Negative photosensitive resin film, multilayer film, dry film, cured product, hollow structure, and printed wiring board

Abstract

A negative photosensitive resin film according to the present invention contains: a trifunctional or higher polyfunctional epoxy compound that is in a solid state at 23°C; an epoxy compound that is in a liquid state at 23°C; a cationic photopolymerization initiator; and a solvent. The content of the solvent is 0.05 mass% to 1.5 mass% inclusive with respect to the total mass of the negative photosensitive resin film. The present invention also provides a multilayer film, a dry film, a cured product, a hollow structure, and a printed wiring board, each of which uses the negative photosensitive resin film. With the negative photosensitive resin film, it is possible to achieve both releasability during separation of a base material film and suppression of the generation of cut waste.

Description

Negative photosensitive resin film, laminated film, dry film, cured material, hollow structure, printed wiring board

[0001] The present invention relates to a negative-type photosensitive resin film, a laminate film, a dry film, a cured product, a hollow structure, and a printed wiring board. This application claims priority to Japanese Patent Application No. 2024-026473, filed on February 26, 2024, the contents of which are incorporated herein by reference.

[0002] In recent years, development of radio frequency (RF) electronic devices such as surface acoustic wave (SAW) filters and bulk acoustic wave (BAW) filters has progressed. Packages that encapsulate such electronic devices include hollow structures with hollow encapsulation structures that ensure the propagation of acoustic waves and the mobility of movable components of the electronic devices. The hollow structures are fabricated by molding a photosensitive material over a wiring substrate on which interdigital electrodes and other components are formed, while maintaining the hollow space. The photosensitive material used here requires a thin, strong cured film.

[0003] As a photosensitive material for producing the hollow structural body, a negative photosensitive resin composition containing an epoxy group-containing resin, a metal oxide, and a specific photocationic polymerization initiator that generates a relatively strong acid upon exposure to light has been disclosed. Also disclosed is a photosensitive resist film (dry film) in which a negative photosensitive resin film formed using the negative photosensitive resin composition and a cover film are laminated in this order on a substrate film (see Patent Document 1).

[0004] JP 2018-36533 A

[0005] When preparing the hollow structure, the release properties of the dry film when peeling off the base film are important. The cover film is removed from the dry film, and the resulting laminate film, consisting of the base film and the negative photosensitive resin film, is placed in a predetermined location. If the release force is too strong when peeling the base film from the laminate film, the base film cannot be easily peeled off, making it difficult to form a hollow sealed structure. Alternatively, if the release force is too strong when peeling the base film from the laminate film, the peeling action of the base film stops during peeling, resulting in streaks, which affect the formation of the structure and reduce yield.

[0006] One approach to address this issue is to reduce the amount of liquid components in the negative photosensitive resin film to reduce the film's adhesiveness and weaken the release force required to peel the base film from the laminated film. However, this approach can easily generate chips due to cracks on the cut surface when the base film is cut while being unwound from the dry film during film replacement during hollow structure fabrication. The chips then adhere to the wafer, resulting in poor yield.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a negative photosensitive resin film that can achieve both good releasability when peeling off a base film and the ability to suppress the generation of cutting debris, as well as a laminate film, a dry film, a cured product, a hollow structure, and a printed wiring board that use the same.

[0008] In order to solve the above problems, the present invention employs the following configuration.

[0009] That is, a first aspect of the present invention is a negative-type photosensitive resin film containing a tri- or higher functional polyfunctional epoxy compound that is solid at 23°C, an epoxy compound that is liquid at 23°C, a photocationic polymerization initiator, and a solvent, wherein the content of the solvent is 0.05 mass% or more and 1.5 mass% or less with respect to the total mass of the negative-type photosensitive resin film.

[0010] A second aspect of the present invention is a laminate film comprising a base film and the negative photosensitive resin film according to the first aspect on the base film.

[0011] A third aspect of the present invention is a dry film in which the negative photosensitive resin film according to the first aspect and a cover film are laminated in this order on a base film.

[0012] A fourth aspect of the present invention is a cured product obtained by curing the negative photosensitive resin film according to the first aspect.

[0013] A fifth aspect of the present invention is a hollow structure comprising a substrate having interdigital electrodes, side walls formed on the substrate so as to surround the interdigital electrodes, and a top plate portion formed on the side walls so as to face the substrate, wherein at least one of the side walls and the top plate portion is formed from a cured product according to the fourth aspect.

[0014] The sixth aspect of the present invention is a Si substrate, SiO ２ A printed wiring board comprising: a substrate selected from the group consisting of a silicon substrate, a silicon nitride substrate, a copper substrate, an tantalum nitride substrate, and an insulating layer formed from the cured product according to the fourth aspect.

[0015] According to the present invention, it is possible to provide a negative photosensitive resin film that can achieve both good releasability when peeling off a base film and the ability to suppress the generation of cutting debris, as well as a laminate film, a dry film, a cured product, a hollow structure, and a printed wiring board that use the same.

[0016] FIG. 1 is a cross-sectional view showing an embodiment of a dry film. FIG. 2 is a schematic diagram illustrating an embodiment of step (1) in a method for manufacturing a hollow structure. In the embodiment shown in FIG. 2, a substrate 10 having interdigital electrodes (not shown) and a dry film are used to form side walls 120Hw on the substrate 10 having the interdigital electrodes. FIG. 3 is a schematic diagram illustrating an embodiment of step (2) in a method for manufacturing a hollow structure. In the embodiment shown in FIG. 3, a substrate 10 having side walls 120Hw formed to surround the interdigital electrodes and a dry film are used to produce a hollow structure 200 having a top plate portion 120Hr formed on the side walls 120Hw so as to face the substrate 10.

[0017] In this specification and claims, "aliphatic" is a relative concept to aromatic, and is defined as meaning a group or compound that does not have 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. A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group have been substituted with halogen atoms, and examples of such halogen atoms include fluorine, chlorine, bromine, and iodine atoms. A "fluorinated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group have been substituted with fluorine atoms. A "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "optionally has a substituent" refers to the case in which a hydrogen atom (-H) is replaced with a monovalent group, and the case in which a methylene group (-CH ２ The term "exposure" encompasses both cases where the radical (-) is substituted with a divalent group and cases where the radical (-) is substituted with a divalent group. The term "exposure" encompasses all cases of irradiation with radiation.

[0018] The dry film according to one embodiment of the present invention is characterized by a negative photosensitive resin film that constitutes a resist layer, and known techniques can be applied to the components other than the resist layer.

[0019] FIG. 1 is a cross-sectional view in the film thickness direction showing one embodiment of a dry film. In the drawings, components may be shown schematically to make them easier to see, and some components may be shown on a different scale. In FIG. 1, the dry film 100 is formed by laminating a negative photosensitive resin film 120 and a cover film 150, in this order, on a substrate film 110. The dry film 100 is provided, for example, as a roll wound around a core.

[0020] (Negative Photosensitive Resin Film) One embodiment of the negative photosensitive resin film contains a trifunctional or higher polyfunctional epoxy compound that is solid at 23° C., an epoxy compound that is liquid at 23° C., a photocationic polymerization initiator, and a solvent. The content of the solvent is 0.05% by mass or more and 1.5% by mass or less with respect to the total mass of the negative photosensitive resin film.

[0021] 1 includes the negative photosensitive resin film 120 of this embodiment, and therefore has good releasability, allowing the base film 110 to be easily peeled off from the laminated film 130 of the base film 110 and the negative photosensitive resin film 120 after the cover film 150 has been removed and the dry film 100 is placed in a predetermined location. In addition, since the dry film 100 includes the negative photosensitive resin film 120 of this embodiment, cracks are less likely to occur when the base film 110 is cut while being wound up from the dry film 100 during film replacement during production, and the generation of cutting debris is reduced.

[0022] When the negative photosensitive resin film of this embodiment is selectively exposed to light, the cationic moiety of the photocationic polymerization initiator decomposes in the exposed areas of the negative photosensitive resin film to generate an acid. The acid causes ring-opening polymerization of the epoxy groups in the epoxy compound, reducing the solubility of the epoxy compound in a developer containing an organic solvent (organic developer). Meanwhile, the solubility of the epoxy compound in an organic developer remains unchanged in the unexposed areas of the negative photosensitive resin film, resulting in a difference in solubility in an organic developer between the exposed and unexposed areas of the negative photosensitive resin film. Therefore, when the negative photosensitive resin film is developed with an organic developer, the unexposed areas are dissolved and removed, and the exposed areas become an afterimage, forming a negative pattern.

[0023] <Tri- or Higher Functional Polyfunctional Epoxy Compound That Is Solid at 23°C> As the tri- or higher functional polyfunctional epoxy compound (hereinafter also referred to as "component (A1)") that is solid at 23°C and contained in the negative photosensitive resin film of this embodiment, one having a sufficient number of epoxy groups to form a negative pattern by exposure is used.

[0024] Component (A1) is solid at 23° C. and has a softening point of, for example, 50° C. or higher, and may be 55° C. or higher, 60° C. or higher and 80° C. or lower, or 65° C. or higher and 75° C. In this specification, the softening point of the epoxy compound is a value measured by the ring and ball method.

[0025] The epoxy equivalent of component (A1) is preferably 180 g / eq. or more and 300 g / eq. or less, and more preferably 200 g / eq. or more and 240 g / eq. or less. In this specification, the epoxy equivalent of the epoxy compound can be measured by potentiometric titration as described in JIS K-7236. Methods for measuring the 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 a hydrogen bromide-acetic acid solution.

[0026] The component (A1) is preferably a bisphenol novolac epoxy resin. Examples of bisphenol novolac epoxy resins include polyfunctional epoxy resins produced by reacting bisphenol novolac resin with epichlorohydrin, and polyfunctional epoxy resins obtained by novolacizing bisphenol glycidyl ether. Among these, bisphenol A novolac epoxy resins are preferred because of their easy availability.

[0027] Suitable examples of bisphenol novolac epoxy resins include resins represented by the following general formula (A1-1):

[0028] [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. ｐ１ may be the same or different. ｐ２ may be the same or different. １ is an integer from 1 to 5. ＥＰis an epoxy group-containing group. ＥＰ may be the same or different from each other.

[0029] In the formula (A1-1), R ｐ１ , R ｐ２ 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 the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group, and examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among these, R ｐ１ , R ｐ２ is preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, and particularly preferably a hydrogen atom or a methyl group. ｐ１ may be the same or different. ｐ２ may be the same as or different from each other.

[0030] In the formula (A1-1), n １ is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0031] In the formula (A1-1), R ＥＰ is an epoxy group-containing group. ＥＰThe epoxy group-containing group is not particularly limited, and examples thereof include a group consisting of only epoxy groups; a group consisting of only alicyclic epoxy groups; and a group having an epoxy group or 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, specifically a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups. The hydrogen atoms of these alicyclic groups may be substituted with alkyl groups, alkoxy groups, hydroxyl groups, or the like. 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 the alicyclic epoxy group is bonded via the divalent linking group bonded to an oxygen atom (—O—) in the formula.

[0032] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0033] Regarding the divalent hydrocarbon group which may have a substituent: The divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure.

[0034] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and 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 The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and 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 alkylmethylene 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 alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２-, -CH ２ CH (CH ３ ) CH ２ CH ２ Examples of alkyl groups include alkyl tetramethylene groups such as -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0035] Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which two hydrogen atoms have 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. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0036] The aromatic hydrocarbon group in the 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 the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene groups or heteroarylene groups); groups in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., groups in which one further hydrogen atom has been removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and particularly preferably 1 carbon atom.

[0037] The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.

[0038] 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 a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the alicyclic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, and -S(=O) ２ -, -S(=O) ２ —O— is preferred.

[0039] In the aromatic hydrocarbon group as a divalent hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the alicyclic hydrocarbon group.

[0040] Regarding the divalent linking group containing a hetero atom: The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0041] In the divalent linking group containing a hetero atom, 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 or an acyl group); -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 -OC(=O)-Y ２２ -, 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. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group or acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. 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 -OC(=O)-Y ２２ -Middle, Y２１ and Y ２２ are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group. Y ２１ As Y, 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 an ethylene group is particularly preferred. ２２ is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a 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. ２１ -C(=O)-O] ｍ” -Y ２２ In the group represented by -, m" is an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1. That is, the group represented by the formula -[Y ２１ -C(=O)-O] ｍ” -Y ２２ The group represented by - includes the group represented by the formula -Y ２１ -C(=O)-O-Y ２２ Among them, groups represented by the formula -(CH ２ ) ａ’ -C(=O)-O-(CH ２ ) ｂ’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0042] Among them, R ＥＰ The epoxy group-containing group in is preferably a glycidyl group.

[0043] Alternatively, the component (A1) may suitably be a trifunctional epoxy compound having three epoxy groups in the molecule, such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, or a trifunctional epoxy compound represented by the following general formula (A1-2):

[0044] [In formula (A1-2), R ｐ３ , R ｐ４ and R ｐ５ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ＥＰ is an epoxy group-containing group. ＥＰ may be the same or different from each other.

[0045] In the 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 the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group, and examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among these, R ｐ３ , R ｐ４ and R ｐ５ Each of the groups is preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, further preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

[0046] In the formula (A1-2), Rm ＥＰ is an epoxy group-containing group, and R ＥＰ A glycidyl group is preferred. ＥＰ may be the same as or different from each other.

[0047] Specific examples of the trifunctional epoxy compound represented by formula (A1-2) are shown below.

[0048]

[0049] As the trifunctional epoxy compound, compounds having a structure in which the distance between the three epoxy groups is large within the molecule are preferred, as they are less likely to undergo an intramolecular crosslinking reaction; tris(4-hydroxyphenyl)methane triglycidyl ether or the trifunctional epoxy compound represented by the above general formula (A1-2) are more preferred; the trifunctional epoxy compound represented by the above general formula (A1-2) is even more preferred; one selected from the group consisting of the trifunctional epoxy compounds represented by the above formulas (A1-2-1) and (A1-2-2), respectively, is particularly preferred; and the trifunctional epoxy compound represented by the above formula (A1-2-1) is most preferred.

[0050] Alternatively, the component (A1) may suitably be a novolac epoxy resin having a structural unit represented by the following general formula (anv1):

[0051] [In the formula, R ＥＰ is an epoxy group-containing group. ａ２２ and R ａ２３ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0052] In the formula (anv1), R ａ２２ , R ａ２３ The alkyl group having 1 to 5 carbon atoms is R ｐ１ , R ｐ２ The alkyl group having 1 to 5 carbon atoms is the same as the alkyl group having 1 to 5 carbon atoms. ａ２２ , R ａ２３ In the formula (anv1), the halogen atom is preferably a chlorine atom or a bromine atom. ＥＰ represents R in the formula (A1-1). ＥＰ and a glycidyl group is preferred.

[0053] Specific examples of the structural unit represented by the formula (anv1) are shown below.

[0054]

[0055] The component (A1) may be a resin consisting solely of the structural unit (anv1), or it may be a resin containing the structural unit (anv1) and other structural units. Examples of resins consisting solely of the structural unit (anv1) include phenol novolac epoxy resins and cresol novolac epoxy resins. Examples of such other structural units include the structural units represented by the following general formulas (anv2) to (anv3):

[0056] [In the formula, R ａ２４ R is a hydrocarbon group which may have a substituent. ａ２５ ~R ａ２６ , R ａ２８ ~R ａ３０ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. ａ２７ represents an epoxy group-containing group or a hydrocarbon group which may have a substituent.

[0057] In the formula (anv2), R ａ２４ is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include a linear or branched alkyl group, and a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0058] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, with an isopropyl group being preferred.

[0059] R ａ２４When 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 an aliphatic hydrocarbon group that is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferred. As the monocycloalkane, one having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As an aliphatic hydrocarbon group that is a polycyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferred, and as the polycycloalkane, one having 7 to 12 carbon atoms is preferred, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0060] R ａ２４ When the cyclic hydrocarbon group of the formula (I) is 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. R ａ２４Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (an aryl group or a heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and particularly preferably 1 carbon atom.

[0061] In the formulas (anv2) and (anv3), R ａ２５ ~R ａ２６ , R ａ２８ ~R ａ３０ are each 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 independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. ａ２２ , R ａ２３ is the same as:

[0062] In the formula (anv3), R ａ２７ R is an epoxy group-containing group or a hydrocarbon group which may have a substituent. ａ２７ The epoxy group-containing group is R ＥＰ It is the same as R ａ２７ The hydrocarbon group which may have a substituent is R ａ２４ is the same as:

[0063] Specific examples of the structural units represented by the formulae (anv2) to (anv3) are shown below.

[0064]

[0065] When the component (A1) contains other structural units in addition to the structural unit (anv1), there are no particular limitations on the proportion of each structural unit within the component (A1), but the total amount of structural units having an epoxy group, relative to the total amount of all structural units constituting the component (A1), is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %.

[0066] Commercially available products of the component (A1) include, for example, jER-152, jER-154, jER-157S70, and 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, and EPICLON N-740. Examples of such a binder 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.).

[0067] As the component (A1), one type may be used alone, or two or more types may be used in combination. In the negative-type photosensitive resin film of this embodiment, the content of the component (A1) is preferably 80% by mass or more, more preferably 80 to 95% by mass, still 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 resin film.

[0068] <Epoxy Compound That Is Liquid at 23°C> The epoxy compound that is liquid at 23°C (hereinafter also referred to as "component (A2)") contained in the negative photosensitive resin film of this embodiment is an epoxy compound that has a sufficient number of epoxy groups to form a negative pattern by exposure.

[0069] The epoxy equivalent of component (A2) is, for example, 200 g / eq. or less, preferably 90 g / eq. or more and 180 g / eq. or less, and more preferably 120 g / eq. or more and 150 g / eq. or less. The molecular weight of component (A2) is, for example, 300 or less, preferably 100 or more and 290 or less, and more preferably 200 or more and 270 or less.

[0070] Examples of the component (A2) include aliphatic epoxy resins that are liquid at 23° C. Examples of the aliphatic epoxy resin include compounds containing a partial structure represented by the following general formula (A2-m1) (hereinafter also referred to as "component (m1)").

[0071] [In the formula, n ２ is an integer from 1 to 4.

[0072] In formula (A2-m1), n ２ is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0073] Examples of the component (m1) include compounds in which a plurality of partial structures represented by the general formula (A2-m1) are bonded via a divalent linking group or a single bond. Among these, compounds in which a plurality of partial structures 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 suitable examples include divalent hydrocarbon groups which may have a substituent and divalent linking groups which contain a heteroatom. The divalent hydrocarbon groups which may have a substituent and divalent linking groups which contain a heteroatom are preferably the R ＥＰ The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are the same as those explained in (epoxy group-containing group), and among these, the divalent linking group containing a hetero atom is preferred. ２１ a group represented by —C(═O)—O—, —C(═O)—O—Y ２１ A group represented by - is more preferred. ２１As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred.

[0074] Examples of the component (m1) include compounds represented by the following chemical formula: In the following chemical formula, l represents an integer of 1 to 10, and m represents an integer of 1 to 30. R represents an alkylene group having 1 to 8 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or an isopropylene group). n1 and n2 each represent an integer of 1 to 30.

[0075]

[0076] Further, suitable examples of the aliphatic epoxy resin include compounds represented by the following general formula (A2-m2) (hereinafter also referred to as "component (m2)"):

[0077] [In the formula, R ＥＰ is an epoxy group-containing group. ＥＰ may be the same or different from each other.

[0078] In the formula (A2-m2), R ＥＰ is an epoxy group-containing group, and R ＥＰ is the same as:

[0079] Further examples of the 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, and inositol hexaglycidyl ether.

[0080] In the negative-type photosensitive resin film of this embodiment, the component (A2) may be used alone or in combination of two or more. The component (A2) preferably contains at least one selected from the group consisting of the component (m1) and the component (m2), and more preferably contains the component (m2).

[0081] Commercially available products of component (A2) include, for example, ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (all manufactured by ADEKA Corporation); CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EPOLEAD PB 3600, and EPOLEAD PB 3600. 4700 (manufactured by Daicel Corporation); Epocalic THI-DE, DE-102, and DE-103 (manufactured by ENEOS Corporation); Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-622, and EX-850L (manufactured by Nagase ChemteX Corporation); TEPIC series such as TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, and TEPIC-UC (manufactured by Nissan Chemical Industries, Ltd.); MA-DGIC, DA-MGIC, and TOIC (manufactured by Shikoku Chemical Industry Co., Ltd.).

[0082] In the negative-type photosensitive resin film of this embodiment, the content of component (A2) is preferably 1 to 10 parts by mass, more preferably 1.5 to 9 parts by mass, and even more preferably 2 to 8 parts by mass, per 100 parts by mass of component (A1). When the content of component (A2) is at or above the lower limit of the preferred range, for example, when the substrate film is cut while being wound from the dry film during film replacement during the production of a hollow structure, the generation of cutting debris due to cracks occurring on the cut surface is easily suppressed. On the other hand, when the content is at or below the upper limit of the preferred range, the peel strength when peeling the substrate film from the laminate film is reduced, thereby improving releasability.

[0083] <Cationic Photopolymerization Initiator> The cationic photopolymerization initiator (hereinafter also referred to as "component (I)") contained in the negative photosensitive resin film of this embodiment is a compound that generates cations upon irradiation with active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF or ArF, X-rays, electron beams, etc., and the cations can serve as a polymerization initiator. Examples of the component (I) include onium borate salts (hereinafter also referred to as "component (I1)") and cationic photopolymerization initiators other than component (I1) (other cationic photopolymerization initiators).

[0084] <<Onium Borate Salt>> Onium borate salt (component (I1)) generates a relatively strong acid upon exposure. Therefore, by forming a pattern using a negative-type photosensitive resin film containing component (I1), sufficient sensitivity can be obtained, resulting in the formation of a good pattern. Furthermore, the use of component (I1) also reduces the risk of toxicity and metal corrosion. Suitable examples of component (I1) include compounds represented by the following general formula (I1):

[0085] [In the formula, R ｂ０１ ~R ｂ０４ are each independently an aryl group which may have a substituent, or a fluorine atom; q is an integer of 1 or more; ｑ＋ is a q-valent organic cation.

[0086] Anion part In the formula (I1), R ｂ０１ ~R ｂ０４ The aryl group in R preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include naphthyl, phenyl, and anthracenyl groups, with the phenyl group being preferred because of its ease of availability. ｂ０１ ~R ｂ０４The aryl group in formula (I1) may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably having 1 to 5 carbon atoms), or a halogenated alkyl group, more preferably a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms, and particularly preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. When the aryl group has a fluorine atom, the polarity of the anion moiety is increased, which is preferable. Among these, R in formula (I1) ｂ０１ ~R ｂ０４ As each of the groups, a fluorinated phenyl group is preferred, and a perfluorophenyl group is particularly preferred.

[0087] A preferred example of the anion moiety 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 ] － Among them, tetrakis(pentafluorophenyl)borate ([B(C ６ F ５ ) ４ ] － ) is particularly preferred.

[0088] Cation moiety In the formula (I1), Qｑ＋ Suitable examples of the cation include sulfonium cations and iodonium cations, and the organic cations represented by the following general formulae (ca-1) to (ca-5) are particularly preferred.

[0089] [In the formula, R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ R each independently represents an aryl group, a heteroaryl group, an alkyl group, or an alkenyl group, which may have a substituent. ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ may be bonded to each other to form a ring together with the sulfur atom in the formula. ２０８ ~R ２０９ R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２１０ represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted —SO ２ -containing cyclic group. ２０１ represents —C(═O)— or —C(═O)—O—. ２０１ each independently represents an arylene group, an alkylene group, or an alkenylene group; x is 1 or 2. ２０１ represents a (x+1)-valent linking group.

[0090] R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. ２０１ ~R ２０７ , and R ２１１ ~R ２１２Examples of the heteroaryl group in the formula (I) include those in which some of the carbon atoms constituting the aryl group have been substituted with heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of this heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthene; and examples of the substituted heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthen-9-one. R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkyl group in R is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkenyl group in R preferably has 2 to 10 carbon atoms. ２０１ ~R ２０７ , and R ２１０ ~R ２１２ Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (═O), an aryl group, and groups represented by the following formulas (car-r-1) to (car-r-10):

[0091] [In the formula, R' ２０１ are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group.

[0092] In the above formulae (car-r-1) to (car-r-10), R' ２０１ are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group.

[0093] Optionally substituted cyclic group: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0094] 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 the substituent. ２０１ Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in R' 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 or the like. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. ２０１ Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic ring (an aryl group: for example, a phenyl group, a naphthyl group, or an anthracenyl group), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group), a group in which one hydrogen atom has been removed from a ring in which some of the hydrogen atoms constituting the aromatic ring have been substituted with an oxo group or the like (for example, anthraquinone), and a group in which one hydrogen atom has been removed from an aromatic heterocycle (for example, 9H-thioxanthene or 9H-thioxanthen-9-one). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and particularly preferably 1.

[0095] R' ２０１ Examples of the cyclic aliphatic hydrocarbon group in the formula (I) include aliphatic hydrocarbon groups containing a ring within their structure. Examples of aliphatic hydrocarbon groups containing a ring within their structure include alicyclic hydrocarbon groups (groups in 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 within a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be either a polycyclic group or a monocyclic group. Preferred monocyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a monocycloalkane. Preferred monocycloalkanes have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. Preferred polycyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a fused ring system, such as a cyclic group having a steroid skeleton.

[0096] Among them, R' ２０１ The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0097] 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. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and 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 As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and 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 alkylmethylene 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 alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0098] A chain alkyl group which may have a substituent: R' ２０１ The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, and docosyl groups. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0099] A chain alkenyl group which may have a substituent: R' ２０１ The chain alkenyl group may be either 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, propenyl (allyl), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl groups. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0100] R' ２０１ Examples of the substituent in the cyclic group, chain alkyl group or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, the above-mentioned R' ２０１ Examples of the groups include a cyclic group, an alkylcarbonyl group, and a thienylcarbonyl group.

[0101] Among them, R' ２０１ is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

[0102] R ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ When they are bonded to each other to form a ring together with the sulfur atom in the formula, they are not substituted with heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, or with 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.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0103] In the formula (ca-3), R ２０８ ~R ２０９ each 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, and when they are alkyl groups, they may be bonded to each other to form a ring.

[0104] In the formula (ca-3), R ２１０represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted —SO ２ -containing cyclic group. ２１０ The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. ２１０ The alkyl group in R is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. ２１０ The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

[0105] In the formulas (ca-4) and (ca-5), Y ２０１ each independently represents an arylene group, an alkylene group, or an alkenylene group. ２０１ The arylene group in ２０１ Examples of the aromatic hydrocarbon group in the above formula include groups in which one hydrogen atom has been removed from the aryl groups exemplified in the formula Y. ２０１ The alkylene group and alkenylene group in R' ２０１ Examples of the chain alkyl group and the chain alkenyl group include groups in which one hydrogen atom has been removed from the groups exemplified above as the chain alkyl group and the chain alkenyl group.

[0106] In the formulas (ca-4) and (ca-5), x is 1 or 2. ２０１ is a (x+1)-valent linking group, i.e., a divalent or trivalent linking group. ２０１ The divalent linking group in the formula (A1-1) is preferably a divalent hydrocarbon group which may have a substituent. ＥＰ The same groups as the optionally substituted divalent hydrocarbon groups exemplified by W are preferred. ２０１ The divalent linking group in may be linear, branched, or cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting of only an arylene group is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred. ２０１ The trivalent linking group in ２０１Examples of the divalent linking group include a group in which one hydrogen atom has been removed from the divalent linking group shown in the formula: and a group in which the divalent linking group is further bonded to the divalent linking group shown in the formula: ２０１ The trivalent linking group in the formula (I) is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0107] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0108]

[0109] [In the formula, R” ２０１ is a hydrogen atom or a substituent. The substituent includes the above-mentioned R ２０１ ~R ２０７ and R ２１０ ~R ２１２ The substituents are the same as those exemplified as the substituents that may be possessed by

[0110] As the cation represented by the formula (ca-1), cations represented by the following general formulae (ca-1-25) to (ca-1-35) are also preferred.

[0111]

[0112] [In the formula, R' ２１１ is an alkyl group. ｈａｌ is a hydrogen atom or a halogen atom.

[0113] As the cation represented by the formula (ca-1), cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are also preferred.

[0114]

[0115] As the cation represented by the formula (ca-1), cations having a benzoylphenyl group represented by the following chemical formulas (ca-1-49) to (ca-1-54) are also preferred.

[0116]

[0117] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0118] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0119]

[0120] Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0121]

[0122] 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.

[0123] [In the formula, R' ２１２ is an alkyl group or a hydrogen atom. ２１１ is an alkyl group.

[0124] Among the above, the cation part [(Q ｑ＋ ) １／ｑ is preferably a cation represented by general formula (ca-1), more preferably a cation represented by each of formulas (ca-1-1) to (ca-1-54), and even more preferably a cation represented by each of formulas (ca-1-49) to (ca-1-54).

[0125] <<Other Photocationic Polymerization Initiators>> Examples of photocationic polymerization initiators other than the component (I1) include compounds represented by the following general formula (I2-1) or (I2-2) (hereinafter referred to as “component (I2)”); and compounds represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as “component (I3)”).

[0126] Regarding the component (I2): The component (I2) is a compound represented by the following general formula (I2-1) or (I2-2): The component (I2) generates a relatively strong acid upon exposure. Therefore, when a pattern is formed using a negative-type photosensitive resin film containing the component (I2), sufficient sensitivity is obtained and a good pattern is formed.

[0127] [In the formula, R ｂ０５ is a fluorine atom or a fluorinated alkyl group which may have a substituent. ｂ０５ may be the same or different from each other. q is an integer of 1 or more, and Q ｑ＋ is a q-valent organic cation.

[0128] [In the formula, R ｂ０６ is a fluorine atom or a fluorinated alkyl group which may have a substituent. ｂ０６ may be the same or different from each other. q is an integer of 1 or more, and Q ｑ＋ is a q-valent organic cation.

[0129] Anion part In the formula (I2-1), R ｂ０５ is a fluorine atom or a fluorinated alkyl group which may have a substituent. ｂ０５ may be the same or different. ｂ０５ The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms. ｂ０５ As the alkyl group, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferred, and a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group is even more preferred.

[0130] The anion moiety of the compound represented by formula (I2-1) is preferably represented by the following general formula (b0-2a).

[0131] [In the formula, R ｂｆ０５ represents a fluorinated alkyl group which may have a substituent. １ is an integer from 1 to 5.

[0132] In formula (b0-2a), R ｂｆ０５ The optionally substituted fluorinated alkyl group in R ｂ０５ In formula (b0-2a), nb is the same as the optionally substituted fluorinated alkyl group listed above. １ is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.

[0133] In the formula (I2-2), R ｂ０６ is a fluorine atom or a fluorinated alkyl group which may have a substituent. ｂ０６ may be the same or different. ｂ０６ The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms. ｂ０６ As the alkyl group, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferred, and a fluorine atom is even more preferred.

[0134] In formula (I2-1) and formula (I2-2), q is an integer of 1 or more, and Q ｑ＋ is a q-valent organic cation. ｑ＋ As the group, Q in the above formula (I1) ｑ＋ Among them, cations represented by general formula (ca-1) are preferred, and cations represented by formulas (ca-1-1) to (ca-1-54) are more preferred.

[0135] Regarding the component (I3): The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0136] [In the formula, R ｂ１１ ~Rｂ１２ is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom. m is an integer of 1 or more, and M ｍ＋ are each independently an m-valent organic cation.

[0137] {Component (I3-1)} Anion portion In formula (I3-1), R ｂ１２ is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and is ２０１ Among the cyclic groups, chain alkyl groups, and chain alkenyl groups in the explanation of R, those having no substituents or those having a substituent other than a halogen atom are exemplified. ｂ１２ is preferably a chain alkyl group which may have a substituent other than a halogen atom, or an aliphatic cyclic group which may have a substituent other than a halogen atom. The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have a substituent other than a halogen atom); or a group in which one or more hydrogen atoms have been removed from camphor, etc. ｂ１２ The hydrocarbon group may have a substituent other than a halogen atom, and examples of the substituent include R ｂ１１ Examples include the same substituents other than halogen atoms as those which may be possessed by the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in (1). Here, the phrase "may have a substituent other than halogen atoms" not only excludes cases in which a substituent consisting of only halogen atoms is possessed, but also excludes cases in which a substituent containing at least one halogen atom is possessed (for example, cases in which the substituent is a fluorinated alkyl group, etc.).

[0138] Specific examples of preferred anion moieties of the component (I3-1) are shown below.

[0139]

[0140] Cation moiety In formula (I3-1), M ｍ＋ is an m-valent organic cation. ｍ＋ Suitable examples of the organic cation include the same cations as those 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. ２０１ , R ２０２ , R ２０３ A sulfonium cation 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 a substituent is particularly preferred, as it improves resolution and roughness characteristics. The substituent that the organic group may have is the same as above, and examples thereof include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (═O), an aryl group, and groups represented by the above formulas (car-r-1) to (car-r-10). The number of carbon atoms in the 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, and such M ｍ＋ Suitable examples of the organic cation include 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), and among these, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0141] {Component (I3-2)} Anion portion In formula (I3-2), R ｂ１１ is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and is ２０１Among the cyclic groups, chain alkyl groups and chain alkenyl groups in the explanation of (1), those which have no substituent or those which have a substituent other than a halogen atom are exemplified.

[0142] Among these, R ｂ１１ is preferably an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a chain alkyl group which may have a substituent other than a halogen atom. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the following general formulas (y-al-1) to (y-al-7). In the following general formulas (y-al-1) to (y-al-7), R in the above formula (I3-2) ｂ１１ The bond to V' in the following general formulae (y-al-1) to (y-al-7) is １０１ is.

[0143] [In the formula, V' １０１ is a single bond or an alkylene group having 1 to 5 carbon atoms. １０２ is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.

[0144] V' １０２ The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0145] V' １０１ and V' １０２ The alkylene group in V' may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group. １０１ and V' １０２ Specific examples of the alkylene group in ２ -]; -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 alkylmethylene groups such as -; ethylene groups [-CH ２ CH ２ -]; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, etc.; a trimethylene group (n-propylene group) [—CH ２ CH ２ CH ２ -]; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ an alkyltrimethylene group such as -; a tetramethylene group [-CH ２ CH ２ CH ２ CH ２ -]; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ -, etc.; an alkyltetramethylene group such as a pentamethylene group [—CH ２ CH ２ CH ２ CH ２ CH ２ -]. Also, V'１０１ or V' １０２ In the above formula, some methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is represented by R' ２０１ A divalent group obtained by further removing one hydrogen atom from a cyclic aliphatic hydrocarbon group (a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group) of the above formula (I) is preferred, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferred.

[0146] The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group. The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The chain alkyl group preferably has 1 to 10 carbon atoms, and specific examples include 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.

[0147] R ｂ１１ is preferably a cyclic group which may have a substituent other than a halogen atom. Specific examples of preferred anion moieties of component (I3-2) are shown below.

[0148]

[0149] Cation moiety In formula (I3-2), M ｍ＋ is an m-valent organic cation, and M in the formula (I3-1) ｍ＋ is the same as:

[0150] Furthermore, from the viewpoints of increasing the elasticity of the photosensitive resin film and facilitating the formation of a fine structure without residue, component (I) is preferably a photocationic polymerization initiator that generates an acid with a pKa (acid dissociation constant) of -5 or less upon exposure. By using a photocationic polymerization initiator that generates an acid with a pKa of more preferably -6 or less, and even more preferably -8 or less, high sensitivity to exposure can be achieved. The lower limit of the pKa of the acid generated by component (I) is preferably -15 or more. By using a photocationic polymerization initiator that generates an acid with such a suitable pKa, high sensitivity can be achieved. Here, "pKa (acid dissociation constant)" refers to a commonly used index indicating the acid strength of a target substance. Note that the pKa in this specification is a value measured at a temperature of 25°C. The pKa value can be determined by known measurement techniques. Alternatively, values ​​calculated using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development Co.) can also be used.

[0151] As the component (I), one type may be used alone, or two or more types may be used in combination. In the negative-type photosensitive resin film used in this embodiment, the component (I) is preferably at least one type selected from the group consisting of the component (I1), the component (I2), and the component (I3), and it is more preferable to use the component (I1).

[0152] In the negative-type photosensitive resin film used in 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, relative to 100 parts by mass of component (A1). When the content of component (I) is at least the lower limit of the above-mentioned preferred range, sufficient sensitivity is obtained, and the lithography properties of the pattern are further improved. In addition, the strength of the negative-type photosensitive resin film is further increased. On the other hand, when the content is at most the upper limit of the above-mentioned preferred range, sensitivity is appropriately controlled, making it easier to obtain a pattern with a good shape.

[0153] <Solvent> Examples of the solvent (hereinafter also referred to as "component (S)") contained in the negative photosensitive resin film of this embodiment include 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 an ester bond such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; and monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the polyhydric alcohols or compounds having an ester bond. Examples of the (S) component include derivatives of polyhydric alcohols such as compounds having an ether bond, such as monoalkyl ethers or monophenyl ethers (among which, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; 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, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethyl sulfoxide (DMSO). The (S) component may be used alone or as a mixed solvent of two or more.

[0154] In the negative photosensitive resin film of this embodiment, the content of the solvent (component (S)) is 0.05% by mass or more and 1.5% by mass or less, preferably 0.1% by mass or more and 1.0% by mass or less, and more preferably 0.5% by mass or more and 1.0% by mass or less, relative to the total mass of the negative photosensitive resin film. If the content of the component (S) in the negative photosensitive resin film of this embodiment is equal to or greater than the lower limit of the above range, cracks are less likely to occur when the substrate film is cut while being wound from the dry film during film replacement during production, and the generation of cutting debris is suppressed. On the other hand, if the content is equal to or less than the upper limit of the above range, the substrate film can be easily peeled from a laminate film of a substrate film and a negative photosensitive resin film, and releasability is good. The content of the component (S) in the negative photosensitive resin film can be adjusted in the production of the laminate film, for example, by controlling the heating conditions (e.g., temperature, heating time) when forming the negative photosensitive resin film.

[0155] The negative-type photosensitive resin film of the above-mentioned embodiment may have, for example, an embodiment in which the content of the component (A1) is 80% by mass or more relative to the total mass of the negative-type photosensitive resin film, the content of the component (A2) is 1 to 10 parts by mass per 100 parts by mass of the component (A1), and the content of the component (I) is 0.05 to 5 parts by mass. The negative-type photosensitive resin film of the above-mentioned embodiment may have, for example, an embodiment in which the content of the component (A1) is 80 to 95% by mass relative to the total mass of the negative-type photosensitive resin film, the content of the component (A2) is 1.5 to 9 parts by mass per 100 parts by mass of the component (A1), and the content of the component (I) is 0.1 to 3 parts by mass. The negative-type photosensitive resin film of the above-mentioned embodiment may have, for example, an embodiment in which the content of the component (A1) is 85 to 95% by mass relative to the total mass of the negative-type photosensitive resin film, the content of the component (A2) is 2 to 8 parts by mass per 100 parts by mass of the component (A1), and the content of the component (I) is 0.15 to 3 parts by mass. The negative-type photosensitive resin film of the above-mentioned embodiment may have, for example, an embodiment in which the content of the component (A1) is 90 to 95% by mass relative to the total mass of the negative-type photosensitive resin film, the content of the component (A2) is 2 to 8 parts by mass per 100 parts by mass of the component (A1), and the content of the component (I) is 0.2 to 2 parts by mass.

[0156] In the negative-type photosensitive resin film of this embodiment, the mixing ratio of the photocationic polymerization initiator to the solvent, expressed as a mass ratio of solvent / photocationic polymerization initiator, is preferably 0.04 to 1.1, more preferably 0.05 to 0.7, and even more preferably 0.4 to 0.7. When the mass ratio expressed as solvent / photocationic polymerization initiator is equal to or greater than the lower limit of the above-mentioned preferred range, cracks are less likely to occur when the substrate film is cut while being wound from the dry film during film replacement during production, and the generation of cutting debris is more likely to be suppressed. On the other hand, when the mass ratio is equal to or less than the upper limit of the above-mentioned preferred range, the substrate film can be easily peeled from the laminate film of the substrate film and the negative-type photosensitive resin film, and releasability is improved.

[0157] <Other Components> The negative photosensitive resin film of this embodiment may contain other components as needed in addition to the above-mentioned components (A1), (A2), (I), and (S). If desired, the negative photosensitive resin film of this embodiment may appropriately contain miscible additives, such as epoxy group-containing compounds other than the components (A1) and (A2), silane coupling agents, sensitizer components, metal oxides, additional resins for improving film performance, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and antihalation agents.

[0158] <Silane Coupling Agent> A silane coupling agent can be used as an adhesion aid to improve adhesion between a negative-type photosensitive resin film and a substrate. Examples of silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. A single silane coupling agent may be used alone, or two or more may be used in combination. When a silane coupling agent is included, its content is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3 parts by mass, per 100 parts by mass of component (A1). A silane coupling agent content within the preferred range described above further enhances the strength of the cured film. In addition, the adhesion between the cured film and the substrate is further strengthened.

[0159] As described above, the negative-type photosensitive resin film of this embodiment contains a solvent at a specific content (0.05% by mass or more and 1.5% by mass or less). In this way, in the negative-type photosensitive resin film of this embodiment, the amount of residual solvent in the resist layer after being made into a dry film is controlled by heating conditions, etc.

[0160] 1 includes the negative-type photosensitive resin film 120 of this embodiment as a resist layer, which provides good releasability when peeling the base film 110 from the laminate film 130 after removing the cover film 150 and placing it at a predetermined location. Additionally, since the dry film 100 includes the negative-type photosensitive resin film 120 of this embodiment as a resist layer, cracks are less likely to occur when the base film 110 is cut while being wound from the dry film 100 during film replacement during manufacturing, reducing the amount of cutting waste. Therefore, by utilizing the negative-type photosensitive resin film 120 of this embodiment, the formation of a desired structure is facilitated and yields are improved when manufacturing RF electronic devices.

[0161] The negative-type photosensitive resin film of this embodiment can be suitably used for producing hollow structures. In particular, the negative-type photosensitive resin film of this embodiment is used for producing hollow structures including a substrate having interdigital electrodes, side walls formed on the substrate so as to surround the interdigital electrodes, and a top plate portion formed on the side walls so as to face the substrate, and can be suitably used as a photosensitive material used to form at least one of the side walls and the top plate portion. By using the negative-type photosensitive resin film of this embodiment, when producing hollow structures, as described above, it is possible to achieve both good releasability when peeling off the base film and the ability to suppress the generation of cutting debris, and the film also has excellent lithography performance and performance as a permanent film.

[0162] Alternatively, the negative photosensitive resin film of this embodiment can be suitably used for manufacturing a printed wiring board in which printed wiring is formed on a substrate. In particular, the negative photosensitive resin film of this embodiment can be suitably used for manufacturing a printed wiring board in which printed wiring is formed on a substrate. ２ The negative photosensitive resin film of the present embodiment can be suitably used when the substrate is selected from the group consisting of a silicon nitride substrate, a silicon nitride substrate, a copper substrate, an tantalum nitride substrate, and an tantalum nitride substrate. When a printed wiring board is produced using the negative photosensitive resin film of the present embodiment, as described above, it is possible to achieve both good releasability when peeling off the substrate film and the ability to suppress the generation of cutting debris, and the lithography performance is also excellent.

[0163] (Laminate Film) One embodiment of the laminate film includes a base film and the negative-type photosensitive resin film of the above-described embodiment on the base film. In Fig. 1, the laminate film 130 includes a base film 110 and a negative-type photosensitive resin film 120 on the base film 110.

[0164] The substrate film may be a known film, such as a thermoplastic resin film. Examples of such thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 to 150 μm. The thickness of the negative photosensitive resin film is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0165] The laminate film of this embodiment can be produced, for example, by applying a negative-type photosensitive resin composition containing the above-described components (A1), (A2), (I), and (S) to a substrate film and then baking (post-applied bake (PAB)) the composition at, for example, 90 to 120°C for 3 to 5 minutes to form a negative-type photosensitive resin composition layer (negative-type photosensitive resin film). The content of component (S) in the negative-type photosensitive resin composition is appropriately set depending on the coating film thickness, etc. For example, the content of component (S) can be adjusted so that the solids concentration of the negative-type photosensitive resin composition is 60% by mass or more, or can also be adjusted so that the solids concentration is 70% by mass or more. The negative-type photosensitive resin composition can be applied to the substrate film using an appropriate method such as a blade coater, lip coater, comma coater, or film coater.

[0166] (Dry Film) In one embodiment of the dry film, the negative photosensitive resin film of the above-described embodiment and a cover film are laminated in this order on a base film. In Fig. 1, the dry film 100 is formed by laminating the negative photosensitive resin film 120 and the cover film 150 in this order on a base film 110. Alternatively, the dry film 100 is formed by laminating the lamination film 130 and the cover film 150 such that the negative photosensitive resin film 120 and the cover film 150 are in contact with each other.

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

[0168] Known materials can be used for the cover film, such as a thermoplastic resin film. Examples of the thermoplastic resin include polyethylene film and polypropylene film. The cover film is preferably a film whose adhesive strength with the negative photosensitive resin film is smaller than the adhesive strength between the base film and the negative photosensitive resin 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.

[0169] The dry film of this embodiment can be produced, for example, by applying a negative-type photosensitive resin composition containing the above-mentioned components (A1), (A2), (I), and (S) to a substrate film, drying the composition to form a negative-type photosensitive resin composition layer (negative-type photosensitive resin film), and then laminating a cover film on the negative-type photosensitive resin composition layer (negative-type photosensitive resin film). The negative-type photosensitive resin composition can be applied to the substrate film by an appropriate method using a blade coater, lip coater, comma coater, film coater, or the like.

[0170] When a negative-type photosensitive resin film is formed using the dry film of this embodiment described above and selectively exposed to light, the cationic moiety of component (I) decomposes in the exposed areas of the negative-type photosensitive resin film to generate an acid, which then causes ring-opening polymerization of the epoxy groups in components (A1) and (A2). As a result, the solubility of components (A1) and (A2) in a developer containing an organic solvent decreases in the exposed areas of the negative-type photosensitive resin film, while the solubility of components (A1) and (A2) in a developer containing an organic solvent remains unchanged in the unexposed areas of the negative-type photosensitive resin film. Therefore, a difference in solubility in a developer containing an organic solvent occurs between the exposed and unexposed areas of the negative-type photosensitive resin film. Therefore, when the negative-type photosensitive resin film is developed with a developer containing an organic solvent, the unexposed areas are dissolved and removed, forming a negative pattern.

[0171] The negative photosensitive resin film included in the dry film of this embodiment is typically made 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.

[0172] (Cured Product) One embodiment of the cured product is obtained by curing the negative photosensitive resin film of the above-described embodiment.

[0173] The cured product of the present embodiment can be produced by a production method including a step (i) of forming a negative photosensitive resin layer (photosensitive film) on a support using the negative photosensitive resin film of the above-described embodiment, and a step (ii) of curing the photosensitive film to obtain a cured product.

[0174] [Step (i)] The operation of step (i) can be carried out in the same manner as in the <<Film formation operation>> described later. As the support, a conventionally known support can be used, for example, a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. More specifically, silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO ３ ), niobium, lithium niobate (LiNbO ３Examples of the substrate include a substrate made of a metal such as palladium, titanium tungsten, copper, chromium, iron, or aluminum, and a glass substrate. Materials that can be used for the wiring pattern include copper, aluminum, nickel, gold, and stainless steel. In this embodiment, for example, a lithium tantalate (LiTaO) substrate for a SAW device mounted on a communication terminal is used. ３ ) substrate, lithium niobate (LiNbO ３ The baking treatment can be carried out, for example, at a temperature of 60 to 150° C. for 40 to 600 seconds.

[0175] [Step (ii)] The curing treatment in step (ii) can be carried out, for example, at a temperature of 100 to 250° C. for 0.5 to 2 hours.

[0176] The method for producing a cured product of the present embodiment may include other steps in addition to step (i) and step (ii). For example, an exposure operation (described later) may be included between step (i) and step (ii), and a cured product may be obtained by selectively exposing the photosensitive film formed in step (i) and curing the photosensitive film (pre-cured film) that has been subjected to post-exposure bake (PEB) treatment as needed.

[0177] (Hollow Structure) One embodiment of the hollow structure includes a substrate having interdigital electrodes, side walls formed on the substrate so as to surround the interdigital electrodes, and a top plate formed on the side walls so as to face the substrate. In the hollow structure of this embodiment, at least one of the side walls and the top plate is formed from the cured product of the above-described embodiment.

[0178] 2 and 3 are schematic diagrams showing a series of operations in the method for manufacturing a hollow structure. The method for manufacturing a hollow structure will be described below with reference to the drawings.

[0179] The hollow structure of this embodiment can be manufactured by using a manufacturing method including the following steps (1) and (2): Step (1): Forming a side wall on a substrate having interdigital electrodes; and Step (2): Forming a top plate portion on the side wall to manufacture a hollow structure.

[0180] [Step (1)] In step (1), a sidewall is formed on a substrate having an interdigital electrode. One embodiment of step (1) is a form in which the following operations (1-1), (1-2), (1-3), (1-4), (1-5), and (1-6) are performed in this order. FIG. 2 is a schematic diagram illustrating one embodiment of step (1) in the method for manufacturing a hollow structure. In the embodiment shown in FIG. 2, a substrate 10 having an interdigital electrode (not shown) and a dry film are used to form a sidewall 120Hw on the substrate 10 having the interdigital electrode.

[0181] Regarding operation (1-1): <<Film formation operation>> First, the cover film is removed from the dry film, and a laminate film 130 made of a base film 110 and a negative photosensitive resin film 120 is placed on a substrate 10 having interdigital electrodes. At this time, the laminate film 130 and the substrate 10 are bonded together so that the negative photosensitive resin film 120 and the substrate 10 having interdigital electrodes are in contact with each other. The laminate film 130 and the substrate 10 may be bonded together appropriately using a known method such as a laminator.

[0182] The substrate 10 may be made of silicon, silicon nitride, silicon dioxide, titanium, tantalum, or lithium tantalate (LiTaO ３ ), niobium, lithium niobate (LiNbO ３ ), palladium, titanium tungsten, copper, chromium, iron, aluminum, or the like, or a glass substrate.

[0183] Regarding operation (1-2): <<Substrate film peeling operation>> In operation (1-2), the substrate film 110 is peeled from the negative photosensitive resin film 120 in the laminate film 130. Since the laminate film 130 includes the negative photosensitive resin film 120 according to the present embodiment described above, the substrate film 110 is easily peeled off and has excellent releasability.

[0184] Regarding operation (1-3): <<Exposure operation>> Next, the negative photosensitive resin film 120 arranged on the substrate 10 having the interdigital electrodes is selectively exposed (arrow) through a mask 60 (mask pattern) on which a predetermined pattern is formed, using a known exposure device.

[0185] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet light having a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm), or visible light is selectively irradiated (exposed). Sources of these radiations include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, and the like. The radiation dose is appropriately set depending on the type and amount of each component in the film, the thickness of the coating film, and the like.

[0186] Regarding operation (1-4): <Post-exposure baking operation> After the exposure operation in operation (1-3), the exposed negative photosensitive resin film 120 is subjected to a post-exposure baking (PEB) operation. The temperature of the post-exposure baking operation in operation (1-4) is, for example, 80 to 150°C, and the duration of the post-exposure baking operation is, for example, 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds. By the post-exposure baking operation in operation (1-4), the exposed negative photosensitive resin film 120 becomes an exposed portion 120B in which the epoxy groups in the components (A1) and (A2) have undergone ring-opening polymerization, and an unchanged unexposed portion 120D.

[0187] Regarding operation (1-5): <Developing operation> After operation (1-4), the exposed negative photosensitive resin film 120 (exposed portions 120B, unexposed portions 120D) is developed with a developer containing an organic solvent (organic developer) to form a negative pattern (exposed portions 120B). By the development in operation (1-5), the unexposed portions 120D are dissolved and removed so as to surround the interdigital electrodes, and a negative pattern is formed (the exposed portions 120B remain as residual images).

[0188] The organic solvent contained in the organic developer can be appropriately selected from known organic solvents, and specific examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0189] Known additives can be blended into the organic developer as needed. Examples of such additives include surfactants. The surfactant is not particularly limited, but examples include ionic and nonionic fluorine-based and / or silicon-based surfactants. Nonionic surfactants are preferred, and nonionic fluorine-based surfactants or nonionic silicon-based surfactants are more preferred. When a surfactant is blended, the blending amount is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the organic developer.

[0190] The development process can be carried out by a known development method, for example, a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying the developer onto the surface of the support (spray method), a method of continuously applying the developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method), etc.

[0191] After the development operation, a rinse treatment is preferably carried out. The rinse treatment (cleaning treatment) can be carried out by a known rinse method. Examples of the rinse treatment method include a method in which a rinse solution is continuously applied onto a support rotating at a constant speed (spin coating method), a method in which the support is immersed in the rinse solution for a certain period of time (dip method), and a method in which the rinse solution is sprayed onto the surface of the support (spray method). For the rinse treatment, a rinse solution containing an organic solvent is preferably used.

[0192] Regarding operation (1-6): <<Heating (post-baking) operation>> After the development operation in operation (1-5), a heating (post-baking) operation is performed. The negative pattern (exposed portion 120B) after the development operation is further heated to harden it. As a result, a sidewall 120Hw is formed on the substrate 10 so as to surround the interdigital electrode. The temperature of the heating (post-baking) operation in operation (1-6) is, for example, 100°C or higher, preferably 100°C or higher and 250°C or lower, more preferably 150°C or higher and 200°C or lower. The duration of the heating (post-baking) operation is, for example, 30 minutes or higher, preferably 30 minutes or higher and 120 minutes or lower, more preferably 30 minutes or higher and 90 minutes or lower.

[0193] [Step (2)] In step (2), a top plate portion is formed on the side wall formed in step (1) to produce a hollow structure. One embodiment of step (2) is a form in which the following operations (2-1), (2-2), (2-3), (2-4), (2-5), and (2-6) are performed in this order. FIG. 3 is a schematic diagram illustrating one embodiment of step (2) in the method for producing a hollow structure. In the embodiment shown in FIG. 3, a hollow structure 200 is produced, which includes a substrate 10 on which side walls 120Hw are formed to surround the interdigital electrodes, and a cured body 120H using a dry film and having a top plate portion 120Hr formed on the side walls 120Hw so as to face the substrate 10.

[0194] Regarding operation (2-1): In operation (2-1), first, the cover film is removed from the dry film, and the laminate film 130 made of the base film 110 and the negative photosensitive resin film 120 is placed on the sidewall 120Hw so as to face the substrate 10 having the interdigital electrodes. At this time, the laminate film 130 is placed so that the negative photosensitive resin film 120 is in contact with the upper surface of the sidewall 120Hw. In FIG. 3, the laminate film 130 is placed so as to face the substrate 10 via the sidewall 120Hw. Then, a hollow, sealed space is formed surrounded by the substrate 10, the sidewall 120Hw, and the negative photosensitive resin film 120.

[0195] Regarding operation (2-2): In operation (2-2), the base film 110 is peeled off from the negative photosensitive resin film 120 in the laminate film 130. Since the laminate film 130 includes the negative photosensitive resin film 120 according to the present embodiment described above, the base film 110 is easily peeled off and has excellent releasability.

[0196] Regarding operations (2-3) to (2-6): In operation (2-3), selective exposure (arrow) is performed on the negative photosensitive resin film 120 arranged on the side wall 120Hw using a known exposure device through a mask 60 (mask pattern) on which a predetermined pattern is formed.

[0197] Regarding operation (2-4): After the exposure operation in operation (2-3), a post-exposure bake (PEB) operation is performed on the exposed negative photosensitive resin film 120. By the post-exposure bake operation in operation (2-4), the exposed negative photosensitive resin film 120 becomes an exposed portion 120B in which the epoxy groups in the components (A1) and (A2) have undergone ring-opening polymerization, and an unchanged unexposed portion 120D.

[0198] Regarding operation (2-5): After operation (2-4), the exposed negative photosensitive resin film 120 (exposed area 120B, unexposed area 120D) is developed with a developer containing an organic solvent (organic developer) to form a negative pattern (exposed area 120B). By the development in operation (2-5), the unexposed area 120D is dissolved and removed, and a negative pattern is formed (the exposed area 120B remains as an afterimage).

[0199] Regarding operation (2-6): After the development operation in operation (2-5), a heating (post-bake) operation is performed. The negative pattern (exposed portion 120B) after the development operation is further heated to harden it. As a result, a top plate portion 120Hr is formed on the side wall 120Hw so as to face the substrate 10 having the interdigital electrodes. In FIG. 3, the dotted line between the side wall 120Hw and the top plate portion 120Hr indicates the imaginary interface. In FIG. 3, a cured body 120H in which the side wall 120Hw and the top plate portion 120Hr are integrated is formed by the heating operation. Then, a hollow structure 200 in which interdigital electrodes are arranged is produced in a hollow, sealed space surrounded by the substrate 10 and the cured body 120H.

[0200] The explanation of each of the steps (2-3) to (2-6) is the same as the explanation of the steps (1-3), (1-4), (1-5) and (1-6) described above.

[0201] When producing the hollow structure of this embodiment, the negative-type photosensitive resin film of this embodiment described above is used in operations (1-2) and (2-2). Therefore, the base film is easily peeled from the negative-type photosensitive resin film in the laminate film, resulting in excellent releasability when peeling the base film. In addition, because the negative-type photosensitive resin film of this embodiment described above is used in operations (1-1) and (2-1), when replacing the dry film during the production of the hollow structure, cracks are less likely to occur when the base film is wound and cut from the dry film, reducing the generation of cutting debris. The hollow structure of this embodiment described above can be suitably used for hollow packages used in radio frequency (RF) electronic devices such as surface acoustic wave (SAW) filters and bulk acoustic wave (BAW) filters.

[0202] In the above description of the method for producing a hollow structural body, a laminate film 130 of a base film 110 and a negative photosensitive resin film 120 is used in both step (1) and step (2), but this is not limited thereto, and a laminate film 130 may be used in only one of step (1) or step (2). That is, both of the side walls and the top plate that constitute the hollow structural body may be formed from the cured product of the above-mentioned embodiment, or either the side walls or the top plate may be formed from the cured product of the above-mentioned embodiment.

[0203] (Printed Wiring Board) One embodiment of the printed wiring board is a Si substrate, SiO ２ The present invention comprises a substrate selected from the group consisting of a silicon nitride substrate, a silicon nitride substrate, a copper substrate, a lithium tantalate (LT) substrate, and a lithium niobate (LN) substrate, and the cured product of the above-described embodiment. The cured product of the above-described embodiment can be suitably used for forming an insulating layer of a printed wiring board, such as an interlayer insulating layer. When manufacturing the printed wiring board of the present embodiment, the negative photosensitive resin film of the present embodiment described above is used, thereby achieving both releasability when peeling off the base film and suppression of cutting debris generation, thereby improving yield. In addition, the negative photosensitive resin film of the present embodiment described above is used, resulting in excellent lithography performance for negative patterns and enabling high-precision processing.

[0204] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0205] <Preparation of Negative Photosensitive Composition> The components shown in Tables 1 and 2 were mixed and dissolved, and the mixture was filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Corporation) to prepare a negative photosensitive composition with a solids concentration of 78% by mass.

[0206]

[0207]

[0208] In Tables 1 and 2, the abbreviations have the following meanings: The numbers in brackets [ ] are the amounts of each component blended (parts by mass; solid content equivalent).

[0209] (A1)-1: Novolac epoxy resin represented by the following chemical formula (A1-1-1). Product name "jER-157S70", manufactured by Mitsubishi Chemical Corporation. Softening point: 70°C, epoxy equivalent: 200 to 220 g / eq. (A1)-2: Monomer represented by the following chemical formula (A1-2-1). Product name "TECHMORE VG3101L", manufactured by Printec Co., Ltd. Softening point: 39 to 46°C, epoxy equivalent: 200 to 220 g / eq. (A1)-3: Cresol novolac epoxy resin represented by the following chemical formula (A1-3). Product name "YDCN-704", manufactured by Nippon Steel Chemical & Material Co., Ltd. Softening point: 87 to 97°C, epoxy equivalent: 200 to 220 g / eq. (A1)-4: Phenol novolac epoxy resin represented by the following chemical formula (A1-4). Product name: "EPICLON N-770", manufactured by DIC Corporation. Softening point: 65-75°C, epoxy equivalent: 180-200g / eq.

[0210]

[0211] (A2)-1: A compound represented by the following chemical formula (A2-1). Trade name "Celloxide 2021P", manufactured by Daicel Corporation. Molecular weight: 252.31, epoxy equivalent: 120 to 140 g / eq.; viscosity (25°C): 0.250 Pa·s. (A2)-2: Pentaerythritol tetraglycidyl ether represented by the following chemical formula (A2-2). Molecular weight: 360.4, epoxy equivalent: 90 to 100 g / eq.; viscosity (25°C): 0.310 Pa·s. (A2)-3: A compound represented by the following chemical formula (A2-3). Trade name "Epocalic THI-DE", manufactured by ENEOS Corporation. Molecular weight: 152.19, epoxy equivalent: 80 to 100 g / eq. Viscosity (25°C) 0.080 Pa·s (A2)-4: A compound represented by the following chemical formula (A2-4). Product name "Celloxide 8010", manufactured by Daicel Corporation. Molecular weight 194, epoxy equivalent 80 to 100 g / eq. Viscosity (25°C) 0.030 Pa·s

[0212]

[0213] (I)-1: A cationic photopolymerization initiator represented by the following chemical formula (I-1): Add-1: γ-glycidyloxypropyltrimethoxysilane represented by the following chemical formula (SC-1):

[0214]

[0215] (S)-1: Methyl ethyl ketone (MEK) (S)-2: Propylene glycol monomethyl ether acetate (PGMEA) (S)-3: Propylene glycol monomethyl ether (PGME) (S)-4: γ-butyrolactone (GBL) (S)-5: Methoxybutyl acetate (MBA)

[0216] <Preparation of Laminated Films> Each of the negative photosensitive compositions shown in Tables 1 and 2 was applied to a substrate film using an applicator and dried in an oven at 70°C for varying heating times. This resulted in the formation of 45 μm-thick photosensitive resin films with different solvent contents (amounts of residual solvent), yielding photosensitive laminated films. A 50 μm-thick polyethylene terephthalate (PET) film was used as the substrate film. The negative photosensitive compositions used were the above-described compositions (1-1) to (1-14) and compositions (2-1) to (2-14). That is, a laminated film was obtained comprising a 45 μm-thick negative photosensitive resin film on a 50 μm-thick PET film.

[0217] [Measurement of Solvent Content Remaining in Negative Photosensitive Resin Film] The solvent content (residual solvent amount) remaining in the negative photosensitive resin film constituting the laminate film was measured and calculated using a gas chromatograph (GC) under the following measurement conditions. The results are shown in Tables 3 and 4. Gas chromatograph (GC) measurement conditions: Apparatus: Agilent 6850 Column: Agilent J&W DB-WAX, 30 m x 0.25 mm x 0.25 μm Sample amount used: 1 microliter Helium flow rate: 132 mL / min Sample temperature at introduction: 250°C Detector: Hydrogen flame ionization detector Measurement method: After introduction of the sample, the sample was held at 40°C for 5 minutes, heated to 220°C at a heating rate of 10°C / min, and held at that temperature for 3 minutes to measure.

[0218] <Evaluation> The laminated films prepared above were evaluated for releasability when peeling off the substrate film and suppression of generation of cutting debris as follows. The results are shown in Tables 3 and 4.

[0219] [Releasability when peeling off the base film] The laminated film was laminated onto a Si substrate using a laminator manufactured by Taisei Laminator Co., Ltd., so that the Si substrate and the negative photosensitive resin film were in contact. After lamination, only the PET film directly on the negative photosensitive resin film was cut to a width of 20 mm, and the peel strength (N) was measured using a light-load type adhesive / film peeling analyzer VPA-3 manufactured by Kyowa Interface Science Co., Ltd., under the conditions of a load cell of 0.1 N and a peel angle of 90°. Using this peel strength (N) as an index, the releasability when peeling off the base film was evaluated.

[0220] [Suppression of Cutting Dust Generation] The laminated film was placed on the cutting stage of a TEAM-100ARF manufactured by Takatori Corporation, with the cutting stage surface and the negative photosensitive resin film in contact. The film was cut to fit the wafer size using a film cutter heated to 60°C. The cut edge portion (cut surface) of the negative photosensitive resin film after cutting was observed under a microscope, and the suppression of cutting dust generation was evaluated by rating cracked and broken films as NG and OK, respectively.

[0221]

[0222]

[0223] From the results shown in Table 3, it was confirmed that the negative-type photosensitive resin films of Examples 1 to 14, in which the solvent content relative to the total mass of the negative-type photosensitive resin film was 0.05 mass % or more and 1.5 mass % or less, had peel strengths in the range of 0.01 to 0.09 N, and that the cut edge portions (cut surfaces) were free of cracks and breakage.

[0224] From the results shown in Table 4, it was confirmed that, in the negative photosensitive resin films of Comparative Examples 1 to 14, those in which the solvent content relative to the total mass of the negative photosensitive resin film was less than 0.05% by mass had a low peel strength of 0.01 N, but that cracks had occurred at the cut edge portion (cut surface). Also, those in which the solvent content relative to the total mass of the negative photosensitive resin film was more than 1.5% by mass had a high peel strength of 0.1 N, but that the cut edge portion (cut surface) was not cracked or broken.

[0225] From the above, it is recognized that the negative photosensitive resin film to which the present invention is applied can achieve both good releasability when peeling off the substrate film and the ability to suppress the generation of cutting debris.

[0226] In addition, from the results shown in Table 3, it can be confirmed that the negative photosensitive resin films of Examples 1 to 14, in which the mass ratio represented by solvent / photocationic polymerization initiator in the negative photosensitive resin film was 0.04 or more and 1.1 or less, had peel strengths in the range of 0.01 to 0.09 N, and the cut edge portion (cut surface) was free from cracks and breakage.

[0227] In addition, from the results shown in Table 4, it was confirmed that, among the negative photosensitive resin films of Comparative Examples 1 to 14, those in which the mass ratio represented by solvent / photocationic polymerization initiator in the negative photosensitive resin films was less than 0.04 had a low peel strength of 0.01 N, but that cracks had occurred in the cut edge portion (cut surface). Also, it was confirmed that those in which the mass ratio represented by solvent / photocationic polymerization initiator in the negative photosensitive resin films was more than 1.1 had a high peel strength of 0.1 N, but that the cut edge portion (cut surface) was not cracked or broken.

[0228] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Addition, omission, substitution, and other modifications of the configuration are possible within the scope of the spirit of the present invention. The present invention is not limited by the above description, but is limited only by the scope of the appended claims.

[0229] 10 substrate, 60 mask, 100 dry film, 110 base film, 120 negative photosensitive resin film, 120B exposed area, 120D unexposed area, 120H cured body, 120Hw side wall, 120Hr top plate portion, 130 laminated film, 150 cover film, 200 hollow structure

Claims

1. A negative-type photosensitive resin film containing a trifunctional or higher polyfunctional epoxy compound that is solid at 23°C, an epoxy compound that is liquid at 23°C, a photocationic polymerization initiator, and a solvent, wherein the content of the solvent is 0.05% by mass or more and 1.5% by mass or less relative to the total mass of the negative-type photosensitive resin film.

2. The negative photosensitive resin film according to claim 1, wherein the mixing ratio of the photocationic polymerization initiator to the solvent is 0.04 or more and 1.1 or less as a mass ratio expressed as solvent / photocationic polymerization initiator.

3. A negative photosensitive resin film according to claim 1 or 2, which is used to manufacture a hollow structure comprising a substrate having interdigital electrodes, side walls formed on the substrate so as to surround the interdigital electrodes, and a top plate portion formed on the side walls so as to face the substrate, and which is used to form at least one of the side walls and the top plate portion.

4. The negative photosensitive resin film according to claim 1 or 2, which is used for producing a printed wiring board having printed wiring formed on a substrate.

5. The substrate is a Si substrate, SiO ２ 5. The negative photosensitive resin film according to claim 4, wherein the substrate is selected from the group consisting of a silicon substrate, a silicon nitride substrate, a copper substrate, a tantalum nitride substrate, and an iron nitride substrate.

6. A laminated film comprising a base film and the negative photosensitive resin film according to claim 1 or 2 on the base film.

7. A dry film comprising a base film and a negative photosensitive resin film according to claim 1 or 2 and a cover film laminated in this order on the base film.

8. A cured product obtained by curing the negative photosensitive resin film according to claim 1 or 2.

9. A hollow structure comprising a substrate having interdigital electrodes, side walls formed on the substrate so as to surround the interdigital electrodes, and a top plate portion formed on the side walls so as to face the substrate, wherein at least one of the side walls and the top plate portion is formed from the cured product according to claim 8.

10. Si substrate, SiO ２ A printed wiring board comprising: a substrate selected from the group consisting of a silicon nitride substrate, a silicon nitride substrate, a copper substrate, an tantalum nitride substrate, and an tantalum nitride substrate; and an insulating layer formed from the cured product according to claim 8 .

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