyl groups. Branched alkyl groups preferably have 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0101] A chain-like alkenyl group which may have substituents: R' ２０１ The linear alkenyl group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the linear alkenyl groups listed above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0102] R' ２０１ Examples of substituents in the cyclic group, linear alkyl group, or alkenyl group include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, oxo groups, and the above R' ２０１ Examples include cyclic groups, alkylcarbonyl groups, and thienylcarbonyl groups in this material.

[0103] Among them, R' ２０１ The preferably substituted cyclic group and the preferably substituted linear alkyl group are both cyclic and linear alkyl groups.

[0104] R ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ When these atoms bond to each other and form a ring with the sulfur atom in the formula, they can be heteroatoms such as sulfur, oxygen, and nitrogen atoms, or carbonyl groups, -SO-, -SO ２ -, -SO ３ -, -COO-, -CONH- or -N(R Ｎ )-(the R Ｎ is an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring is preferably a 3 to 10-membered ring, and particularly preferably a 5 to 7-membered ring, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthlene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthlene ring, a phenoxatiyine ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, and the like.

[0105] In the above formula (ca-3), R ２０８ ~R ２０９ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. If an alkyl group is formed, it may bond to each other to form a ring.

[0106] In the above formula (ca-3), R ２１０This may be an aryl group having a substituent, an alkyl group having a substituent, an alkenyl group having a substituent, or an -SO group having a substituent. ２ - Contains a cyclic group. R ２１０ Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. ２１０ The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. ２１０ The alkenyl group in this compound preferably has 2 to 10 carbon atoms.

[0107] In the above equations (ca-4) and (ca-5), Y ２０１ These independently represent an arylene group, an alkylene group, or an alkenylene group. ２０１ The arylene group in this case is R' ２０１ An example of an aromatic hydrocarbon group in this context is the aryl group exemplified above, with one hydrogen atom removed. ２０１ In this case, the alkylene group and alkenylene group are R' ２０１ Examples of the chain-like alkyl groups and chain-like alkenyl groups mentioned above include groups obtained by removing one hydrogen atom from the exemplified groups.

[0108] In the above equations (ca-4) and (ca-5), x is either 1 or 2. ２０１ This is a (x+1) valence, i.e., a divalent or trivalent linking group. ２０１ In the above formula (A1-1), the divalent linking group is preferably a divalent hydrocarbon group which may have substituents, and R ＥＰ A group similar to the divalent hydrocarbon group which may have substituents as exemplified is preferred. ２０１ The divalent linking group in may be linear, branched, or cyclic, but cyclic is preferred. Among these, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting only of an arylene group, is preferred. Examples of arylene groups include phenylene groups and naphthylene groups, with phenylene groups being particularly preferred. ２０１ The trivalent linking group in is the aforementioned W ２０１Examples include a group obtained by removing one hydrogen atom from a divalent linking group, and a group in which another divalent linking group is bonded to the aforementioned divalent linking group. ２０１ In this compound, a trivalent linking group is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0109] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0110]

[0111] [In the formula, R” ２０１ is a hydrogen atom or a substituent. The substituent is R. ２０１ ~R ２０７ and R ２１０ ~R ２１２ These are the same as those listed as substituents that may be present.

[0112] Furthermore, as the cation represented by the formula (ca-1), cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferred.

[0113]

[0114] [In the formula, R' ２１１ R is an alkyl group. ｈａｌ This is a hydrogen atom or a halogen atom.

[0115] Furthermore, as the cation represented by the formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are also preferred.

[0116]

[0117] Furthermore, as the cation represented by the formula (ca-1), cations represented by the following chemical formulas (ca-1-49) to (ca-1-54), each having a benzoylphenyl group, are also preferred.

[0118]

[0119] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0120] Specific examples of suitable cations represented by the above formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0121]

[0122] Specific examples of suitable cations represented by the above formula (ca-4) include the cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0123]

[0124] Furthermore, as the cation represented by the formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferred.

[0125] [In the formula, R' ２１２ R' is an alkyl group or a hydrogen atom. ２１１ It is an alkyl group.

[0126] Among the above, the cation part [(Q ｑ＋ ) １／ｑ The cation portion of the antimonate salt in this embodiment is preferably represented by the general formula (ca-1), more preferably by the cations represented by formulas (ca-1-1) to (ca-1-54), and even more preferably by the cations represented by formulas (ca-1-26), (ca-1-48) to (ca-1-54). ｑ＋ ) １／ｑ As for the cation, the cation represented by formula (ca-1-26) is particularly preferred.

[0127] <<Borate Salts>> Borate salts generate relatively strong acids upon exposure. Therefore, by forming patterns using negative-type photosensitive film containing borate salts, sufficient sensitivity can be obtained and good patterns can be formed. Furthermore, the use of borate salts has a low risk of toxicity and metal corrosion. Suitable borate salts include, for example, compounds represented by the following general formula (I1).

[0128] [In the formula, R ｂ０１ ~R ｂ０４ Each is independently an aryl group which may have substituents, or a fluorine atom. q is an integer of 1 or more, where Q ｑ＋ This is a q-valent organic cation.

[0129] - In the anion part of formula (I1), R ｂ０１ ~R ｂ０４ The aryl group in is preferably 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specifically, examples include naphthyl, phenyl, and anthracenyl groups, with the phenyl group being preferred due to its availability. ｂ０１ ~R ｂ０４ The aryl group in formula (I1) may have substituents. These substituents are not particularly limited, but are preferably halogen atoms, hydroxyl groups, alkyl groups (linear or branched alkyl groups are preferred, and the number of carbon atoms is preferably 1 to 5), halogenated alkyl groups, more preferably halogen atoms or halogenated alkyl groups having 1 to 5 carbon atoms, and particularly preferably fluorine atoms or fluorinated alkyl groups having 1 to 5 carbon atoms. The presence of a fluorine atom in the aryl group is preferable because it increases the polarity of the anionic moiety. Among these, R in formula (I1) is particularly preferable. ｂ０１ ~R ｂ０４ As for the groups, fluorinated phenyl groups are preferred, and perfluorophenyl groups are particularly preferred.

[0130] A preferred specific example of the anionic portion of the compound represented by formula (I1) is tetrakis(pentafluorophenyl)borate ([B(C ６ F ５ ) ４ ]－ ); tetrakis[(trifluoromethyl)phenyl]borate([B(C ６ H ４ CF ３ ) ４ ] － ); difluorobis(pentafluorophenyl)borate ([(C ６ F ５ ) ２ BF ２ ] － ); trifluoro(pentafluorophenyl) borate ([(C ６ F ５ ) BF ３ ] － ); tetrakis(difluorophenyl) borate ([B(C ６ H ３ F ２ ) ４ ] － Examples include ) and others. Among them, tetrakis(pentafluorophenyl) borate ([B(C ６ F ５ ) ４ ] － ) is particularly preferable.

[0131] - In the cation part of formula (I1), q is an integer of 1 or more, and Q ｑ＋ This is a q-valent organic cation. The cation portion of this borate salt [(Q ｑ＋ ) １／ｑ ] is the [(Q ｑ＋ ) １／ｑ Examples include those similar to the above, with a cation represented by the general formula (ca-1) being preferred, cations represented by formulas (ca-1-1) to (ca-1-54) being more preferred, and cations represented by formulas (ca-1-48) to (ca-1-54) being even more preferred.

[0132] <<Other Photocationic Polymerization Initiators>> Examples of photocationic polymerization initiators other than the antimonate salts and borate salts mentioned above include the compound represented by the following general formula (I2-1) (hereinafter referred to as "component (I2)"); and the compound represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "component (I3)").

[0133] Regarding component (I2): Component (I2) is a compound represented by the following general formula (I2-1). Since component (I2) generates a relatively strong acid upon exposure, sufficient sensitivity is obtained and a good pattern is formed when a negative-type photosensitive film containing component (I2) is used to form a pattern.

[0134] [In the formula, R ｂ０５ R is a fluorinated alkyl group which may have substituents, or a fluorine atom. ｂ０５ They may be the same or different from each other. q is an integer greater than or equal to 1, and Q ｑ＋ This is a q-valent organic cation.

[0135] - In the anion part of formula (I2-1), R ｂ０５ R is a fluorinated alkyl group which may have substituents, or a fluorine atom. ｂ０５ They may be identical or different from one another. ｂ０５ The fluorinated alkyl group in is preferably one to ten carbon atoms, more preferably one to eight, and even more preferably one to five. Specifically, examples include alkyl groups having one to five carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms. Among these, R ｂ０５ Preferably, the group is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms; more preferably, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms; and even more preferably, a fluorine atom, a trifluoromethyl group, or a pentafluoroethyl group.

[0136] The anionic portion of the compound represented by formula (I2-1) is preferably represented by the following general formula (b0-2a).

[0137] [In the formula, R ｂｆ０５ This is a fluorinated alkyl group which may have substituents. １ [This is an integer between 1 and 5.]

[0138] In formula (b0-2a), R ｂｆ０５ The fluorinated alkyl group which may have substituents in R is ｂ０５This is similar to the fluorinated alkyl groups that may have substituents listed above. In formula (b0-2a), nb １ The integer is preferably between 1 and 4, more preferably between 2 and 4, and most preferably 3.

[0139] - In the cation formula (I2-1), q is an integer of 1 or more, and Q ｑ＋ This is a q-valent organic cation. This cation part [(Q ｑ＋ ) １／ｑ ] is the [(Q ｑ＋ ) １／ｑ Similar examples can be given.

[0140] Regarding component (I3): Component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0141] [In the formula, R ｂ１１ ~R ｂ１２ m is a cyclic group which may have substituents other than halogen atoms, a linear alkyl group which may have substituents other than halogen atoms, or a linear alkenyl group which may have substituents other than halogen atoms. m is an integer of 1 or more, and M ｍ＋ These are, independently, m-valent organic cations.

[0142] - In the anion part of formula (I3-1), R ｂ１２ Examples include cyclic groups which may have substituents other than halogen atoms, linear alkyl groups which may have substituents other than halogen atoms, or linear alkenyl groups which may have substituents other than halogen atoms, and which are either unsubstituted or have substituents other than halogen atoms. ｂ１２Preferably, the group is a linear alkyl group which may have substituents other than halogen atoms, or an aliphatic cyclic group which may have substituents other than halogen atoms. The linear alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents other than halogen atoms); or a group obtained by removing one or more hydrogen atoms from camphor, etc.

[0143] R ｂ１２ The hydrocarbon group may have substituents other than halogen atoms, and examples of such substituents include hydroxyl groups, oxo groups, alkyl groups, aryl groups, lactone-containing cyclic groups, ether bonds, ester bonds, or combinations thereof. The phrase "may have substituents other than halogen atoms" here excludes not only the case of substituents consisting only of halogen atoms, but also the case of substituents containing at least one halogen atom (for example, when the substituent is a fluorinated alkyl group).

[0144] In the formula (I3-2), R ｂ１１ Examples include cyclic groups which may have substituents other than halogen atoms, linear alkyl groups which may have substituents other than halogen atoms, or linear alkenyl groups which may have substituents other than halogen atoms, and which are unsubstituted or have substituents other than halogen atoms. Among these, R ｂ１１ Preferred alternatives include aromatic hydrocarbon groups which may have substituents other than halogen atoms, aliphatic cyclic groups which may have substituents other than halogen atoms, or linear alkyl groups which may have substituents other than halogen atoms. Examples of substituents these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, lactone-containing cyclic groups, ether bonds, ester bonds, or combinations thereof.

[0145] The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The linear alkyl group is preferably having 1 to 10 carbon atoms, and specifically includes linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0146] R ｂ１１ As such, a cyclic group which may have substituents other than halogen atoms is preferred.

[0147] - In the cation portion, in formulas (I3-1) and (I3-2) above, M ｍ＋ M is an organic cation with an m-valence. ｍ＋ Suitable organic cations include those similar to the cations represented by the general formulas (ca-1) to (ca-5) above, and among these, the cation represented by the general formula (ca-1) above is more preferred. Among these, R in the general formula (ca-1) above is preferred. ２０１ , R ２０２ , R ２０３Sulfonium cations in which at least one of the groups is an organic group having 16 or more carbon atoms (aryl group, heteroaryl group, alkyl group, or alkenyl group) which may have substituents are particularly preferred because they improve resolution and roughness characteristics. The substituents that the organic group may have are the same as above, and include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the above formulas (ca-r-1) to (ca-r-10). The number of carbon atoms in the above organic group (aryl group, heteroaryl group, alkyl group, or alkenyl group) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18. ｍ＋ Suitable organic cations include, for example, the cations represented by the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), (ca-1-46), and (ca-1-47), respectively, and among these, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0148] The following are specific examples of component (I).

[0149]

[0150] In the negative-type photosensitive film of this embodiment, component (I) may be used alone or in combination of two or more types. In the negative-type photosensitive film used in this embodiment, component (I) is preferably a sulfonium salt. Alternatively, in the negative-type photosensitive film used in this embodiment, component (I) is preferably at least one photoacid generator selected from the group consisting of the above-mentioned antimonate salt, borate salt, component (I2), and component (I3). From the viewpoint of adhesion to the substrate, at least one photoacid generator selected from the group consisting of the above-mentioned antimonate salt and borate salt is more preferable, and using the above-mentioned antimonate salt is even more preferable.

[0151] In the negative-type photosensitive film of this embodiment, the content of component (I) is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, even more preferably 0.15 to 3 parts by mass, and particularly preferably 0.2 to 2 parts by mass, per 100 parts by mass of component (A1). If the content of component (I) is above the lower limit of the above preferred range, sufficient sensitivity is obtained and the lithography characteristics of the pattern are further improved. In addition, the strength of the negative-type photosensitive film is further increased. On the other hand, if it is below the upper limit of the above preferred range, the sensitivity is appropriately controlled and it becomes easier to obtain a pattern with a good shape.

[0152] <Adhesion Enhancer> The adhesion enhancer contained in the negative-type photosensitive film of this embodiment has a functional group that generates a hydroxyl group upon hydrolysis, and works to increase the bonding strength between the cured negative-type photosensitive film and the substrate. The adhesion enhancer can be any agent that has a functional group that generates a hydroxyl group upon hydrolysis, such as a silane coupling agent.

[0153] Suitable silane coupling agents include compounds represented by the following general formula (c0).

[0154] [In the formula, R Ｘ R represents a reactive group that chemically bonds with organic materials. Ｙ１ , R Ｙ２ and R Ｙ３ Each of these is an alkyl group having 1 to 20 carbon atoms, which may have substituents, and R Ｙ１ , R Ｙ２ and R Ｙ３ They may be the same or different.

[0155] In the above formula (c0), R Ｘ The reactive group in R can be any functional group that chemically bonds with the organic material, for example, an organic group having a vinyl group, epoxy group, amino group, methacryloyloxy group, acryloyloxy group, mercapto group, carboxyl group or isocyanate group. Among these, R Ｘ The reactive group in is preferably an epoxy group-containing group, and R in the above formula (A1-1) ＥＰSimilar to the above, a suitable reactant is the one represented as "glycidyl group-O-(alkylene group with 1 to 10 carbon atoms)-*". * indicates a bond that connects to Si in formula (c0).

[0156] In the above formula (c0), R Ｙ１ , R Ｙ２ and R Ｙ３ The alkyl groups in each are preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably methyl or ethyl groups, with methyl groups being particularly preferred.

[0157] Examples of silane coupling agents include γ-(methacryloyloxy)propyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 8-(glycidyloxy)octyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0158] In the negative-type photosensitive film of this embodiment, one adhesion enhancer may be used alone, or two or more may be used in combination. In the negative-type photosensitive film used in this embodiment, the adhesion enhancer is preferably a silane coupling agent, more preferably a silane coupling agent having a trialkoxysilyl group, and even more preferably a compound represented by the above general formula (c0).

[0159] In this embodiment, the content of the adhesion enhancer in the negative-type photosensitive film is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 3 to 7 parts by mass, per 100 parts by mass of component (A1). If the content of the adhesion enhancer is above the lower limit of the preferred range, the adhesion between the cured negative-type photosensitive film and the substrate is more easily improved. On the other hand, if it is below the upper limit of the preferred range, the generation of foreign matter during pattern formation is more easily suppressed.

[0160] <Other Components> In addition to the components (A1), (I), and adhesion enhancers described above, the negative-type photosensitive film of this embodiment may contain other components as needed. The negative-type photosensitive film of this embodiment may optionally contain miscible additives, such as resins other than trifunctional or polyfunctional epoxy resins, sensitizers, solvents, metal oxides, additional resins to improve the performance of the film, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and anti-halation agents.

[0161] <Other Resins> The negative-type photosensitive film of this embodiment may optionally contain other resins other than the <trifunctional or polyfunctional epoxy resin> described above. Examples of other resins include bifunctional epoxy resins, monofunctional epoxy resins, and resin components other than epoxy resins.

[0162] <<Sensitizer>> In the negative-type photosensitive film of this embodiment, it is preferable to further include a sensitizer, as this makes it easier to improve the adhesion between the cured negative-type photosensitive film and the substrate. The sensitizer is not particularly limited as long as it can absorb the energy from exposure and transfer that energy to other substances.

[0163] Specifically, known photosensitizers such as benzophenone-based photosensitizers including benzophenone and p,p'-tetramethyldiaminobenzophenone; carbazole-based photosensitizers; acetophen-based photosensitizers; naphthalene-based photosensitizers including 1-naphthol and 1,5-dihydroxynaphthalene; phenol-based photosensitizers; anthracene-based photosensitizers including 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9-ethoxyanthracene; thioxanthone-based photosensitizers including 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone; and biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone can be used.

[0164] In the negative-type photosensitive film of this embodiment, one type of sensitizer may be used alone, or two or more types may be used in combination. Among these, compounds having a thioxanthone skeleton, a naphthalene skeleton, or anthracene skeleton are preferred as the sensitizer, and at least one sensitizer selected from the group consisting of the above-mentioned naphthalene-based photosensitizers, anthracene-based photosensitizers, and thioxanthone-based photosensitizers is more preferred. When a sensitizer is included, the content of the sensitizer in the negative-type photosensitive film of this embodiment is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of component (A1). When the content of the sensitizer is within the above preferred range, the adhesion between the cured negative-type photosensitive film and the substrate is more easily improved. Furthermore, sensitivity and resolution are further improved during pattern formation.

[0165] As described above, the negative-type photosensitive film of this embodiment contains a polyfunctional epoxy resin with three or more functions and a photoacid generator, as well as an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis, and also contains water in a specific amount (0.1% by mass or more and 1% by mass or less). The negative-type photosensitive film of this embodiment controls the amount of moisture in the photosensitive composition layer after dry film formation. In such a negative-type photosensitive film, an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis is used. The generation of hydroxyl groups forms a bond with the substrate. If hydrolysis does not proceed sufficiently (the amount of moisture is too low), there will be insufficient hydroxyl groups to be generated, and a sufficient bond with the substrate cannot be formed. On the other hand, if hydrolysis proceeds too much (the amount of moisture is too high), the photosensitive composition layer containing an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis is prone to defects during pattern formation. In such a negative-type photosensitive film, the hydrolysis reactivity of the adhesion enhancer is controlled at a specific moisture content (0.1% by mass or more and 1% by mass or less), thereby improving adhesion to the substrate and reducing the likelihood of foreign matter formation.

[0166] (Laminated Film) One embodiment of a laminated film is formed by laminating a base film and the negative-type photosensitive film of the above-described embodiment. In Figure 1, the laminated film 130 is formed by laminating a base film 110 and a negative-type photosensitive film 120.

[0167] A known base film can be used, such as a thermoplastic resin film. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm. The thickness of the negative-type photosensitive film is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0168] [Formation of Negative Photosensitive Film and Fabrication of Laminated Film] The laminated film of this embodiment can be manufactured, for example, by applying a negative photosensitive composition for forming a negative photosensitive film onto a base film, and then performing a bake (post-application bake (PAB)) treatment, for example, at 90 to 120°C for 5 to 10 minutes to form a photosensitive composition layer (negative photosensitive film). The application of the negative photosensitive composition onto the base film can be carried out using an appropriate method such as a blade coater, lip coater, comma coater, or film coater.

[0169] Regarding negative-type photosensitive compositions: As an example, a negative-type photosensitive composition for forming a negative-type photosensitive film can be used, which is obtained by dissolving the above-mentioned components (A1) and (I), the adhesion enhancer and other components in a solvent (component (S)).

[0170] The solvent (component (S)) contained in the negative-type photosensitive composition may include, for example, water; lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having ester bonds such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; and monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc., of the polyhydric alcohols or compounds having ester bonds. Examples include derivatives of polyhydric alcohols such as compounds having ether bonds, such as methyl ether or monophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene, and dimethyl sulfoxide (DMSO). In the negative-type photosensitive composition, component (S) may be used alone or as a mixture of two or more solvents.

[0171] The content of component (S) in the negative-type photosensitive composition is appropriately set according to the coating thickness, etc. For example, the content of component (S) can be adjusted so that the solid content concentration of the negative-type photosensitive composition is 60% by mass or more, or it can be adjusted so that it is 70% by mass or more. However, if water is included, the water is added in a range that can be controlled so that the moisture content of the target negative-type photosensitive film is 0.1% by mass or more and 1% by mass or less. For example, it is preferable that the water content in the negative-type photosensitive composition is adjusted to 0.1 parts by mass or more and 1 part by mass or less per 100 parts by mass of component (A1).

[0172] Alternatively, as another example, embodiments of the negative-type photosensitive composition for forming a negative-type photosensitive film may also be used that substantially do not contain component (S) (i.e., embodiments in which the solid content concentration is 100% by mass).

[0173] (Dry Film) One embodiment of the dry film is one in which the negative-type photosensitive film of the above embodiment and a cover film are laminated on a base film in that order. In Figure 1, the dry film 100 is made by laminating the negative-type photosensitive film 120 and the cover film 150 on a base film 110 in that order. Alternatively, the dry film 100 is made by laminating the laminated film 130 and the cover film 150 so that the negative-type photosensitive film 120 and the cover film 150 are in contact.

[0174] A known base film can be used, such as a thermoplastic resin film. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm. The thickness of the negative-type photosensitive film is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0175] A known cover film can be used, such as a thermoplastic resin film. Examples of thermoplastic resins include polyethylene film and polypropylene film. The cover film is preferably one in which the adhesive strength to the negative-type photosensitive film is less than the adhesive strength between the base film and the negative-type photosensitive film. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm. The base film and the cover film may be made of the same film material or different film materials.

[0176] The dry film of this embodiment can be manufactured, for example, by applying the above-described negative-type photosensitive composition onto a base film, drying it to form a photosensitive composition layer (negative-type photosensitive film), and then laminating a cover film onto the photosensitive composition layer (negative-type photosensitive film). The application of the negative-type photosensitive composition onto the base film can be carried out using an appropriate method such as a blade coater, lip coater, comma coater, or film coater.

[0177] When a negative-type photosensitive film is formed using the dry film of this embodiment described above, and the negative-type photosensitive film is selectively exposed, the photoacid generator decomposes in the exposed areas of the negative-type photosensitive film to generate acid, and the epoxy groups in the epoxy resin undergo ring-opening polymerization due to the action of this acid. As a result, the solubility of the epoxy resin in the developer containing an organic solvent decreases in the exposed areas of the negative-type photosensitive film, while the solubility of the epoxy resin in the developer containing an organic solvent remains unchanged in the unexposed areas of the negative-type photosensitive film. Therefore, a difference in solubility in the developer containing an organic solvent occurs between the exposed and unexposed areas of the negative-type photosensitive film. Consequently, when the negative-type photosensitive film is developed with a developer containing an organic solvent, the unexposed areas are dissolved and removed, forming a negative-type pattern.

[0178] Here, the negative-type photosensitive film of the dry film of this embodiment is typically composed of a B-stage (semi-cured) resin material. The dry film of this embodiment is provided, for example, as a roll wound around a core.

[0179] (Pattern Forming Method) One embodiment of the pattern forming method is a method for forming a pattern that includes the steps of: forming a photosensitive composition layer (negative-type photosensitive film) on a support using the dry film of the above embodiment (hereinafter referred to as the "film forming step"), exposing the photosensitive composition layer (negative-type photosensitive film) to light (hereinafter referred to as the "exposure step"), and developing the exposed photosensitive composition layer (negative-type photosensitive film) with a developer solution containing an organic solvent to form a negative-type pattern (hereinafter referred to as the "development step"). The pattern forming method of this embodiment can be carried out, for example, as follows.

[0180] [Film Formation Process] First, a photosensitive composition layer (negative-type photosensitive film) is bonded to a support using the dry film of the above embodiment.

[0181] The support material is not particularly limited and conventionally known materials can be used, such as substrates for electronic components, substrates with predetermined wiring patterns formed thereon, and resins suitable for forming microchannels. More specifically, silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO) ３ ), niobium, lithium niobate (LiNbO ３ Examples of substrates include metal substrates such as palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. For wiring patterns, materials such as copper, aluminum, nickel, and gold can be used. Examples of resins include acrylic resin, polypropylene, polycarbonate resin, cycloolefin resin, polystyrene resin, polyester resin, urethane resin, vinyl chloride resin, silicone resin, and fluoropolymer resin.

[0182] The thickness of the photosensitive composition layer (negative-type photosensitive film) formed by the dry film is not particularly limited, but is preferably about 10 to 100 μm. The dry film of the above embodiment can also obtain good properties even when a thick film is formed.

[0183] [Exposure Process] Next, the formed photosensitive composition layer (negative-type photosensitive film) is subjected to selective exposure using a known exposure apparatus, either by exposure through a mask (mask pattern) on which a predetermined pattern has been formed, or by drawing by direct irradiation with an electron beam without going through a mask pattern. Then, if necessary, a bake (post-exposure bake (PEB)) process is performed for 40 to 1200 seconds, preferably 40 to 1000 seconds, more preferably 60 to 900 seconds, at a temperature of, for example, 80 to 150°C.

[0184] The wavelength used for exposure is not particularly limited; radiation, such as ultraviolet rays with wavelengths of 300-500 nm, i-rays (wavelength 365 nm), or visible light, is selectively irradiated (exposed). Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc., can be used as radiation sources. Here, radiation refers to ultraviolet rays, visible light, far-ultraviolet rays, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc., but for example, when using an ultra-high-pressure mercury lamp, it is 100-2000 mJ / cm². ２ That is the case.

[0185] The photosensitive composition layer (negative-type photosensitive film) after the exposure process has high transparency, and for example, the haze value when irradiated with i-line light (wavelength 365 nm) is preferably 3% or less, more preferably 1.0 to 2.5%. Thus, the photosensitive composition layer (negative-type photosensitive film) formed using the dry film of the above-described embodiment has high transparency. Therefore, when exposed during pattern formation, light transmittance is increased, and it is easy to obtain a negative-type pattern with good lithography characteristics. The haze value of such a photosensitive composition layer (negative-type photosensitive film) after the exposure process is measured using a method in accordance with JIS K 7136 (2000).

[0186] [Development Process] Next, the photosensitive composition layer (negative-type photosensitive film) after exposure is developed with a developer containing an organic solvent (organic developer). After development, a rinsing treatment is preferably performed. A bake treatment (post-bake) may be performed if necessary.

[0187] The organic solvent contained in the organic developer can be any solvent capable of dissolving component (A1) (component (A1) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0188] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0189] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, pro Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples include ethyl acid, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like.Among these, butyl acetate or PGMEA is preferred as the ester solvent.

[0190] Examples of nitrile solvents include acetonitrile, propionitol, valeronitrile, and butyronitrile.

[0191] Organic developers may contain known additives as needed. Examples of such additives include surfactants. While the surfactant is not particularly limited, examples include ionic and nonionic fluorine-based and / or silicone-based surfactants. Nonionic surfactants are preferred, and nonionic fluorine-based surfactants or nonionic silicone-based surfactants are more preferred. When a surfactant is added, the amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the organic developer.

[0192] The development process can be carried out by known development methods, such as the dipping method (immersing the support in a developer solution for a certain period of time), the paddle method (building up the developer solution on the surface of the support using surface tension and leaving it still for a certain period of time), the spray method (spraying the developer solution onto the surface of the support), and the dynamic dispensing method (continuously dispensing the developer solution while scanning a developer dispensing nozzle at a constant speed onto a support that is rotating at a constant speed.

[0193] Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method). It is preferable to use a rinsing solution containing an organic solvent for the rinsing process.

[0194] A negative-type pattern can be formed by the film formation process, exposure process, and development process described above. In the pattern formation method of the embodiment described above, since the dry film of the embodiment described above is used, the generation of foreign matter during negative-type pattern formation is suppressed.

[0195] The pattern forming method of this embodiment may also include a step of curing the negative pattern (hereinafter referred to as the "curing step") after obtaining a support on which a negative pattern has been formed, following the film formation step, exposure step, and development step described above. The curing step can be carried out, for example, at a temperature of 100 to 250°C for 0.5 to 2 hours under a nitrogen atmosphere. Through the curing step described above, the negative pattern hardens and becomes a cured body. In the pattern forming method of the embodiment having a curing step, the dry film of the embodiment described above is used, so the adhesion between the cured body and the support can be improved. The pattern forming method of this embodiment is a useful method when manufacturing electronic components such as packages.

[0196] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0197] <Preparation of Negative Photosensitive Compositions> Each component shown in Table 1 was mixed and dissolved, and filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Inc.) to prepare a photosensitive composition which is a methyl ethyl ketone (MEK) solution with a solid content of 75% by mass.

[0198]

[0199] In Table 1, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount of each component (parts by mass; on a solid content basis).

[0200] Epoxy resin A-1: ​​Bisphenol A novolac type epoxy resin represented by the following chemical formula (A-1). Epoxy equivalent weight 200-220 g / eq. A-2: Cresol novolac type epoxy resin represented by the following chemical formula (A-2). Epoxy equivalent weight 202-214 g / eq. A-3: Phenol novolac type epoxy resin represented by the following chemical formula (A-3). Epoxy equivalent weight 183-193 g / eq. A-4: Trisphenol type epoxy resin represented by the following chemical formula (A-4). Epoxy equivalent weight 205-215 g / eq.

[0201]

[0202] Photoacid generator B-1: A photocationic polymerization initiator represented by the following chemical formula (B-1). B-2: A photocationic polymerization initiator represented by the following chemical formula (B-2). B-3: A photocationic polymerization initiator represented by the following chemical formula (B-3).

[0203]

[0204] Adhesion enhancers C-1: Silane coupling agent; represented by the following chemical formula (C-1), 3-glycidyloxypropyltrimethoxysilane C-2: Silane coupling agent; represented by the following chemical formula (C-2), 8-(glycidyloxy)octyltrimethoxysilane C-3: Silane coupling agent; represented by the following chemical formula (C-3), 3-trimethoxysilylpropylsuccinic anhydride

[0205]

[0206] Sensitizers D-1: 1-naphthol, represented by the following chemical formula (D-1) D-2: 9,10-dibutoxyanthracene, represented by the following chemical formula (D-2) D-3: 2,4-diethylthioxanthone, represented by the following chemical formula (D-3)

[0207]

[0208] Solvents: S-1: Water, S-2: Methyl ethyl ketone (MEK)

[0209] <Formation of Negative-Type Photosensitive Film and Fabrication of Laminated Film> (Example 1) The above negative-type photosensitive composition (1) was applied to a 50 μm thick release polyethylene terephthalate (PET) film (base film) using an applicator, and dried in an oven at 70°C for 10 minutes to form a photosensitive composition layer (negative-type photosensitive film) with a thickness of 20 μm, thereby fabricating a laminated film.

[0210] (Examples 2-14, Comparative Example 2) As shown in Table 2, a photosensitive composition layer (negative photosensitive film) with a thickness of 20 μm was formed in the same manner as in Example 1, except that the negative photosensitive composition was changed in each case, and a laminated film was prepared.

[0211] (Comparative Example 1) As shown in Table 2, a photosensitive composition layer (negative type photosensitive film) with a thickness of 20 μm was formed in the same manner as in Example 1, except that the heating conditions were changed to drying in an oven at 90°C for 10 minutes, and a laminated film was prepared.

[0212] <Manufacturing of Dry Film> A dry film was manufactured by laminating a 30 μm thick release PET film (cover film) onto the photosensitive composition layer (negative-type photosensitive film) of the laminated film described above, under the conditions of a temperature of 40°C, a pressure of 0.3 MPa, and a density of 0.5 m / min.

[0213] [Measurement of Moisture Content of Negative Photosensitive Film] The above dry film was cut into a 10 mm x 50 mm rectangle, and the photosensitive composition layer (negative photosensitive film) obtained by peeling off the cover film and base film was used as the measurement sample, and the moisture content (mass %) was measured. The measurement results are shown in Table 2. For the measurement of moisture content, the Karl Fischer electrocautery method was used with CA-200 (manufactured by Nitto Seikou Analytech Co., Ltd.) (reagent: Aquamicron AKX, heating temperature: 110°C, carrier gas: dry N ２ ) was used.

[0214] <Evaluation> The above dry film was used to evaluate its adhesion to the substrate and its resistance to the generation of foreign matter. The evaluation results are shown in Table 2.

[0215] [Evaluation of adhesion to the substrate] After removing the cover film from the dry film, it was laminated onto a silicon substrate under the conditions of a temperature of 80°C, a pressure of 0.3 MPa, and a density of 0.5 m / min so that the photosensitive composition layer (negative type photosensitive film) and the silicon substrate were in contact, and then the base film was peeled off.

[0216] Next, using an aligner exposure machine, the photosensitive composition layer (negative-type photosensitive film) attached to the silicon substrate was irradiated with GHI rays through a mask having a 100 μm × 100 μm square pattern. The exposure dose was as follows: • Exposure dose for Examples 1, 3, 5-14 and Comparative Examples 1 and 2: 200 mJ / cm² ２ - Exposure dose for Example 2: 400 mJ / cm ２ - Exposure dose for Example 4: 800 mJ / cm ２

[0217] Next, the photosensitive composition layer (negative-type photosensitive film) after exposure was subjected to post-exposure heating on a hot plate at 90°C for 5 minutes. Then, the photosensitive composition layer (negative-type photosensitive film) after post-exposure heating was paddle-developed at 23°C for 90 seconds using propylene glycol monomethyl ether acetate (PGMEA) as the developer to form a 100 μm × 100 μm square negative-type pattern. Furthermore, the film was cured by heat treatment in a bake oven (200°C, 60 minutes, nitrogen atmosphere) to obtain a cured body.

[0218] Next, a bond tester Condor Sigma (manufactured by XYZTEC) was used to measure the breaking load [N] between the cured body with a 100 μm x 100 μm square negative pattern and the silicon substrate. The adhesion to the substrate was evaluated according to the following criteria: Criteria A: Breaking load between the cured body and the silicon substrate is 50 N or more B: Breaking load between the cured body and the silicon substrate is less than 50 N

[0219] [Evaluation of Resistance to Foreign Matter Generation] The above dry film was cut into a rectangle of about 250 mm × 300 mm. Next, the cover film of the dry film was peeled off, and this was laminated on a silicon substrate using TEAM-100ARF (device name, manufactured by Takatori Corporation) under the conditions of a stage temperature of 50°C, a roller temperature of 50°C, a pressure of 200 kPa, and a speed of 16 mm / s so that the photosensitive composition layer (negative photosensitive film) and the silicon substrate were in contact, and then the base film was peeled off.

[0220] The silicon substrate with the photosensitive composition layer (negative photosensitive film) attached was heated at 95°C for 3 minutes, and then the photosensitive composition layer (negative photosensitive film) was removed from the silicon substrate with PGMEA. Then, using NSX220 (device name, manufactured by Onto Innovation), the number of defects within a circle with a diameter of 160 mm on the silicon substrate was measured. From this measurement result, the number of defects with a diameter of 1 μm or more per 1 cm ２ [number / cm ２ ] was calculated, and the resistance to foreign matter generation was evaluated according to the following criteria. Criteria A: The number of defects is less than 50 / cm ２ B: The number of defects is 50 / cm ２ or more

[0221]

[0222] From the results shown in Table 2, it can be confirmed that according to the negative photosensitive films of Examples 1 to 14 having a moisture content of 0.1% by mass or more and 1% by mass or less, the adhesion to the substrate can be enhanced and foreign matter is less likely to occur.

[0223] As described above, the preferred embodiments of the present invention have been described, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other changes can be made without departing from the spirit of the present invention. The present invention is not limited by the foregoing description and is limited only by the appended claims.

[0224] 100 Dry film, 110 Base film, 120 Negative photosensitive film, 130 Laminated film, 150 Cover film

Claims

1. A negative-type photosensitive film comprising a polyfunctional epoxy resin with three or more functions, a photoacid generator, and an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis, wherein the moisture content is 0.1% by mass or more and 1% by mass or less.

2. The negative-type photosensitive film according to claim 1, wherein the adhesion enhancing agent is a silane coupling agent having a trialkoxysilyl group.

3. The negative-type photosensitive film according to claim 1, wherein the photoacid generator is a sulfonium salt.

4. The negative-type photosensitive film according to claim 1, further comprising a sensitizer, wherein the sensitizer is a compound having a thioxanthone skeleton, a naphthalene skeleton, or an anthracene skeleton.

5. A laminated film comprising a base film and a negative-type photosensitive film according to any one of claims 1 to 4.

6. A dry film in which a negative-type photosensitive film according to any one of claims 1 to 4 and a cover film are laminated on a base film in this order.

7. A negative-type photosensitive composition comprising a polyfunctional epoxy resin with three or more functions, a photoacid generator, an adhesion enhancer having a functional group that generates a hydroxyl group upon hydrolysis, and water, wherein the water content is 0.1 parts by mass or more and 1 part by mass or less per 100 parts by mass of the polyfunctional epoxy resin with three or more functions.

Images