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

Abstract

To provide a negative photosensitive resin film capable of achieving both releasability during separation of a base material film and suppression of the generation of cut waste, and a multilayer film, a dry film, a cured product, a hollow structure, and a printed wiring board using the same.SOLUTION: 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, 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 photosensitive resin film.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive resin film, a laminated film, a dry film, a cured product, a hollow structure, and a printed wiring board. [Background technology]

[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 have hollow structures with hollow encapsulation structures that ensure the propagation of acoustic waves and the mobility of movable parts of the electronic devices. The hollow structure is produced by molding a photosensitive material onto a wiring substrate on which interdigital electrodes and the like are formed, while maintaining the hollow space. The photosensitive material used here is required to form a thin and 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 this negative photosensitive resin composition and a cover film are laminated in this order on a substrate film (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-36533 Summary of the Invention [Problem to be solved by the invention]

[0005] When producing the hollow structural body, the release property of the dry film when peeling off the base film is important. When the cover film is removed from the dry film and the laminate film 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, causing streaks, which affect the formation of the structure and reduce the 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. [Means for solving the problem]

[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 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 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] A sixth aspect of the present invention is a printed wiring board comprising a substrate selected from the group consisting of a Si substrate, a SiO2 substrate, a SiN substrate, a Cu substrate, a LT substrate, and an LN substrate, and an insulating layer formed from the cured product according to the fourth aspect. [Effects of the Invention]

[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. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 is a cross-sectional view illustrating an embodiment of a dry film. [Figure 2] 2 is a schematic diagram illustrating an 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. [Figure 3] 3 is a schematic diagram illustrating an embodiment of step (2) in the method for manufacturing a hollow structure. In the embodiment shown in Fig. 3, a substrate 10 having side walls 120Hw formed to surround interdigital electrodes and a dry film are used to fabricate a hollow structure 200 having a top plate portion 120Hr formed on the side walls 120Hw so as to face the substrate 10. DETAILED DESCRIPTION OF THE INVENTION

[0017] In this specification and claims, the term "aliphatic" is a relative concept to aromatic, and is defined to mean a group or compound that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of such halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The term "fluorinated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "optionally substituted" includes both cases where a hydrogen atom (-H) is replaced with a monovalent group and where a methylene group (-CH2-) is replaced with a divalent group. The term "exposure" is a general concept that includes 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 different scales. 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 base 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] The dry film 100 shown in FIG. 1 includes the negative photosensitive resin film 120 of this embodiment, and therefore after removing the cover film 150 and placing it in a predetermined location, the base film 110 can be easily peeled off from the laminated film 130 of the base film 110 and the negative photosensitive resin film 120, providing good releasability. In addition, since the dry film 100 is equipped with the negative photosensitive resin film 120 of this embodiment, when the film is replaced during production, cracks are less likely to occur when the base film 110 is cut while being wound up from the dry film 100, and the generation of cutting waste is reduced.

[0022] When the negative photosensitive resin film of this embodiment is selectively exposed to light, the cationic portion of the photocationic polymerization initiator decomposes in the exposed portion of the negative photosensitive resin film to generate an acid. The acid causes ring-opening polymerization of the epoxy group 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 portion of the negative photosensitive resin film, resulting in a difference in solubility in an organic developer between the exposed and unexposed portions of the negative photosensitive resin film. Therefore, when the negative photosensitive resin film is developed with an organic developer, the unexposed portion is dissolved and removed, and the exposed portion becomes a residual image, forming a negative pattern.

[0023] <Trifunctional or higher polyfunctional epoxy compounds that are solid at 23°C> 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 has sufficient epoxy groups to form a negative pattern by exposure.

[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 or lower. 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 the 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 an epoxy compound can be measured by potentiometric titration as described in JIS K-7236. Examples of 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 novolakizing 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] [ka] [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. n1 is an integer of 1 to 5. R EP is an epoxy group-containing group. EP may be the same or different from each other.

[0029] In the formula (A1-1), R p1 , R p2The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of 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 them, R p1 , R p2 As the alkyl group, a hydrogen atom or a linear or branched alkyl group is preferred, a hydrogen atom or a linear alkyl group is more preferred, and a hydrogen atom or a methyl group is particularly preferred. In the formula (A1-1), a plurality of R p1 may be the same or different. p2 may be the same as or different from each other.

[0030] In the formula (A1-1), n1 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. R EP The 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. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure, which is a three-membered ring ether, and specifically, a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that forms the basic skeleton of 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, alkoxy, or hydroxyl groups. 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 linked 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 optionally substituted divalent hydrocarbon groups: Such a 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 straight-chain or branched-chain 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, even more preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)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. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene 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 an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. 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 thereof 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 the aromatic ring 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 the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle 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 hydrogen atom has been further 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 number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[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, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or 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, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or 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, more 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, with a fluorine atom being 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 have been 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 heteroatom, and the heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[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 the hydrogen atom of the alicyclic hydrocarbon group.

[0040] Regarding divalent linking groups containing heteroatoms: The heteroatom in the divalent linking group containing a heteroatom 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)-, -OC(=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-, and groups represented by the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 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, acyl, etc. 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 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or- Y 21 -OC(=O)-Y 22 -Medium, Y 21 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 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. Y 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. Formula − [Y 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 - is a group represented by the formula -Y 21-C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) 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] [ka] [In formula (A1-2), R p3 , R p4 and R p5 Rm each independently represents 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 p5The 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 them, 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 and a glycidyl group is preferred. Multiple Rm EP may be the same as or different from each other.

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

[0048] [ka]

[0049] As the trifunctional epoxy compound, compounds having a structure in which the distance between the three epoxy groups within the molecule is large 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 formula (A1-2-1) and the above formula (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] [ka] [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 represented by R p1 , R p2 The alkyl group has 1 to 5 carbon atoms. R a22 , R a23 The halogen atom is preferably a chlorine atom or a bromine atom. In the formula (anv1), R EP represents R in the formula (A1-1). EP and a glycidyl group is preferred.

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

[0054] [ka]

[0055] The component (A1) may be a resin consisting solely of the structural unit (anv1), or 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 structural units represented by the following general formulae (anv2) to (anv3).

[0056] [ka] [In the formula, R a24 R is a hydrocarbon group which may have a substituent. a25 ~R a26 , R a28 ~R a30 R 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, an n-pentyl group, etc. 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 a24 When 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. The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has 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.

[0060] R a24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring 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 the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings. R a24Specific examples of the aromatic hydrocarbon group in the formula (I) include a group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle; 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., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, 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 defined as R 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 Similar to 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] [ka]

[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 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 HP5000 (all 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 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, even more preferably 85 to 95% by mass, and particularly preferably 90 to 95% by mass, relative to the total mass of the negative photosensitive resin film.

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

[0069] The epoxy equivalent of the 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 the (A2) component 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 a compound containing a partial structure represented by the following general formula (A2-m1) (hereinafter also referred to as "component (m1)").

[0071] [ka] [In the formula, n2 is an integer of 1 to 4.]

[0072] In formula (A2-m1), n2 represents 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 a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, etc. The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are represented by 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)—OY 21A group represented by Y - is more preferred. 21 As 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), and n1 and n2 each represent an integer of 1 to 30.

[0075] [ka]

[0076] Furthermore, 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] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different from each other.

[0078] In the above 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 photosensitive resin film of this embodiment, the component (A2) may be used alone or in combination of two or more types. The component (A2) preferably contains at least one selected from the group consisting of the component (m1) and the component (m2), and among these, the component (m2) is more preferred.

[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 (all manufactured by Daicel Corporation); Epocalic THI-DE, DE-102, and DE-103 (all manufactured by ENEOS Corporation); Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-622, and EX-850L (all manufactured by Nagase ChemteX Corporation); the 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 the 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 the component (A1). When the content of component (A2) is equal to or greater than the lower limit of the above-mentioned 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 equal to or less than the upper limit of the above-mentioned preferred range, the peel strength when peeling the substrate film from the laminate film is reduced, and releasability is improved.

[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 when irradiated with active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF or ArF, X-rays, or electron beams, and the cations can serve as polymerization initiators. 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 salts Onium borate salts (component (I1)) generate a relatively strong acid upon exposure to light. 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) is less likely to be toxic or corrosive to metals. Suitable examples of the component (I1) include compounds represented by the following general formula (I1).

[0085] [ka] [In the formula, R b01 ~Rb04 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 section In the formula (I1), R b01 ~R b04 The aryl group in the formula (I) preferably has 5 to 30 carbon atoms, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include a naphthyl group, a phenyl group, and an anthracenyl group, with a phenyl group being preferred because of its easy availability. R b01 ~R b04 The aryl group in 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 enhanced, which is preferable. Among them, 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(C6F5)4] - );Tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - );Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ); Trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - );Tetrakis(difluorophenyl)borate ([B(C6H3F2)4] -) etc. Among them, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferred.

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

[0089] [ka] [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 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 represents -C(=O)- or -C(=O)-O-. Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0090] R 201 ~R 207 , and R 211 ~R 212The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 , and R 211 ~R 212 Examples of the heteroaryl group in the above 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; 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 the formula (I) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 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 (ca-r-1) to (ca-r-10):

[0091] [ka] [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 formulas (ca-r-1) to (ca-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 groups: 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. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0094] R' 201 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R' 201 Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R' 201Specific 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 to 2, and particularly preferably 1.

[0095] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in 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 straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which one or more 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 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 bridged ring polycyclic skeleton, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a fused ring polycyclic skeleton, 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 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0098] An optionally substituted chain alkyl group: R' 201 The chain alkyl group may be either a straight chain or a branched chain. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heneicosyl group, and a docosyl group. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10. 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] An optionally substituted chain alkenyl group: 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 the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the chain alkenyl groups mentioned above, linear alkenyl groups are preferred, vinyl groups 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 may not contain a heteroatom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(applicable R Nis 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 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in the formula (I) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

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

[0106] In the above formulas (ca-4) and (ca-5), x is 1 or 2. W 201 is an (x+1)-valent, i.e., a divalent or trivalent linking group. W 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 an arylene group alone is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred. W 201 The trivalent linking group in 201 Examples 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 (1), and a group in which the divalent linking group is further bonded to the divalent linking group shown in the formula (1). 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] [ka]

[0109] [ka] [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 the group

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

[0111] [ka]

[0112] [ka] [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] [ka]

[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] [ka]

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

[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] [ka]

[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] [ka]

[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] [ka] [In the formula, R' 212 R' 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 cationic photopolymerization 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] (I2) Ingredients: 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 to light, and therefore, when a negative-type photosensitive resin film containing the component (I2) is used to form a pattern, sufficient sensitivity is obtained and a good pattern is formed.

[0127] [ka] [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] [ka] [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 section In the above formula (I2-1), R b05 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b05 may be the same as or different from each other. R b05The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. 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. Among them, R b05 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and further preferably a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group.

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

[0131] [ka] [In the formula, R bf05 nb is a fluorinated alkyl group which may have a substituent. 1 is an integer between 1 and 5.

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

[0133] In the above formula (I2-2), R b06 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b06 may be the same as or different from each other. R b06 The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. 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. Among them, R 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] Cation part 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. This Q q+ As the 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] (I3) Ingredients: The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0136] [ka] [In the formula, R b11 ~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. m is an integer of 1 or more, and M m+ are each independently an m-valent organic cation.

[0137] {Component (I3-1)} Anion section 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 R' 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. R b12 The alkyl group 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. The aliphatic cyclic group is preferably a group in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like (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, or the like. R b12 The hydrocarbon group may have a substituent other than a halogen atom, and examples of the substituent include R b11 Examples of the substituents include those similar to the substituents other than halogen atoms that may be contained in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above formula. The phrase "may have a substituent other than a halogen atom" as used herein not only excludes cases where a substituent consists of only halogen atoms, but also excludes cases where a substituent contains at least one halogen atom (for example, when the substituent is a fluorinated alkyl group).

[0138] Preferred examples of the anion moiety of the component (I3-1) are shown below.

[0139] [ka]

[0140] Cation part In formula (I3-1), M m+ is an m-valent organic cation. M 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 above 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 because it improves resolution and roughness characteristics. The substituents that the organic group may have are the same as those described above, and 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 (ca-r-1) to (ca-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. m+ Suitable organic cations include those 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 section 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 R' 201 Among 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 As the substituent, 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 is preferred. 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 connected 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 formulas (y-al-1) to (y-al-7) is 101 is.

[0143] [ka] [In the formula, V' 101 V' 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 may be a straight-chain alkylene group or a branched-chain alkylene group, and is preferably a straight-chain alkylene group. V' 101 and V' 102Specific examples of the alkylene group in the formula (I) include a methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; an ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3)CH2 -, etc.; a trimethylene group (n-propylene group) [-CH2CH2CH2-]; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; a tetramethylene group [-CH2CH2CH2CH2-]; alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and a pentamethylene group [-CH2CH2CH2CH2CH2-]. Also, V' 101 or V' 102 In the above, 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 removing one hydrogen atom from a cyclic aliphatic hydrocarbon group (a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group) 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 thereof include straight-chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched-chain alkyl groups such as 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.

[0147] R b11 As the aryl group, a cyclic group which may have a substituent other than a halogen atom is preferred. Preferred examples of the anion moiety of the component (I3-2) are shown below.

[0148] [ka]

[0149] Cation part 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, the component (I) is preferably a cationic photopolymerization initiator that generates an acid with a pKa (acid dissociation constant) of -5 or less upon exposure. By using a cationic photopolymerization 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 the component (I) is preferably -15 or more. By using a cationic photopolymerization initiator that generates an acid with such a suitable pKa, high sensitivity can be easily achieved. Here, "pKa (acid dissociation constant)" refers to a commonly used index indicating the acid strength of a substance of interest. In this specification, pKa is a value at a temperature of 25°C. The pKa value can be determined by measurement using known methods. Alternatively, a calculated value using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development) 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 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 the 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 the component (A1). When the content of component (I) is equal to or greater than the lower limit of the preferred range, sufficient sensitivity is obtained, and the lithography characteristics of the pattern are further improved. In addition, the strength of the negative-type photosensitive resin film is further increased. On the other hand, when the content is equal to or less than the upper limit of the preferred range, the sensitivity is appropriately controlled, and a pattern with a good shape is easily obtained.

[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 suitable organic solvents 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 component (S) may be used alone or as a mixed solvent of two or more types.

[0154] In the negative-type photosensitive resin film of the present embodiment, the content of the solvent (component (S)) is from 0.05% by mass to 1.5% by mass, preferably from 0.1% by mass to 1.0% by mass, and more preferably from 0.5% by mass to 1.0% by mass, relative to the total mass of the negative-type photosensitive resin film. When 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, when the content is equal to or less than the upper limit of the above range, the substrate film can be easily peeled from the laminate film of the substrate film and the 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 a laminate film, for example, by controlling the heating conditions (e.g., temperature, heating time) when forming the negative photosensitive resin film.

[0155] In the negative-type photosensitive resin film of the present 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 or more and 1.1 or less, more preferably 0.05 or more and 0.7 or less, and even more preferably 0.4 or more and 0.7 or less. When the mass ratio of 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 waste is easily 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 photosensitive resin film, and releasability is improved.

[0156] <Other ingredients> The negative photosensitive resin film of the present embodiment may contain other components as needed in addition to the above-described components (A1), (A2), (I) and (S). If desired, the negative-type photosensitive resin film of the present embodiment may 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.

[0157] <Silane coupling agents> The silane coupling agent can be used as an adhesion aid to improve the adhesion between the negative photosensitive resin film and the substrate. Examples of the silane coupling agent include silane coupling agents having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, etc. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The silane coupling agents may be used alone or in combination of two or more. When a silane coupling agent is included, the content thereof 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 the component (A1). When the content of the silane coupling agent is within the above-mentioned preferred range, the strength of the cured film is further increased, and in addition, the adhesion between the cured film and the substrate is further strengthened.

[0158] 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 remaining solvent in the resist layer after being made into a dry film is controlled by heating conditions, etc.

[0159] 1 includes the negative photosensitive resin film 120 of this embodiment as a resist layer, and therefore provides good releasability when peeling the base film 110 from the laminate film 130 after removing the cover film 150 and placing the dry film 100 at a predetermined location. In addition, since the dry film 100 includes the negative 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 up from the dry film 100 during film replacement during production, and the generation of cutting waste is reduced. Therefore, by using the negative photosensitive resin film 120 of this embodiment, when manufacturing RF electronic devices, it becomes easier to form the desired structure, and the yield improves.

[0160] The negative-type photosensitive resin film of this embodiment can be suitably used for manufacturing a hollow structure, particularly a hollow structure including 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, and can be suitably used as a photosensitive material for forming at least one of the side walls and the top plate. By using the negative photosensitive resin film of this embodiment, when producing a hollow structure, 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 it also has excellent lithography performance and performance as a permanent film.

[0161] Alternatively, the negative-type 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-type photosensitive resin film of this embodiment can be suitably used when the substrate is selected from the group consisting of a Si substrate, a SiO2 substrate, a SiN substrate, a Cu substrate, a LT substrate, and an LN substrate. By using the negative photosensitive resin film of this embodiment, when producing a printed wiring board, 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 lithography performance is also excellent.

[0162] (Laminated film) One embodiment of the laminate film comprises a base film and the negative photosensitive resin film of the above-described embodiment on the base film. In FIG. 1, the laminated film 130 includes a negative photosensitive resin film 120 on a base film 110 .

[0163] The substrate film may be a known film, such as a thermoplastic resin film. Examples of the thermoplastic resin 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.

[0164] The laminate film of the present embodiment can be produced, for example, by applying a negative-type photosensitive resin composition containing the above-mentioned components (A1), (A2), (I), and (S) onto 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 the component (S) in the negative photosensitive resin composition is appropriately set depending on the coating film thickness, etc. For example, the content of the component (S) can be adjusted so that the solids concentration of the negative photosensitive resin composition is 60% by mass or more, or the content of the component (S) can also be adjusted so that the solids concentration is 70% by mass or more. The negative photosensitive resin composition may be applied to the substrate film by a suitable method using a blade coater, lip coater, comma coater, film coater, or the like.

[0165] (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. 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 base film 110. Alternatively, the dry film 100 is formed by laminating a laminate film 130 and a cover film 150 such that the negative photosensitive resin film 120 and the cover film 150 are in contact with each other.

[0166] The substrate film may be a known film, such as a thermoplastic resin film. Examples of the thermoplastic resin 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.

[0167] The cover film may be a known 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 to 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.

[0168] The dry film of the present embodiment can be produced, for example, by applying a negative-type photosensitive resin composition containing the above-mentioned components (A1), (A2), (I), and (S) onto 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 photosensitive resin composition may be applied to the substrate film by a suitable method using a blade coater, lip coater, comma coater, film coater, or the like.

[0169] When a negative-type photosensitive resin film is formed using the dry film of the present embodiment described above and the negative-type photosensitive resin film is 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, and the epoxy groups in components (A1) and (A2) undergo ring-opening polymerization due to the action of the acid. As a result, the solubility of the 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 the 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.

[0170] Here, 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.

[0171] (cured product) One embodiment of the cured product is obtained by curing the negative photosensitive resin film of the above-described embodiment.

[0172] The cured product of this 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-mentioned embodiment, and a step (ii) of curing the photosensitive film to obtain a cured product.

[0173] [Step (i)] The operation of step (i) can be carried out in the same manner as in the <<Membrane Forming Operation>> described later. The support may be a conventionally known one, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. More specifically, examples include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO), niobium, lithium niobate (LiNbO), palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. Examples of 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 (LiTaO3) substrate or a lithium niobate (LiNbO3) substrate for use in a SAW device mounted on a communication terminal can be suitably used. The baking treatment can be carried out, for example, at a temperature of 60 to 150° C. for 40 to 600 seconds.

[0174] [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.

[0175] The method for producing a cured product of the present embodiment may include other steps in addition to steps (i) and (ii). For example, an "exposure operation" described below may be included between steps (i) and (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 a post-exposure bake (PEB) treatment as needed.

[0176] (Hollow structure) One embodiment of the hollow structure comprises a substrate having an interdigital electrode, a sidewall formed on the substrate so as to surround the interdigital electrode, and a top plate portion formed on the sidewall so as to face the substrate. In the hollow structural body of this embodiment, at least one of the side wall and the top plate portion is formed from the cured product of the above-described embodiment.

[0177] 2 and 3 show a schematic diagram of a series of operations in the method for producing a hollow structure. The method for manufacturing the hollow structural body will be described below with reference to the drawings.

[0178] The hollow structure of this embodiment can be manufactured by using the manufacturing method including steps (1) and (2) shown below. Step (1): Forming a sidewall on a substrate having an interdigital electrode. Step (2): A step of forming a top plate portion on the side wall to produce a hollow structure.

[0179] [Process (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 carried out in this order. 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.

[0180] Regarding operation (1-1): ≪Film formation operation≫ First, the cover film is removed from the dry film, and the laminated film 130 made of the base film 110 and the negative photosensitive resin film 120 is placed on the substrate 10 having the interdigital electrodes. At this time, the laminated film 130 and the substrate 10 are bonded together so that the negative photosensitive resin film 120 and the substrate 10 having the interdigital electrodes are in contact with each other. The laminated film 130 and the substrate 10 may be bonded together by a known method using a laminator or the like.

[0181] Examples of the substrate 10 include metal substrates such as silicon, silicon nitride, silicon dioxide, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates.

[0182] Regarding operation (1-2): <<Substrate film peeling operation>> In operation (1-2), the base film 110 is peeled off from the negative photosensitive resin film 120 in the laminated film . Since the laminated film 130 includes the negative photosensitive resin film 120 according to the present embodiment described above, the base film 110 can be easily peeled off, providing excellent releasability.

[0183] Regarding operations (1-3): <Exposure operation> Next, a negative photosensitive resin film 120 placed on a substrate 10 having interdigital electrodes is selectively exposed (arrow) through a mask 60 (mask pattern) on which a predetermined pattern is formed, using a known exposure device.

[0184] 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). As the radiation source for these radiations, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc. can be used. Here, radiation means ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose is appropriately set depending on the type and amount of each component in the film, the thickness of the coating film, etc.

[0185] Regarding operations (1-4): <Post-exposure heating operation> After the exposure operation in operation (1-3), the exposed negative photosensitive resin film 120 is subjected to a post-exposure bake (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, more preferably 60 to 900 seconds. By the post-exposure heating operation in operation (1-4), the negative photosensitive resin film 120 after exposure becomes an exposed portion 120B where the epoxy groups in the components (A1) and (A2) have undergone ring-opening polymerization, and an unexposed portion 120D where no change occurs.

[0186] Regarding operations (1-5): <Developing operations> After operation (1-4), 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 development in operation (1-5), the unexposed area 120D is dissolved and removed so as to surround the interdigital electrodes, forming a negative pattern (exposed area 120B remains as an afterimage).

[0187] 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.

[0188] The organic developer may contain known additives as needed. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants. The surfactant is preferably a nonionic surfactant, and more preferably a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant. When a surfactant is added, the amount added is usually 0.001 to 5 mass %, preferably 0.005 to 2 mass %, and more preferably 0.01 to 0.5 mass %, based on the total amount of the organic developer.

[0189] The development process can be carried out by a known development method, such as 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), or 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).

[0190] After the development operation, a rinsing treatment is preferably carried out. The rinse treatment (cleaning treatment) can be carried out by a known rinse method, such as 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 a support is immersed in a rinse solution for a certain period of time (dip method), or a method in which a rinse solution is sprayed onto the surface of the support (spray method). The rinsing treatment is preferably carried out using a rinsing liquid containing an organic solvent.

[0191] Regarding operations (1-6): <Heating (post-bake) operation> After the development step in step (1-5), a heating (post-baking) step is carried out. The negative pattern (exposed portion 120B) after the development process is further heated to harden it, thereby forming a sidewall 120Hw on the substrate 10 so as to surround the interdigital electrodes. 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 longer, preferably 30 minutes or higher and 120 minutes or lower, more preferably 30 minutes or higher and 90 minutes or lower.

[0192] [Process (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 the step (2) is a form in which the following operations (2-1), (2-2), (2-3), (2-4), (2-5), and (2-6) are carried out in this order. Fig. 3 is a schematic diagram illustrating one embodiment of step (2) in the method for manufacturing a hollow structure. In the embodiment shown in Fig. 3, a hollow structure 200 is produced, which includes a substrate 10 having side walls 120Hw formed to surround interdigital electrodes, and a cured body 120H having a top plate portion 120Hr formed on the side walls 120Hw using a dry film so as to face the substrate 10.

[0193] Regarding operation (2-1): In operation (2-1), first, the cover film is removed from the dry film, and the laminated film 130 of the base film 110 and the negative photosensitive resin film 120 is placed on the side wall 120Hw so as to face the substrate 10 having the interdigital electrodes. At this time, the laminated film 130 is placed so that the negative photosensitive resin film 120 comes into contact with the upper surface of the side wall 120Hw. 3, the laminated film 130 is disposed so as to face the substrate 10 via the sidewall 120Hw. A hollow, sealed space is formed surrounded by the substrate 10, the sidewall 120Hw, and the negative photosensitive resin film 120.

[0194] Regarding operation (2-2): In operation (2-2), the base film 110 is peeled off from the negative photosensitive resin film 120 in the laminated film . Since the laminated film 130 includes the negative photosensitive resin film 120 according to the present embodiment described above, the base film 110 can be easily peeled off, providing excellent releasability.

[0195] Regarding steps (2-3) to (2-6): In operation (2-3), the negative photosensitive resin film 120 placed on the side wall 120Hw is selectively exposed (arrow) through a mask 60 (mask pattern) on which a predetermined pattern is formed, using a known exposure device.

[0196] Regarding operation (2-4): After the exposure operation in operation (2-3), the exposed negative photosensitive resin film 120 is subjected to a post-exposure bake (PEB) operation. By the post-exposure heating operation in operation (2-4), the negative photosensitive resin film 120 after exposure becomes an exposed portion 120B where the epoxy groups in the components (A1) and (A2) have undergone ring-opening polymerization, and an unexposed portion 120D where no change occurs.

[0197] Regarding operation (2-5): After the 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 the operation (2-5), the unexposed area 120D is dissolved and removed, forming a negative pattern (the exposed area 120B remains as an afterimage).

[0198] Regarding operation (2-6): After the development step in step (2-5), a heating (post-baking) step is carried out. The negative pattern (exposed portion 120B) after the development process 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. 3, a hardened body 120H is formed by integrating the sidewalls 120Hw and the top plate portion 120Hr through a heating operation. Then, a hollow structure 200 is produced in which interdigital electrodes are arranged in a hollow, sealed space surrounded by the substrate 10 and the hardened body 120H.

[0199] 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.

[0200] When producing the hollow structure of this embodiment, the negative photosensitive resin film of this embodiment described above is used in operations (1-2) and (2-2), so the base film is easily peeled from the negative photosensitive resin film in the laminated film, and the releasability when peeling the base film is excellent. In addition, in operations (1-1) and (2-1), the negative photosensitive resin film of the present embodiment described above is used, so when the dry film is replaced during the manufacture of the hollow structure, cracks are less likely to occur when the base film is wound up and cut from the dry film, and the generation of cutting debris is reduced. 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.

[0201] 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 the 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.

[0202] (Printed wiring board) One embodiment of a printed wiring board includes a substrate selected from the group consisting of a Si substrate, a SiO2 substrate, a SiN substrate, a Cu 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 to form an insulating layer of a printed wiring board, such as an interlayer insulating layer. When manufacturing the printed wiring board of this embodiment, since the negative photosensitive resin film of this embodiment described above is used, both releasability when peeling off the base film and suppression of cutting waste generation are achieved, thereby improving yield. In addition, since the negative photosensitive resin film of this embodiment described above is used, the lithography performance of the negative pattern is excellent, enabling high-precision processing. [Example]

[0203] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0204] <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.

[0205] [Table 1]

[0206] [Table 2]

[0207] In Tables 1 and 2, the abbreviations have the following meanings: The values ​​in brackets [ ] are the blending amounts of each component (parts by mass; solid content equivalent).

[0208] (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: 200-220 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: 39-46°C, epoxy equivalent: 200-220g / 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: 87-97°C, epoxy equivalent: 200-220g / 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.

[0209] [ka]

[0210] (A2)-1: A compound represented by the following chemical formula (A2-1). Product name: "Celloxide 2021P," manufactured by Daicel Corporation. Molecular weight: 252.31, epoxy equivalent: 120-140 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: 90-100 g / eq., viscosity (25°C): 0.310 Pa s (A2)-3: A compound represented by the following chemical formula (A2-3). Product name: "Epocalic THI-DE", manufactured by ENEOS Corporation. Molecular weight: 152.19, epoxy equivalent: 80-100 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: 80-100 g / eq., viscosity (25°C): 0.030 Pa s

[0211] [ka]

[0212] (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).

[0213] [ka]

[0214] (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)

[0215] <Preparation of laminated film> Each of the negative photosensitive compositions shown in Tables 1 and 2 was applied onto a substrate film using an applicator, and then 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 remaining solvent), and photosensitive laminate films were obtained. A 50 μm-thick polyethylene terephthalate (PET) film was used as the base film. The negative-type photosensitive compositions were the compositions (1-1) to (1-14) and the compositions (2-1) to (2-14). That is, a laminated film was obtained in which a 45 μm-thick negative-type photosensitive resin film was placed on a 50 μm-thick PET film.

[0216] [Measurement of the amount of solvent remaining in negative photosensitive resin film] The content of the solvent remaining in the negative photosensitive resin film constituting the laminate film (amount of remaining solvent) 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: Equipment: Agilent 6850 Column: Agilent J&W, DB-WAX, 30 m x 0.25 mm x 0.25 μm Sample volume: 1 microliter Helium flow rate: 132 mL / min Sample temperature: 250℃ Detector: Hydrogen flame ionization detector Measurement method: After the sample is placed in the container, it is held at 40°C for 5 minutes, then heated to 220°C at a rate of 10°C / min, and held at that temperature for 3 minutes before measurement.

[0217] <Evaluation> The laminated films prepared above were evaluated for releasability when peeling off the base film and suppression of generation of cutting debris as follows. The results are shown in Tables 3 and 4.

[0218] [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 with each other. After lamination, only the PET film directly on top of 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 and film peeling analyzer VPA-3 manufactured by Kyowa Interface Science Co., Ltd., under conditions of a load cell of 0.1 N and a peel angle of 90°. This peel strength (N) was used as an index to evaluate the releasability when peeling the base film.

[0219] [Reduction of cutting debris generation] The laminated film was placed on the cutting stage of TEAM-100ARF manufactured by Takatori Corporation so that the cutting stage surface was in contact with the negative photosensitive resin film. The film was cut to the wafer size using a film cutter heated to 60°C. The cut edge (cut surface) of the negative photosensitive resin film after cutting was observed under a microscope, and those that were cracked or broken were rated as NG, and those that were not cracked or broken were rated as OK to evaluate the ability to suppress the generation of cutting debris.

[0220] [Table 3]

[0221] [Table 4]

[0222] 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.

[0223] 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 mass % had a low peel strength of 0.01 N, but the cut edge portion (cut surface) was cracked and split. Furthermore, negative photosensitive resin films with a solvent content of more than 1.5% by mass relative to the total mass had a high peel strength of 0.1 N, while the cut edge (cut surface) was confirmed to be free of cracks and breakage.

[0224] 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.

[0225] In addition, from the results shown in Table 3, it can be confirmed that the negative-type photosensitive resin films of Examples 1 to 14, in which the mass ratio represented by solvent / photocationic polymerization initiator in the negative-type 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 of cracks and breakage.

[0226] 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 the cut edge portion (cut surface) was cracked. Furthermore, in negative photosensitive resin films where the mass ratio, expressed as solvent / photocationic polymerization initiator, exceeds 1.1, the peel strength is a high value of 0.1 N, while it can be confirmed that the cut edge portion (cut surface) is free of cracks and breakage.

[0227] 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. [Explanation of symbols]

[0228] 10 boards, 60 masks, 100 dry film, 110 base film, 120 negative photosensitive resin film, 120B exposure section, 120D unexposed area, 120H hardened body, 120Hw side wall, 120Hr top plate, 130 laminated film, 150 cover film, 200 Hollow structure

Claims

1. 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; A solvent, A negative photosensitive resin film comprising: 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 photosensitive resin film.

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

3. a substrate having an interdigital electrode, a side wall formed on the substrate so as to surround the interdigital electrode, and a top plate portion formed on the side wall so as to face the substrate, for use in manufacturing a hollow structure; The negative photosensitive resin film according to claim 1 or 2, which is used to form at least one of the side wall and the top plate portion.

4. 3. The negative photosensitive resin film according to claim 1, 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 laminate 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 substrate film, the negative photosensitive resin film according to claim 1 or 2, and a cover film laminated in this order on the substrate film.

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

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

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

Images