Negative photosensitive composition and method for producing hollow structure

Abstract

To provide a negative photosensitive composition and a method for producing a hollow structure, capable of preventing deformation of a top plate portion caused by heat treatment.SOLUTION: A negative photosensitive composition for forming a top plate portion of a hollow structure contains an epoxy group-containing compound, a cationic polymerization initiator, a polyfunctional (meth)acrylate compound, and a photoradical polymerization initiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive composition and a method for producing a hollow structure. This application claims priority based on Japanese Patent Application No. 2021-018152, filed on February 8, 2021, the contents of which are incorporated herein by reference. [Background technology]

[0002] In recent years, the development of microelectronic devices such as surface acoustic wave (SAW) filters has progressed. The packages that encapsulate such electronic devices have a hollow structure to ensure the propagation of surface acoustic waves and the mobility of the moving parts of the electronic devices. A photosensitive composition is used to form the hollow structure, and the package is manufactured by molding the wiring substrate on which the electrodes are formed while maintaining the hollow structure.

[0003] For example, Patent Document 1 discloses a method for manufacturing a hollow package, which includes a step of forming a cavity-reserving portion to cover a microelectromechanical system (MEMS) formed on a substrate to produce a hollow structure, and a step of sealing the entire hollow structure with a sealing layer by transfer molding. Patent Document 1 also discloses a negative-tone photosensitive composition containing an epoxy group-containing compound and a cationic polymerization initiator.

[0004] The cavity securing portion is formed as follows. After applying a photosensitive composition around the MEMS, sidewalls are created by exposing the composition through a photomask, post-exposure baking (PEB), and developing. Next, the cover film is peeled off from the dry film resist, which is made by laminating a base film, a photosensitive composition layer, and a cover film in this order, and the resulting resist is laminated above the side wall to form a top plate portion. Exposure, PEB, and development are then performed again through a photomask, and unnecessary portions are removed to create the top plate portion, thereby forming a cavity securing portion. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2009 / 151050 Summary of the Invention [Problem to be solved by the invention]

[0006] When producing a hollow structure, generally, in order to increase the strength of the cured film of the photosensitive composition layer, the cavity-reserving portion after development is further subjected to a high-temperature heat treatment (curing operation) at, for example, 200° C. or higher. The heat treatment for PEB and the high-temperature heat treatment for the curing operation when producing a hollow structure may cause the air inside the hollow structure to expand, resulting in a phenomenon known as doming, in which the top plate portion swells. When a conventional negative-type photosensitive composition, such as the negative-type photosensitive composition described in Patent Document 1, is used as a top plate portion of a hollow structure, a doming phenomenon occurs depending on the composition balance, which makes it difficult to reduce the height of an electronic component having a hollow structure.

[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 composition and a method for producing a hollow structural body, which are capable of suppressing deformation of the top plate portion due to heat treatment. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a negative photosensitive composition for forming a top plate portion of a hollow structure, which contains an epoxy group-containing compound, a cationic polymerization initiator, a polyfunctional (meth)acrylate compound, and a photoradical polymerization initiator. In other words, a first aspect of the present invention is the use of a negative-type photosensitive composition containing an epoxy group-containing compound, a cationic polymerization initiator, a polyfunctional (meth)acrylate compound, and a photoradical polymerization initiator to form a top plate portion of a hollow structure.

[0009] A second aspect of the present invention is a method for manufacturing a hollow structure comprising a recess and a top plate portion covering the opening of the recess, wherein the top plate portion is formed using the negative-type photosensitive composition according to the first aspect. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a negative photosensitive composition and a method for producing a hollow structural body, in which deformation of the top plate due to heat treatment is suppressed. [Brief explanation of the drawings]

[0011] [Figure 1] 1A to 1C are schematic diagrams illustrating a method for manufacturing a hollow structure according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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 the 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.

[0013] (Negative Photosensitive Composition) The negative photosensitive composition of the present embodiment (hereinafter may be simply referred to as the "photosensitive composition") contains an epoxy group-containing compound (A) (hereinafter may be referred to as the "component (A)"), a polyfunctional (meth)acrylate compound (B) (hereinafter may be referred to as the "component (B)"), a photoradical polymerization initiator (C) (hereinafter may be referred to as the "component (C)"), and a cationic polymerization initiator (I) (hereinafter may be referred to as the "component (I)"). When a photosensitive resin film is formed using such a photosensitive composition and selectively exposed to light, the cationic moiety of component (I) decomposes in the exposed areas of the photosensitive resin film to generate an acid, which then causes ring-opening polymerization of the epoxy groups in component (A), reducing the solubility of component (A) in a developer containing an organic solvent. Meanwhile, the solubility of component (A) in a developer containing an organic solvent remains unchanged in the unexposed areas of the photosensitive resin film, resulting in a difference in solubility in a developer containing an organic solvent between the exposed and unexposed areas of the photosensitive resin film. Therefore, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed areas are dissolved and removed, forming a negative pattern.

[0014] <Epoxy group-containing compound (A)> The epoxy group-containing compound (component (A)) may be a compound having enough epoxy groups in one molecule to form a negative pattern upon exposure. Examples of the component (A) used in the photosensitive composition of this embodiment include novolac epoxy resins, bisphenol epoxy resins, aliphatic epoxy resins, and acrylic resins.

[0015] <Novolac epoxy resin> Suitable examples of novolac epoxy resins (hereinafter also referred to as "component (A1)") include epoxy resins represented by the following general formula (anv0).

[0016] [ka] [In the formula, 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.

[0017] In the formula (anv0), R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. 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 (anv0), multiple R p1 may be the same or different. p2 may be the same as or different from each other.

[0018] In the formula (anv0), n1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0019] In the formula (anv0), 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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, further 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 alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0025] 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.

[0026] 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-.

[0027] 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.

[0028] 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.

[0029] 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 0 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 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, in 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.

[0030] Among them, R EP The epoxy group-containing group in is preferably a glycidyl group.

[0031] Additionally, suitable examples of the component (A1) include resins having a structural unit represented by the following general formula (anv1):

[0032] [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.

[0033] In the formula (anv1), R a22 , R a23 The alkyl group having 1 to 5 carbon atoms is R p1 , R p2 The alkyl group 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 is R in the above formula (anv0). EP and a glycidyl group is preferred.

[0034] Specific examples of the constitutional unit represented by the formula (anv1) are shown below.

[0035] [ka]

[0036] The component (A1) may be a resin consisting solely of the structural unit (anv1), or it may be a resin containing the structural unit (anv1) in addition to other structural units. Examples of other structural units include structural units represented by the following general formulas (anv2) to (anv3).

[0037] [ka] [In the formula, R a24 R is a hydrocarbon group which may have a substituent. a25 ~R a26 , R a28 ~R a30R 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.

[0038] 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, and even more preferably 1 or 2. 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.

[0039] 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.

[0040] 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 is preferably one having 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0041] 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 a24 Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (an aryl group or a heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 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, and particularly preferably 1.

[0042] 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:

[0043] 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:

[0044] Specific examples of the structural units represented by the formulae (anv2) to (anv3) are shown below.

[0045] [ka]

[0046] 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 %.

[0047] Commercially available products of the component (A1) include, for example, novolac epoxy resins such as 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 (all manufactured by Nippon Kayaku Co., Ltd.), and YDCN-704 (manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0048] As the component (A1), one type may be used alone, or two or more types may be used in combination.

[0049] <Bisphenol-type epoxy resin> The bisphenol-type epoxy resin (hereinafter also referred to as "component (A2)") may be any resin having a structural unit containing a bisphenol skeleton, and among these, solid bisphenol-type epoxy resins are preferred. The solid bisphenol epoxy resin refers to a resin that is solid at 25°C and has a structural unit containing a bisphenol skeleton. The epoxy equivalent of the component (A2) is, for example, preferably 800 g / eq. or more, more preferably 800 to 1200 g / eq., and even more preferably 900 to 1100 g / eq.

[0050] Suitable examples of the component (A2) include epoxy resins represented by the following general formula (abp1):

[0051] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different. a31 and R a32 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. 31 is an integer between 1 and 50.

[0052] In the formula (abp1), R EP is R in the above formula (anv0). EP and a glycidyl group is preferred. In the formula (abp1), R a31 , R a32 The alkyl group having 1 to 5 carbon atoms in the formula (anv0) is R p1 , R p2 The alkyl groups having 1 to 5 carbon atoms are the same as those in the above. a31 , Ra32 are each preferably a hydrogen atom or a methyl group. R a31 , R a32 The fluorinated alkyl group having 1 to 5 carbon atoms in a31 , R a32 Examples of such groups include groups in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with fluorine atoms. In the formula (abp1), na 31 is an integer of 1 to 50, preferably an integer of 4 to 15, and more preferably an integer of 5 to 8.

[0053] Examples of commercially available products that can be used as component (A2) include JER-4005, JER-4007, and JER-4010 (all manufactured by Mitsubishi Chemical Corporation); JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, and JER-1010 (all manufactured by Mitsubishi Chemical Corporation); and EPICLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (all manufactured by DIC Corporation).

[0054] As the component (A2), one type may be used alone, or two or more types may be used in combination.

[0055] <Aliphatic epoxy resin> Suitable examples of aliphatic epoxy resins include compounds represented by the following general formula (ta1) (hereinafter, this compound may also be referred to as "component (A3)"):

[0056] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different from each other.

[0057] In the formula (ta1), R EPis an epoxy group-containing group, and R in the formula (anv0) EP is the same as:

[0058] Commercially available products that can be used as the component (A3) include, for example, the TEPIC series (manufactured by Nissan Chemical Industries, Ltd.), such as TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, and TEPIC-UC; and MA-DGIC, DA-MGIC, and TOIC (manufactured by Shikoku Chemical Industries, Ltd.).

[0059] As the component (A3), one type may be used alone, or two or more types may be used in combination.

[0060] The aliphatic epoxy resin also includes a compound containing a partial structure represented by the following general formula (m1) (hereinafter also referred to as "component (m1)").

[0061] [ka] [In the formula, n2 is an integer of 1 to 4. * indicates a bond.]

[0062] In the formula (m1), n2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0063] Examples of the component (m1) include compounds in which a plurality of partial structures represented by the general formula (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 (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, and a divalent linking group containing a hetero atom. Here, the divalent hydrocarbon group which may have a substituent and the divalent linking group which contains a hetero atom are represented by R in the above formula (anv0). EPThe divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are the same as those described 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 21 A 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.

[0064] Commercially available aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (manufactured by ADEKA Corporation); CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (manufactured by Daicel Corporation); and DENACOL EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation).

[0065] <Acrylic resin> Examples of the acrylic resin include resins having epoxy group-containing units represented by the following general formulas (a1-1) and (a1-2).

[0066] [ka] [wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. 41 is a divalent hydrocarbon group which may have a substituent. 41 is an integer between 0 and 2. a41 and R a42 are epoxy group-containing groups. 42 is 0 or 1. 41is (na 43 +1)valent aliphatic hydrocarbon group. 43 is an integer between 1 and 3.

[0067] In the formula (a1-1), the alkyl group having 1 to 5 carbon atoms for R is preferably linear or branched, and specific examples thereof 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. The halogenated alkyl group having 1 to 5 carbon atoms in R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

[0068] In the formula (a1-1), Va 41 is a divalent hydrocarbon group which may have a substituent, and R in the formula (anv0) EP Examples of the divalent hydrocarbon groups include the same groups as those explained in the above section, which may have a substituent. Among the above, Va 41 The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, still more preferably a linear aliphatic hydrocarbon group, and particularly preferably a linear alkylene group.

[0069] In the formula (a1-1), na 41 is an integer of 0 to 2, with 0 or 1 being preferred.

[0070] In the above formulas (a1-1) and (a1-2), R a41 , R a42 is an epoxy group-containing group, and R in the formula (anv0) EP is the same as:

[0071] In the formula (a1-2), Wa 41 In (na 43 The aliphatic hydrocarbon group having a valence of +1 means a hydrocarbon group that is not aromatic and may be saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, and a group formed by combining a linear or branched aliphatic hydrocarbon group with an aliphatic hydrocarbon group containing a ring in its structure.

[0072] In the formula (a1-2), na 43 is an integer of 1 to 3, with 1 or 2 being preferred.

[0073] Specific examples of the structural unit represented by the formula (a1-1) or (a1-2) are shown below. In the following formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R a51 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. a52 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. a53 represents a hydrogen atom or a methyl group. 51 is an integer between 0 and 10. R a51 , R a52 , R a53 may be the same or different.

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] Furthermore, the acrylic resin may contain structural units derived from other polymerizable compounds in order to appropriately control the physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; hydroxyalkyl (meth)acrylate ... Examples of suitable polymerizable compounds include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[0079] When the acrylic resin has other structural units, the content of the epoxy group-containing units in the resin is preferably 5 to 40 mol %, more preferably 10 to 30 mol %, and even more preferably 15 to 25 mol %.

[0080] The acrylic resin may be used alone or in combination of two or more kinds.

[0081] <Other epoxy group-containing compounds> As the epoxy group-containing compound other than those mentioned above, for example, a resin having a glycidyl ether group in its structure can be used. In addition to the resins described above, the component (A) may also include a compound represented by the following chemical formula (A3-1): Commercially available products that can be used as the compound represented by the following chemical formula (A3-1) include TECHMORE VG-3101L (manufactured by Printec Co., Ltd.), for example.

[0082] [ka]

[0083] In addition to the resins mentioned above, the component (A) may also include a compound represented by the following chemical formula (A3-2).

[0084] [ka]

[0085] Furthermore, examples of epoxy group-containing compounds other than component (A) include 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.

[0086] The content of the component (A) in the photosensitive composition of the embodiment may be adjusted depending on the film thickness of the photosensitive resin film to be formed. For example, in the photosensitive composition of this embodiment, the content of component (A) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 85% by mass or more, relative to 100 parts by mass of the total content of components (A) and (B).

[0087] <Polyfunctional (meth)acrylate compound (B)> The polyfunctional (meth)acrylate compound (component (B)) is a photopolymerizable polyfunctional monomer having a polymerizable functional group. The term "polymerizable functional group" refers to a group that enables compounds to be polymerized by radical polymerization or the like, and is, for example, a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond. Also, as used herein, "multifunctional" means having two or more functional groups. Multifunctional monomers can be, for example, difunctional, trifunctional, tetrafunctional, or can have even more functional groups. For example, multifunctional acrylates include diacrylates, triacrylates, and tetraacrylates. Also, multifunctional methacrylates include dimethacrylates, trimethacrylates, and tetramethacrylates.

[0088] Examples of the polymerizable functional group include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a trifluoroallyl group, a perfluoroallyl group, a trifluoromethylacryloyl group, a nonylfluorobutylacryloyl group, a vinyl ether group, a fluorine-containing vinyl ether group, an allyl ether group, a fluorine-containing allyl ether group, a styryl group, a vinyl naphthyl group, a fluorine-containing styryl group, a fluorine-containing vinyl naphthyl group, a norbornyl group, a fluorine-containing norbornyl group, a silyl group, etc. Among these, a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group are preferred, and an acryloyl group and a methacryloyl group are more preferred.

[0089] [Bifunctional monomer] Examples of bifunctional monomers include alkoxylated aliphatic diacrylates, alkoxylated aliphatic dimethacrylates, alkoxylated neopentyl glycol diacrylates, alkoxylated neopentyl glycol dimethacrylates, 1,4-butanediol diacrylates, 1,4-butanediol dimethacrylates, 1,3-butylene glycol diacrylates, 1,3-butylene glycol dimethacrylates, cyclohexanedimethanol diacrylates, cyclohexanedimethanol dimethacrylates, diethylene glycol diacrylates, diethylene glycol dimethacrylates, dipropylene glycol diacrylates, dipropylene glycol dimethacrylates, 1,12-dodecanediol dimethacrylates, and the like. Bisphenol A dimethacrylate, ethoxylated (2) Bisphenol A dimethacrylate, ethoxylated (3) Bisphenol A diacrylate, ethoxylated (4) Bisphenol A diacrylate, ethoxylated (4) Bisphenol A dimethacrylate, ethoxylated (6) Bisphenol A dimethacrylate, ethoxylated (8) Bisphenol A dimethacrylate, ethoxylated (10) Bisphenol A diacrylate, ethoxylated (10) Bisphenol A dimethacrylate, ethoxylated (30) Bisphenol A diacrylate, ethoxylated (30) Bisphenol A dimethacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyester diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (400) dimethacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (600) dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol (400) dimethacrylate, propoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol dimethacrylate, propoxylated (2) neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, and tripropylene glycol dimethacrylate, and combinations thereof.

[0090] Commercially available bifunctional monomers include, for example, Light Acrylate 3EG-A, 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EAL, and BP-4PA (all manufactured by Kyoeisha Chemical Co., Ltd.).

[0091] [Trifunctional or higher polyfunctional monomers] Examples of photopolymerizable compounds having three or more polymerizable functional groups include photopolymerizable siloxane compounds, photopolymerizable silsesquioxane compounds, and polyfunctional monomers having three or more polymerizable functional groups.

[0092] Examples of photopolymerizable siloxane compounds include compounds having an alkoxysilyl group and a polymerizable functional group in the molecule. Commercially available photopolymerizable siloxane compounds include those manufactured by Shin-Etsu Chemical Co., Ltd. under the product names "KR-513," "X-40-9296," "KR-511," "X-12-1048," and "X-12-1050."

[0093] The photopolymerizable silsesquioxane compound includes a compound having a main chain structure composed of Si-O bonds and having the following chemical formula: [(RSiO 3 / 2 ) n In the formula, R represents an organic group, and n represents a natural number. R represents a monovalent organic group, and examples of the monovalent organic group include monovalent hydrocarbon groups which may have a substituent. Examples of this hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, with alkyl groups having 1 to 12 carbon atoms being preferred. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a benzyl group, a tolyl group, and a styryl group. Examples of the substituent that the monovalent hydrocarbon group may have include a (meth)acryloyl group, a hydroxy group, a sulfanyl group, a carboxy group, an isocyanato group, an amino group, a ureido group, etc. Furthermore, -CH- contained in the monovalent hydrocarbon group may be replaced with -O-, -S-, a carbonyl group, etc. However, the photopolymerizable silsesquioxane compound has three or more polymerizable functional groups, such as vinyl, allyl, methacryloyl, and acryloyl groups.

[0094] Chemical formula: [(RSiO 3 / 2 ) n The compound represented by the formula (I) may be any of a cage type, a ladder type, and a random type. The cage type silsesquioxane compound may be a complete cage type or an incomplete cage type in which the cage is partially open.

[0095] Commercially available photopolymerizable silsesquioxane compounds include, for example, products manufactured by Toagosei Co., Ltd. under the names "MAC-SQ LP-35," "MAC-SQ TM-100," "MAC-SQ SI-20," and "MAC-SQ HDM."

[0096] Examples of polyfunctional monomers having three or more polymerizable functional groups include ethoxylated (3) trimethylolpropane triacrylate, ethoxylated (3) trimethylolpropane trimethacrylate, ethoxylated (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, ethoxylated (15) trimethylolpropane triacrylate, ethoxylated (20) trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, propoxylated (3) glyceryl triacrylate, propoxylated (3) glyceryl triacrylate, propoxylated (5.5) glyceryl triacrylate, propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) trimethylolpropane triacrylate, and trimethylolpropane triacrylate. Examples of the monomer include trifunctional monomers such as propane triacrylate, trimethylolpropane trimethacrylate, tris-(2-hydroxyethyl)-isocyanurate triacrylate, tris-(2-hydroxyethyl)-isocyanurate trimethacrylate, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, and EO,PO-modified trimethylolpropane tri(meth)acrylate; tetrafunctional monomers such as ditrimethylolpropane tetraacrylate, ethoxylated (4) pentaerythritol tetra(meth)acrylate; and pentafunctional or higher monomers such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

[0097] Other than the above-mentioned polyfunctional monomers, hexafunctional monomers and the like can also be used as appropriate within the scope of the effects of the present invention. For example, the compound represented by the following chemical formula (B-1) may be used as the component (B).

[0098] [ka]

[0099] Examples of commercially available products of the polyfunctional monomer include those manufactured by Shin-Nakamura Chemical Co., Ltd. under the product names "A-9300-1CL," "AD-TMP," "A-9550," and "A-DPH," those manufactured by Nippon Kayaku Co., Ltd. under the product name "KAYARAD DPHA," and those manufactured by Kyoeisha Chemical Co., Ltd. under the product name "Light Acrylate TMP-A."

[0100] In the photosensitive composition of this embodiment, the component (B) may be used alone or in combination of two or more. In the photosensitive composition of this embodiment, the component (B) is preferably a tri- or tetrafunctional monomer.

[0101] The content of the component (B) is preferably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 5 to 15 parts by mass, per 100 parts by mass of the total content of the components (A) and (B). When the content of component (B) is equal to or greater than the lower limit of the above-mentioned preferred range, the cured resin film formed using the photosensitive composition has good curability and flowability, whereas when the content of component (B) is equal to or less than the upper limit of the above-mentioned preferred range, the dispersibility of the photosensitive composition is good.

[0102] <Photoradical polymerization initiator (C)> Component (C) is a photopolymerization initiator. The component (C) is a compound that initiates or accelerates polymerization of the component (B) upon exposure to light, and is preferably a photoradical polymerization initiator.

[0103] Examples of the component (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2- Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate , butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl Thioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-Bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone Phenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane , 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]- 4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine; ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanone peroxide; diacyl peroxides such as isobutyryl peroxide and bis(3,5,5-trimethylhexanoyl) peroxide; hydroperoxides such as p-menthane hydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide; 2,5-dimethyl-2,5-bis(t-butyl Examples of suitable peroxy compounds include dialkyl peroxides such as 1,1-bis(t-butylperoxy)hexane; peroxyketals such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane; peroxyesters such as t-butylperoxyneodecanoate and 1,1,3,3-tetramethylperoxyneodecanoate; peroxydicarbonates such as di-n-propylperoxydicarbonate and diisopropylperoxydicarbonate; azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobisisobutyrate; and acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0104] Among the above, preferred are initiators that do not contain a nitrogen atom, such as benzophenone-based initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-2-phenylacetophenone; and acylphosphine oxide-based initiators such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0105] As the component (C), a commercially available product can be used. Commercially available products of component (C) include those manufactured by IGM Resins BV under the product names "Omnirad 184," "Omnirad 651," "Omnirad 819," and "Omnirad TPO."

[0106] In the photosensitive composition of the present embodiment, the component (C) may be used alone or in combination of two or more.

[0107] The content of component (C) is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and even more preferably 0.5 to 25 parts by mass, per 100 parts by mass of component (B). When the content of component (C) is within the above-mentioned preferred range, the photocurability of the photosensitive composition is good.

[0108] <Cationic Polymerization Initiator (I)> The cationic polymerization initiator (component (I)) 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 these cations can serve as polymerization initiators. Examples of the component (I) used in the photosensitive composition of this embodiment include onium borate salts, onium salts containing phosphorus-based anions, sulfonate salts, and carboxylate salts.

[0109] Onium borate salts Onium borate salts (hereinafter also referred to as "component (I1)") generate a relatively strong acid upon exposure. Therefore, by forming a pattern using a photosensitive composition containing component (I1), sufficient sensitivity can be obtained, resulting in the formation of a good pattern. Furthermore, the use of component (I1) also reduces the risk of toxicity and metal corrosion. Suitable examples of the component (I1) include compounds represented by the following general formula (I1).

[0110] [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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] [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.

[0115] 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):

[0116] [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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] Among them, R' 201 is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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) 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.

[0132] 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).

[0133] [ka]

[0134] [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

[0135] 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.

[0136] [ka]

[0137] [ka] [In the formula, R' 211 is an alkyl group. hal is a hydrogen atom or a halogen atom.

[0138] 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.

[0139] [ka]

[0140] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0141] 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).

[0142] [ka]

[0143] 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).

[0144] [ka]

[0145] 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.

[0146] [ka] [In the formula, R' 212 R' is an alkyl group or a hydrogen atom. 211 is an alkyl group.

[0147] 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-1-48), and even more preferably a cation represented by formula (ca-1-25), (ca-1-29), (ca-1-35), (ca-1-47), or (ca-1-48).

[0148] Specific examples of suitable components (I1) are listed below: Among the specific examples shown below, components (I1) represented by the following general formulae (I1-1) and (I1-2) are more preferred.

[0149] [ka]

[0150] As the component (I1), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition of this embodiment, the content of component (I1) is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, and even more preferably 0.5 to 2.0 parts by mass, relative to 100 parts by mass of the total content of the epoxy group-containing compound (component (A)) and the polyfunctional (meth)acrylate compound (component (B)). When the content of component (I1) is equal to or greater than the lower limit of the above-mentioned preferred range, sufficient sensitivity is obtained, and the lithography characteristics of the pattern are further improved. In addition, the strength of the cured film is further increased. On the other hand, when the content is equal to or less than the upper limit of the above-mentioned preferred range, the sensitivity is appropriately controlled, and a pattern with a good shape is easily obtained.

[0151] <Onium salt containing phosphorus-based anion> An example of an onium salt containing a phosphorus-based anion is a compound represented by the following general formula (I2) (hereinafter referred to as "component (I2)").

[0152] Regarding the compound represented by general formula (I2) (component (I2)): The component (I2) is a compound represented by the following general formula (I2). The component (I2) generates a relatively strong acid upon exposure to light, and therefore, when a pattern is formed using a photosensitive composition containing the component (I), sufficient sensitivity is obtained and a good pattern is formed.

[0153] [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.

[0154] Anion section In the formula (I2), 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 b05 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 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.

[0155] The anion moiety of the compound represented by formula (I2) is preferably represented by the following general formula (b0-2a).

[0156] [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.

[0157] 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.

[0158] Cation part In formula (I2), 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 these, cations represented by general formula (ca-1) are preferred, with cations represented by formulas (ca-1-1) to (ca-1-48) being more preferred, and cations represented by formula (ca-1-25), (ca-1-29), (ca-1-35), and (ca-1-47) being even more preferred.

[0159] Specific examples of suitable components (I2) are listed below: Among the specific examples shown below, components (I2) represented by the following general formula (I2-1-1) are more preferred.

[0160] [ka]

[0161] <Sulfonates, carboxylates> Examples of sulfonates include compounds represented by the following general formula (I3-1). Examples of carboxylates include compounds represented by the following general formula (I3-2). Hereinafter, the compounds represented by general formula (I3-1) or (I3-2) will be collectively referred to as "component (I3)".

[0162] [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.

[0163] {Component (I3-1)} Anion section In formula (I3-1), Rb12 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, 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. 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 the substituent may be 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).

[0164] Preferred examples of the anion moiety of the component (I3-1) are shown below.

[0165] [ka]

[0166] 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.

[0167] {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' 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.

[0168] 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.

[0169] [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.]

[0170] 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.

[0171] V' 101 and V' 102The 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' 102 Specific 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.

[0172] 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.

[0173] 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.

[0174] [ka]

[0175] 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:

[0176] Furthermore, from the viewpoints of increasing the elasticity of the resin film and facilitating the formation of a fine structure without residue, the component (I) is preferably a cationic polymerization initiator that generates an acid with a pKa (acid dissociation constant) of -5 or less upon exposure. By using a cationic polymerization initiator that generates an acid with a pKa of more preferably -6 or less, and even more preferably -8 or less, it becomes possible to obtain high sensitivity to exposure. The lower limit of the pKa of the acid generated by the component (I) is preferably -15 or more. By using a cationic polymerization 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.

[0177] Specific examples of suitable components (I3) are listed below.

[0178] [ka]

[0179] In the photosensitive composition of this embodiment, the component (I) contains the component (I1). Suitable examples of the component (I) include those consisting of the component (I1) alone and those containing the component (I1) and the component (I2).

[0180] In the photosensitive composition of this embodiment, the total content of the component (I) is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total content of the component (A) and the component (B). 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 cured film is further increased. On the other hand, when the content is equal to or less than the upper limit of the preferred range, sensitivity is appropriately controlled, and a pattern with a good shape is easily obtained.

[0181] <Other ingredients> The photosensitive composition of the present embodiment may contain other components as needed in addition to the above-described components (A), (B), (C), and (I). If desired, the photosensitive composition of the embodiment may contain miscible additives, such as a metal oxide (M), a silane coupling agent, a sensitizer component, a solvent, an additional resin for improving the performance of the film, a dissolution inhibitor, a basic compound, a plasticizer, a stabilizer, a colorant, and an antihalation agent.

[0182] <Metal oxides (M)> In addition to components (A), (B), (C), and (I), the photosensitive composition of this embodiment may further contain a metal oxide (M) (hereinafter also referred to as "component (M)"), since this facilitates the formation of a cured film with increased strength. Furthermore, the inclusion of component (M) also makes it possible to form a high-resolution pattern with a good shape. Examples of the component (M) include oxides of metals such as silicon (metallic silicon), titanium, zirconium, hafnium, etc. Among these, oxides of silicon are preferred, and among these, it is particularly preferred to use silica.

[0183] Furthermore, the component (M) is preferably in the form of particles. Such particulate component (M) preferably comprises a particle group having a volume average particle diameter of 5 to 40 nm, more preferably a particle group having a volume average particle diameter of 5 to 30 nm, and even more preferably a particle group having a volume average particle diameter of 10 to 20 nm. When the volume average particle diameter of component (M) is equal to or greater than the lower limit of the preferred range, the strength of the cured film tends to be increased. On the other hand, when the volume average particle diameter is equal to or less than the upper limit of the preferred range, residues are less likely to be generated during pattern formation, making it easier to form higher-resolution patterns. In addition, the transparency of the resin film is improved. The particle size of component (M) may be appropriately selected depending on the exposure light source. Generally, it is considered that particles having a particle size of 1 / 10 or less of the wavelength of light are hardly affected by light scattering. For this reason, when forming a fine structure by photolithography using i-line (365 nm), for example, it is preferable to use particles (particularly preferably silica particles) with a primary particle size (volume average) of 10 to 20 nm as component (M).

[0184] Commercially available products of the component (M) include, for example, trade names "MEK-EC-2130Y" and "MEK-AC-2140-Z" manufactured by Nissan Chemical Industries, Ltd.

[0185] As the component (M), one type may be used alone, or two or more types may be used in combination. When the (M) component is contained, the content thereof is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and particularly preferably 20 to 30 parts by mass, relative to 100 parts by mass of the total content of the (A) component and the (B) component. When the content of component (M) is at least the lower limit of the above-mentioned preferred range, the strength of the cured film is further increased, whereas when the content is at most the upper limit of the above-mentioned preferred range, the transparency of the resin film is further increased.

[0186] <Silane coupling agents> The photosensitive composition of this embodiment may further contain an adhesion promoter to improve adhesion to the substrate, and a silane coupling agent is preferred as the adhesion promoter. 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-glycidoxypropyltrimethoxysilane, 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 0.1 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total content of the (A) component and the (B) component. 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.

[0187] <Sensitizer ingredient> The photosensitive composition of this embodiment may further contain a sensitizer component. The sensitizer component is not particularly limited as long as it can absorb energy from exposure and transfer that energy to another substance. Specific examples of the sensitizer component that can be used include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetophenone-based photosensitizers, naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, and known photosensitizers such as biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone. The sensitizer component may be used alone or in combination of two or more. When a sensitizer component is included, the content thereof is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (A). When the content of the sensitizer component is within the above-mentioned preferred range, the sensitivity and resolution can be further improved.

[0188] <Solvent> The photosensitive composition of this embodiment may further contain a solvent (hereinafter sometimes referred to as "component (S)"). Examples of the component (S) 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; monoalkyl ethers or monoalkyl ethers of the above polyhydric alcohols or the above compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether; Examples of suitable organic solvents include derivatives of polyhydric alcohols such as compounds having an ether bond, such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane; and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethyl sulfoxide (DMSO).

[0189] The component (S) may be used alone or as a mixed solvent of two or more types.

[0190] When component (S) is contained, the amount used is not particularly limited, and is set appropriately depending on the thickness of the coating film at a concentration that allows the photosensitive composition to be applied to a substrate or the like without dripping. For example, the (S) component can be used so that the solid content concentration is 50% by mass or more, and the (S) component can be used so that the solid content concentration is 60% by mass or more. It is also possible to employ an embodiment in which the component (S) is substantially not contained (that is, an embodiment in which the solid content concentration is 100% by mass).

[0191] The negative photosensitive composition of the present embodiment described above contains an epoxy group-containing compound (A), a polyfunctional (meth)acrylate compound (B), a photoradical polymerization initiator (C), and a cationic polymerization initiator (I).

[0192] Conventionally known negative photosensitive compositions for forming the top plate portion of a hollow structure, which are composed of an epoxy group-containing compound (A) and a cationic polymerization initiator (I), have a problem in that the film-like top plate portion is easily deformed by the heat treatment of PEB or the high-temperature heat treatment of the curing operation. In the negative-tone photosensitive composition of this embodiment, a polyfunctional (meth)acrylate compound (B) and a photoradical polymerization initiator (C) are further added to a negative-tone photosensitive composition containing an epoxy group-containing compound (A) and a cationic polymerization initiator (I). The epoxy group-containing compound (A) undergoes a crosslinking reaction with the cationic polymerization initiator (I), and the polyfunctional (meth)acrylate compound (B) undergoes a polymerization reaction with the photoradical polymerization initiator (C). Each reaction complicates the skeleton of the cured body that constitutes the top plate, improving thermal deformation resistance and suppressing doming due to deformation caused by heat during curing.

[0193] The negative photosensitive composition of this embodiment is useful as a material for forming a top plate portion of a hollow structure in an electronic component. An example of a hollow structure in an electronic component is a hollow structure consisting of a recess and a top plate portion that closes the opening of the recess, as exemplified in the description of (Method for manufacturing a hollow structure) below.

[0194] Furthermore, the negative photosensitive composition of this embodiment further contains silica nanoparticles, which improves the elastic modulus, thereby further suppressing deformation due to heating during curing.

[0195] (Photosensitive resist film) The photosensitive resist film of this embodiment is obtained by laminating, in this order, a photosensitive resin film formed using the photosensitive composition of the above-described embodiment and a cover film on a substrate film.

[0196] The photosensitive resist film of this embodiment can be produced, for example, by applying the photosensitive composition of the above-described embodiment onto a substrate film, drying it to form a photosensitive resin film, and then laminating a cover film on the photosensitive resin film. The photosensitive 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. The thickness of the photosensitive resin film is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0197] 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.

[0198] The cover film may be a known film, such as a polyethylene film, a polypropylene film, etc. The cover film is preferably a film that has a smaller adhesive strength with the photosensitive resin film than the base 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.

[0199] (Method for manufacturing hollow structure) The method for manufacturing a hollow structure of this embodiment is a method for manufacturing a hollow structure consisting of a recess and a top plate portion that covers the opening surface of the recess, and the top plate portion is formed using the above-mentioned negative photosensitive composition. FIG. 1 is a schematic diagram illustrating a method for manufacturing a hollow structure according to this embodiment. The illustrated method for manufacturing a hollow structure includes a step (first step (S1)) of forming a side wall on a substrate, and a step (second step (S2)) of forming a top plate portion on the side wall to fabricate the hollow structure. The first step (S1) and the second step (S2) will be described in detail below.

[0200] [First step (S1)] In the first step, side walls 20 are formed on a substrate 10 to obtain a substrate 10 having recesses 15 on its surface. In the [First Step] of FIG. 1, the substrate 10 and the sidewalls 20 formed on the substrate 10 are shown, which form a recess 15 on the surface.

[0201] <Substrates with recesses on the surface> Examples of the substrate 10 having the recesses 15 on its surface include a structure in which a pattern is formed on the substrate 10, a stepped substrate, etc. The recesses 15 may be made of either an organic material or an inorganic material. Such a substrate 10 having recesses 15 on its surface can be produced by a method including the steps of forming a photosensitive resin film on a support using a negative photosensitive composition (hereinafter referred to as a "film formation step"), exposing the photosensitive resin film to light (hereinafter referred to as an "exposure step"), and developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern that becomes sidewalls 20 of the recesses 15 (hereinafter referred to as a "development step"). The method for producing such a substrate 10 having recesses 15 on its surface can be performed as follows.

[0202] Film formation process: First, a negative photosensitive composition is applied onto a support by a known method such as spin coating, roll coating, or screen printing, and then baked (post-applied bake (PAB)) for 2 to 60 minutes at a temperature of 50 to 150°C to form a photosensitive resin film. The film forming step can also be carried out by disposing a photosensitive composition layer, which has been prepared in advance using a negative photosensitive composition, on a support.

[0203] The support is not particularly limited, and any conventionally known support can be used, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. More specifically, examples of substrates for electronic components include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. The wiring pattern may be made of a material such as copper, aluminum, nickel, or gold.

[0204] The thickness of the photosensitive resin film formed from the negative photosensitive composition is not particularly limited, but is preferably about 10 to 100 μm.

[0205] Exposure process: Next, the formed photosensitive resin film is selectively exposed using a known exposure device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by drawing using direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) as needed, for example, at a temperature of 80 to 150°C for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds.

[0206] 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 refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc. For example, when an ultra-high pressure mercury lamp is used, it is 100 to 2000 mJ / cm. 2 is.

[0207] The exposure method for the photosensitive resin film may be a normal exposure (dry exposure) carried out in air or an inert gas such as nitrogen, or may be liquid immersion lithography.

[0208] Development process: Next, the exposed photosensitive resin film is developed with a developer containing an organic solvent (organic developer). After development, a rinse treatment is preferably performed. If necessary, a bake treatment (post-bake) may be performed.

[0209] 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.

[0210] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), etc. Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0211] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples of the alkyl esters include ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate.Among these, butyl acetate or PGMEA is preferred as the ester solvent.

[0212] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0213] 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.

[0214] 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).

[0215] The rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method, such as a method in which the rinse solution is continuously applied onto a support rotating at a constant speed (spin coating method), a method in which the support is immersed in the rinse solution for a certain period of time (dipping method), or a method in which the 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.

[0216] By the above-described film forming step, exposure step, and development step, a substrate 10 having recesses 15 on its surface (a structure in which a pattern is formed on a substrate, a stepped substrate) can be manufactured. The thickness (horizontal dimension relative to the support) and height (vertical dimension relative to the support) of the side wall 20 can be set appropriately based on the size of the hollow portion, which is determined according to the type of electronic device to be accommodated in the recess 15.

[0217] [Second process (S2)] In the second step of this embodiment, an exposed portion 30A that will become a top plate portion is formed on the side wall 20 formed in the first step, thereby producing the hollow structural body. The second step in this embodiment includes the following steps (i), (ii), (iii), (iv), and (v).

[0218] Step (i): A step of disposing the photosensitive resist film 30F so that the photosensitive resist film 30F covers the opening of the recess 15 formed by the side wall 20 and the substrate 10, and peeling off the base film from the photosensitive resin film 30 constituting the photosensitive resist film 30F. Step (ii): After step (i), a step of exposing the photosensitive resin film 30 to light. Step (iii): A step of performing a heat treatment on the photosensitive resin film 30 after step (ii). Step (iv): After the step (iii), the photosensitive resin film 30 is developed to form a negative pattern (exposed portion 30A) that covers the opening of the recess 15 formed by the sidewall 20 and the substrate 10 in the substrate 10 having the recess 15 on its surface, which was prepared in the first step (S1). Step (v): A step of further hardening the negative pattern (exposed portion 30A) after step (iv) by heat treatment to obtain a hollow structural body 100 in which the exposed portion 30A, which becomes the top plate portion, is made of the hardened body 40 of the photosensitive resin film.

[0219] The hollow structure manufactured by the manufacturing method according to this embodiment comprises a recess 15 and a top plate portion that closes the opening of the recess 15. The hollow structure can be suitably used for hollow packages used in SAW filters, MEMS, various sensors, etc.

[0220] <About photosensitive resist film> The photosensitive resist film 30F in this embodiment has, for example, a negative photosensitive resin film 30 formed from the above-mentioned negative photosensitive composition.

[0221] When a photosensitive resin film 30 is formed using such a photosensitive resist film 30F and selectively exposed to light, acid is generated from component (I) in the exposed portion 30A of the photosensitive resin film 30. The acid causes ring-opening polymerization of the epoxy groups in component (A), reducing the solubility of component (A) in a developer containing an organic solvent. Meanwhile, the solubility of component (A) in an organic solvent-containing developer remains unchanged in the unexposed portion 30B of the photosensitive resin film 30. This results in a difference in solubility in an organic solvent-containing developer between the exposed portion 30A and the unexposed portion 30B of the photosensitive resin film 30. In other words, the photosensitive resin film 30 is negative-tone. Therefore, when the photosensitive resin film 30 is developed with a developer containing an organic solvent, the unexposed portion 30B is dissolved and removed, forming a negative-tone pattern.

[0222] Here, the negative photosensitive resin film 30 of the photosensitive resist film 30F is typically made of a B-stage (semi-cured) resin material. The photosensitive resist film 30F may be a laminated film in which a photosensitive resin film 30 is laminated on a base film. The photosensitive resist film 30F according to this embodiment is preferably a laminated film in which a photosensitive resin film 30 is laminated on a base film.

[0223] The photosensitive resist film 30F can be produced by applying the above-mentioned negative photosensitive composition onto a substrate film and drying it to form a photosensitive resin film 30. The negative photosensitive composition may be applied to the substrate film by a suitable method using an applicator, blade coater, lip coater, comma coater, film coater, or the like. The thickness of the photosensitive resin film 30 is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0224] 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.

[0225] [[Process (i)]] In step (i), the photosensitive resist film 30F is arranged so that the surface of the photosensitive resin film 30 constituting the photosensitive resist film 30F covers the opening surface of the recess 15. Thereafter, the base film is peeled off from the photosensitive resin film 30 constituting the photosensitive resist film 30F. 1, a photosensitive resin film 30 constituting a photosensitive resist film 30F is disposed so as to face a substrate 10 via a sidewall 20. A hollow, sealed space (cavity) is formed surrounded by the substrate 10, the sidewall 20, and the photosensitive resin film 30.

[0226] [[Step (ii)]] In the step (ii), the photosensitive resin film 30 is exposed to light. For example, the photosensitive resin film 30 is selectively exposed to light using a known exposure device through a photomask 60 on which a predetermined pattern is formed.

[0227] 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.

[0228] [[Step (iii)]] In the step (iii), the exposed photosensitive resin film 30 is subjected to a heat treatment, a so-called post-exposure bake (PEB) treatment. The PEB treatment is carried out, for example, at a temperature of 80 to 150° C. for 40 to 600 seconds, preferably 60 to 300 seconds. By the heat treatment in step (iii), the photosensitive resin film 30 after exposure becomes an exposed portion 30A where the epoxy groups in the component (A) have undergone ring-opening polymerization, and an unexposed portion 30B which remains unchanged.

[0229] [[Step (iv)]] In step (iv), the photosensitive resin film 30 (exposed portion 30A, unexposed portion 30B) after the PEB treatment is developed to form a negative pattern (exposed portion 30A). The development here can be carried out in the same manner as in the above-mentioned [Developing Step]. After the development, a rinsing treatment is preferably carried out. By the development in step (iv), the unexposed portion 30B is dissolved and removed, and the exposed portion 30A remains as a negative pattern. The exposed portion 30A becomes the top plate portion (the roof that covers the opening of the recess).

[0230] [[Process (v)]] In step (v), the developed negative pattern (exposed portion 30A) is further hardened by a heat treatment (curing operation) to obtain a hollow structure 100 in which the exposed portion 30A (top plate portion) is made of a hardened body 40 of the photosensitive resin film 30. In FIG. 1, the cured body 40 is formed by curing the photosensitive resin material that forms the sidewall 20 and the photosensitive resin film 30 and integrating them into one body.

[0231] In the manufacturing method of the hollow structure of the embodiment described above, since the negative photosensitive composition described above is used, deformation and swelling (doming) of the top plate due to the curing operation are suppressed, and thus the height of the electronic component can be reduced stably. [Example]

[0232] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0233] <Preparation of negative-type photosensitive composition> (Examples 1 to 5, Comparative Examples 1 to 3) Each component shown in Table 1 was mixed and dissolved in methyl ethyl ketone (MEK), and the mixture was filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Corporation) to prepare a negative-type photosensitive composition (solution with a solid content concentration of 70 to 75% by mass) for each example.

[0234] [Table 1]

[0235] In Table 1, the abbreviations have the following meanings: The values in brackets [ ] are the amounts of each component blended (parts by mass; solid content equivalent). (A1)-1: Epoxy resin represented by the following chemical formula (A1-1), product name "jER-157S70", manufactured by Mitsubishi Chemical Corporation. (A1)-2: Epoxy resin represented by the following chemical formula (A1-2). Product name: "TECHMORE VG-3101L", manufactured by Printec Co., Ltd. (A1)-3: Epoxy resin represented by the following chemical formula (A1-3). Product name: YDCN-704, manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0236] [ka]

[0237] (B)-1: A polyfunctional acrylate compound represented by the following chemical formula (B-1), trade name "KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.

[0238] [ka]

[0239] (I1)-1: A cationic polymerization initiator represented by the following chemical formula (I1-1). (I1)-2: A cationic polymerization initiator represented by the following chemical formula (I1-2).

[0240] [ka]

[0241] (I2)-1: A cationic polymerization initiator represented by the following chemical formula (I2-1-2).

[0242] [ka]

[0243] (C)-1: A photoradical polymerization initiator represented by the following chemical formula (C-1), product name "Omnirad 651", manufactured by IGM Resins BV. (C)-2: Photoradical polymerization initiator represented by the following chemical formula (C-2), product name "Omnirad 819", manufactured by IGM Resins BV.

[0244] [ka]

[0245] (M)-1: Nanosilica particles (particle size 15 nm) Product name "MEK-EC-2130Y", manufactured by Nissan Chemical Co., Ltd.

[0246] <Manufacturing of hollow structures> Hollow structures of each example were obtained using the negative photosensitive compositions of Examples 1 to 5 and Comparative Examples 1 to 3. The hollow structures were obtained through the following first step (S1) and second step (S2).

[0247] [First step (S1)] By the following film formation process, exposure process, and development process, side walls were formed on the silicon substrate, thereby obtaining a substrate having recesses on its surface.

[0248] Film formation process: TMMFS2000 (Tokyo Ohka Kogyo Co., Ltd., dry film resist with a film thickness of 20 μm) was laminated onto a silicon wafer under conditions of 80° C., 0.3 MPa, and 0.5 m / min to a film thickness of 20 μm.

[0249] Exposure process: The substrate film (base film) in contact with the 20 μm thick photosensitive resin film was peeled off, and the photosensitive resin film was irradiated with 200 mJ / cm 2 using a Canon PLA-501 ghi ray aligner. 2 The photosensitive resin film was irradiated with ghi rays through a mask having an opening pattern of 500 μm×500 μm at an irradiation dose of 1000 μm. Thereafter, the exposed photosensitive resin film was subjected to a heat treatment on a hot plate at 90° C. for 5 minutes.

[0250] Development process: The photosensitive resin film after the heat treatment was subjected to puddle development at 23° C. using propylene glycol monomethyl ether acetate as a developer to form a negative pattern that would become the sidewall. The negative pattern was further cured by heat treatment in an oven (under nitrogen, at 200° C. for 1 hour), to form a substrate made of a cured photosensitive resin film and having recesses on its surface.

[0251] [Second process (S2)] A hollow structure was produced by forming a top plate portion for covering the opening of the recess on the substrate obtained in the first step through the following steps (i) to (v) having recesses on the surface.

[0252] Step (i): A step of disposing a photosensitive resist film so that the photosensitive resist film covers the opening of a recess in a substrate, and peeling off the base film from a photosensitive resin film constituting the photosensitive resist film. Step (ii): After step (i), a step of exposing the photosensitive resin film to light. Step (iii): A step of subjecting the photosensitive resin film after step (ii) to a heat treatment. Step (iv): After step (iii), the photosensitive resin film is developed to form a negative pattern (exposed portion) that covers the opening of the recess formed by the sidewall and the substrate in the substrate having a recess on its surface prepared in the first step (S1). Step (v): A step of further curing the negative pattern (exposed portion) after step (iv) by heat treatment to obtain a hollow structure in which the exposed portion that becomes the top plate portion is made of the cured product of the photosensitive resin film.

[0253] [[Process (i)]] First, the substrate having recesses on its surface obtained in the first step was prepared. The negative photosensitive composition of each example was applied to the substrate film using an applicator, and baked (PAB) in an oven at 70°C for 10 minutes to form a photosensitive resin film with a thickness of 20 to 30 μm, thereby obtaining a photosensitive resist film. The photosensitive resist film was disposed so that the surface of the photosensitive resin film of the photosensitive resist film covered the opening of the side wall of the substrate having the side wall. Thereafter, the base film was peeled off from the photosensitive resin film of the photosensitive resist film, thereby forming a hollow, sealed space (cavity) surrounded by the substrate, the sidewall, and the photosensitive resin film.

[0254] [[Step (ii)]] Then, using a Canon PLA-501 ghi line aligner, the photosensitive resin film was irradiated with 300 mJ / cm 2 The specimen was irradiated with Ghi rays at an exposure dose of .

[0255] [[Step (iii)]] The photosensitive resin film after exposure in the step (ii) was subjected to a heat treatment on a hot plate at 90° C. for 5 minutes (PEB treatment). By the PEB treatment in step (iii), the photosensitive resin film after exposure became an exposed area (top plate area) where the epoxy groups in component (A) had undergone ring-opening polymerization, and an unexposed area where no change occurred.

[0256] [[Step (iv)]] The photosensitive resin film after the heat treatment in the step (iii) was subjected to puddle development at 23° C. using propylene glycol monomethyl ether acetate as a developer to form a negative pattern that would become the top plate portion. By the development in step (iv), the unexposed areas were dissolved and removed, and the exposed areas (top plate areas) remained as a negative pattern.

[0257] [[Process (v)]] The negative pattern after step (iv) was further hardened by heat treatment (curing operation) in an oven to obtain a hollow structure whose top plate was made of a cured photosensitive resin film made of the negative photosensitive composition of each example.

[0258] <Doming evaluation> For each of the hollow structures obtained, the swelling (doming) of the top plate after the high-temperature heat treatment in the curing operation was measured using a stylus profiling system (Dektak XT, manufactured by Bruker). In evaluating doming, the height (H0) from the substrate to the upper surface of the top plate portion before the PEB heat treatment (after step (ii) and before step (iii)) was measured in advance. In Table 2, "After Cure" is the value (H1-H0) obtained by subtracting the height (H0) from the substrate to the top surface of the top plate before the PEB heat treatment from the height (H1) from the substrate to the top surface of the cured body after the high-temperature heat treatment of the curing operation (after step (v)). This value (H1-H0) is shown in Table 2 as the measurement result.

[0259] [Table 2]

[0260] From the results shown in Table 2, it was confirmed that the top plate portions of the hollow structures formed using the negative photosensitive compositions of Examples 1 to 5 to which the present invention was applied were suppressed from doming during the heat treatments performed during the manufacture of the hollow structures, such as the PEB heat treatment and the high-temperature heat treatment during the curing operation. When the negative photosensitive composition of Comparative Example 3 was used, it was not possible to prepare a top plate portion, and no data was obtained.

[0261] 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]

[0262] 10 Substrate 15 recess 20 side wall 30 Photosensitive resin film 30A Exposed area (top panel) 30B Unexposed area 30F Photosensitive Resist Film 40 Hardened body 60 Photomask

Claims

1. an epoxy group-containing compound; a cationic polymerization initiator; a polyfunctional (meth)acrylate compound; a photoradical polymerization initiator; A negative photosensitive composition for forming a top plate portion of a hollow structure, comprising:

2. 2. The negative photosensitive composition according to claim 1, wherein the content of the epoxy group-containing compound is 50 parts by mass or more per 100 parts by mass of the total content of the epoxy group-containing compound and the polyfunctional (meth)acrylate compound.

3. The negative photosensitive composition according to claim 1 or 2, further comprising silica nanoparticles.

4. 4. The negative photosensitive composition according to claim 1, wherein a content of the cationic polymerization initiator is 0.01 to 50 parts by mass relative to 100 parts by mass of a content of the polyfunctional (meth)acrylate compound.

5. A method for manufacturing a hollow structure comprising a recess and a top plate portion that closes an opening of the recess, A method for producing a hollow structural body, comprising forming the top plate portion using the negative photosensitive composition according to any one of claims 1 to 4.

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