Negative photosensitive composition, photosensitive resist film, method for producing hollow structure, and method for forming pattern

Abstract

Provided are: a negative photosensitive composition which is capable of forming a pattern having a good shape and which is capable of improving adhesiveness to a side wall of a hollow structure; a photosensitive resist film which is provided with a photosensitive film that is formed using the negative photosensitive composition; a method for producing a hollow structure using the negative photosensitive composition; and a method for forming a pattern. The negative photosensitive composition contains a trifunctional or higher polyfunctional epoxy compound, a cationic polymerization initiator, and a bifunctional aromatic epoxy compound having a molecular weight of 800 or less. In the negative photosensitive composition, the ratio of the content of the difunctional aromatic epoxy compound to the total content (100% by mass) of the polyfunctional epoxy compound and the difunctional aromatic epoxy compound is 0.6-10% by mass.

Description

Technical Field

[0001] This invention relates to a negative photosensitive composition, a photosensitive resist film, a method for manufacturing a hollow structure, and a method for patterning. This application claims priority based on Japanese Patent Application No. 2023-185656, filed on October 30, 2023, the contents of which are incorporated herein by reference. Background Technology

[0002] In recent years, the development of miniature electronic devices such as surface elastic wave (SAW) filters has been progressing. The encapsulation for sealing such electronic devices features a hollow, sealed structure to ensure the propagation of surface elastic waves and the mobility of the moving parts of the electronic device. Going forward, especially for high-frequency devices such as smartphones, the demand for miniaturization of encapsulations with hollow, sealed structures (hereinafter referred to as hollow structures) is becoming increasingly urgent.

[0003] Figure 3 A schematic cross-sectional view showing an example of the structure of the hollow structure 100.

[0004] The hollow structure 100 includes a substrate 10, a sidewall 20 formed on the substrate 10, and a negative pattern (exposure part 30A, hereinafter also referred to as top plate part) that blocks the opening of the recess 15 formed by the sidewall 20 and the substrate 10.

[0005] The hollow structure 100 is manufactured, for example, in the following manner. First, a photosensitive film formed by coating a photosensitive composition onto a substrate 10 is selectively exposed to manufacture the sidewall 20. Next, the photosensitive film is adhered to the sidewall 20 in a manner that covers the recess 15, and then selectively exposed to manufacture the top plate portion 30A.

[0006] When forming the sidewalls of a hollow structure on a substrate, there is a problem that the periphery of the negative pattern in contact with the substrate is prone to undercut. In response to this, Patent Document 1 discloses a negative photosensitive resin composition containing an epoxy-containing compound and a resin having a specific structural unit.

[0007] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2022-101132 Summary of the Invention

[0008] The problem that the invention aims to solve However, the top plate portion made using the negative photosensitive resin composition of Patent Document 1 has the problem of insufficient adhesion to the sidewalls formed on the substrate.

[0009] Therefore, the objective of this invention is to provide a negative photosensitive composition capable of forming a pattern with a good shape, a negative photosensitive composition capable of improving adhesion to the sidewalls of a hollow structure, a photosensitive resist film having a photosensitive film formed therefrom, a method for manufacturing a hollow structure using the negative photosensitive composition, and a pattern forming method.

[0010] Methods for solving problems The present invention includes the following methods.

[0011] The first aspect of the present invention is a negative photosensitive composition containing a multifunctional epoxy compound with three or more functions, a cationic polymerization initiator, and a difunctional aromatic epoxy compound with a molecular weight of 800 or less. The proportion of the difunctional aromatic epoxy compound is 0.6 to 10% by mass relative to the total content (100% by mass) of the multifunctional epoxy compound and the difunctional aromatic epoxy compound.

[0012] The second aspect of the present invention is a photosensitive resist film, wherein a photosensitive film formed using the negative photosensitive composition involved in the first aspect and a cover film are sequentially stacked on a substrate film.

[0013] The third aspect of the present invention is a method for manufacturing a hollow structure including a recess and a top plate portion that seals the opening of the recess, wherein the aforementioned top plate portion is formed using the negative photosensitive composition involved in the first aspect.

[0014] The fourth aspect of the present invention is a pattern forming method, comprising: a step of forming a photosensitive film on a support using the negative photosensitive composition involved in the first aspect; a step of exposing the aforementioned photosensitive film; and a step of developing the exposed photosensitive film using a developer containing an organic solvent to form a negative pattern.

[0015] Invention Effects According to the present invention, a negative photosensitive composition capable of forming patterns with good shapes, capable of improving adhesion to the sidewalls of a hollow structure, a photosensitive resist film having a photosensitive film formed therefrom, a method for manufacturing a hollow structure using the negative photosensitive composition, and a pattern forming method are provided. Attached Figure Description

[0016] Figure 1 This is a schematic diagram illustrating a method for manufacturing a hollow structure according to an embodiment of the present invention.

[0017] Figure 2 This diagram is used to illustrate the cone angle formed by the residual photosensitive film and the silicon wafer in the embodiment.

[0018] Figure 3A cross-sectional view of the hollow structure in the embodiments of the present invention is shown schematically. Detailed Implementation

[0019] In this specification and claims, the term "aliphatic" is a relative concept compared to aromatic, and is defined as a group or compound that does not have aromatic properties.

[0020] Unless otherwise specified, "alkyl" includes monovalent saturated hydrocarbon groups that are straight-chain, branched, or cyclic. The same applies to alkyl groups within alkoxy groups.

[0021] Unless otherwise specified, "alkylene" includes straight-chain, branched-chain, and cyclic divalent saturated hydrocarbon groups.

[0022] "Halogenated alkyl" is a group obtained by replacing some or all of the hydrogen atoms of an alkyl group with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0023] "Fluoroalkyl" refers to a group obtained by replacing some or all of the hydrogen atoms of an alkyl group with fluorine atoms.

[0024] The cases described as "may have substituents" include both cases where a hydrogen atom (-H) is replaced by a monovalent group and cases where a methylene group (-CH2-) is replaced by a divalent group.

[0025] "Exposure" is a concept that includes exposure to all types of radiation.

[0026] (Negative photosensitizing composition) The negative photosensitive composition involved in this embodiment contains a multifunctional epoxy compound (Ap) with three or more functions, a cationic polymerization initiator (I), and a difunctional aromatic epoxy compound (Am) with a molecular weight of 800 or less.

[0027] Hereinafter, multifunctional epoxy compounds with three or more functions will be referred to as "(Ap) components", and difunctional aromatic epoxy compounds with a molecular weight of less than 800 will be referred to as "(Am) components". Multifunctional epoxy compounds with three or more functions (Ap) and difunctional aromatic epoxy compounds (Am) will also be referred to simply as "epoxide compounds" ("(A) components"). In addition, cationic polymerization initiators (I) will be referred to as "(I) components".

[0028] The proportion of the aforementioned (Am) component is 0.6 to 10% by mass relative to the total content (100% by mass) of the aforementioned (Ap) component and the aforementioned (Am) component.

[0029] When a photosensitive film is formed using the aforementioned negative photosensitive composition and selectively exposed, the cationic portion of the cationic polymerization initiator decomposes to generate acid in the exposed portion of the film. Under the action of this acid, the epoxy groups in component (A) undergo ring-opening polymerization, reducing the solubility of component (A) in a developer containing an organic solvent (organic developer). Conversely, in the unexposed portion of the photosensitive film, the solubility of component (A) in the organic developer remains unchanged. Therefore, a difference in solubility in the organic developer arises between the exposed and unexposed portions of the photosensitive film. Thus, if the photosensitive film is developed with an organic developer, the unexposed portion can be dissolved and removed, forming a negative pattern.

[0030] <Multifunctional epoxy compounds (Ap) with 3 or more functions> As the (Ap) component, a multifunctional epoxy compound with 3 or more functions can be used, which has sufficient epoxy groups for forming negative patterns by exposure.

[0031] Bisphenol Novolac type epoxy resin is preferred as a multifunctional epoxy compound with three or more functions.

[0032] Examples of bisphenol Novolac type epoxy resins include multifunctional epoxy resins produced by reacting bisphenol Novolac resin with epichlorohydrin, and multifunctional epoxy resins obtained by novolacating bisphenol glycidyl ether. Among these, bisphenol A Novolac type epoxy resins are preferred due to their ease of availability.

[0033] As a bisphenol Novolac type epoxy resin, the resin represented by the following general formula (Ap-1) is preferably cited.

[0034] [Chemical Formula 1] In equation (Ap-1), R p1 and R p2 Each is independently an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. Multiple R p1 They can be the same or different. Multiple Rs p2 They can be the same or different. n1 is an integer from 1 to 5. R EP It is a group containing an epoxy group. Multiple R EP They can be the same or different. In the aforementioned equation (Ap-1), R p1 R p2The alkyl group having 1 to 5 carbon atoms is, for example, a straight-chain, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Examples of cyclic alkyl groups include cyclobutyl, cyclopentyl, etc.

[0035] Among them, as R p1 R p2 Preferably, it is a hydrogen atom or a straight-chain or branched alkyl group, more preferably a hydrogen atom or a straight-chain alkyl group, and particularly preferably a hydrogen atom or a methyl group.

[0036] In equation (Ap-1), multiple R p1 They can be the same or different. Multiple Rs p2 They can be the same or different.

[0037] In formula (Ap-1), n1 is an integer from 1 to 5, preferably 2 or 3, and more preferably 2.

[0038] In equation (Ap-1), R EP It is a group containing an epoxy group.

[0039] As R EP The group containing an epoxy group is not particularly limited, but can include groups formed only by epoxy groups; groups formed only by alicyclic epoxy groups; and groups having an epoxy group or alicyclic epoxy group and a divalent linker.

[0040] The so-called alicyclic epoxy group is an alicyclic group that has an oxetine structure as a 3-membered cyclic ether. Specifically, it is a group that has both an alicyclic group and an oxetine structure.

[0041] The alicyclic group that forms the basic skeleton of the alicyclic epoxy group can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. Furthermore, the hydrogen atoms in these alicyclic groups can be replaced by alkyl, alkoxy, or hydroxyl groups.

[0042] In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferred that the epoxy group or the alicyclic epoxy group is bonded by a divalent linking group bonded to the oxygen atom (-O-) in the formula.

[0043] Here, there is no particular limitation on the divalent linking group, and preferred examples include divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms.

[0044] Regarding divalent hydrocarbon groups that can have substituents: The divalent hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0045] The aliphatic hydrocarbon group in the divalent hydrocarbon group can be saturated or unsaturated, but saturated is usually preferred.

[0046] More specifically, examples of this aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0047] The aforementioned linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. As a linear aliphatic hydrocarbon group, a linear alkylene group is preferred, specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0048] The number of carbon atoms in the aforementioned branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and most preferably 2 or 3. As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include 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 1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl 1,4-butylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. As for the alkyl group in the alkyl alkylene group, a straight-chain alkyl group having 1 to 5 carbon atoms is preferred.

[0049] Examples of aliphatic hydrocarbon groups containing rings in their structure include alicyclic hydrocarbon groups (groups formed by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups formed by alicyclic hydrocarbon groups bonded to the ends of straight-chain or branched aliphatic hydrocarbon groups, and groups where alicyclic hydrocarbon groups exist in the middle of straight-chain or branched aliphatic hydrocarbon groups. Examples of straight-chain or branched aliphatic hydrocarbon groups are similar to those described above.

[0050] The number of carbon atoms in the aforementioned alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0051] The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferable to be a group formed by removing two hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, it is preferable to be a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc.

[0052] As a polycyclic alicyclic hydrocarbon group, it is preferred to be a group formed by removing two hydrogen atoms from a polycyclic alkane. As the polycyclic alkane, it is preferred to be a polycyclic alkane with 7 to 12 carbon atoms. Specifically, examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0053] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. There are no particular limitations on the aromatic ring; it can be a cyclic conjugated system having (4n+2) π electrons, and can 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. Examples of aromatic rings include benzene, naphthalene, anthracene, phenanthrene, and other aromatic hydrocarbon rings; and aromatic heterocycles formed by replacing a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0054] Specifically, examples of aromatic hydrocarbon groups include groups formed by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (aryl or heteroaryl); groups formed by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups formed by substituting one hydrogen atom of an aryl or heteroaryl group formed by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (e.g., groups formed by further removing one hydrogen atom from an aryl group among arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms in the alkylene group bonded to the aforementioned aryl or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0055] Divalent hydrocarbon groups can have substituents.

[0056] The divalent hydrocarbon group, whether straight-chain or branched, may or may not have substituents. Examples of substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms substituted by fluorine atoms, and carbonyl groups.

[0057] Alicyclic hydrocarbon groups, which are divalent hydrocarbon groups and contain a ring in their structure, may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and carbonyl groups.

[0058] Regarding the alkyl group used as the aforementioned substituent, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl, ethyl, propyl, n-butyl, and tert-butyl are most preferred.

[0059] Regarding the alkoxy group used as the aforementioned substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, and methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy are preferred, with methoxy and ethoxy being the most preferred.

[0060] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine being the preferred option.

[0061] Regarding the alkyl halogroups that are the aforementioned substituents, examples can be given of groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are replaced by the aforementioned halogen atoms.

[0062] For alicyclic hydrocarbon groups, a portion of the carbon atoms constituting the ring structure can be replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0063] For aromatic hydrocarbon groups that are divalent hydrocarbon groups, the hydrogen atoms in the aromatic hydrocarbon group can be replaced by substituents. For example, the hydrogen atoms of the aromatic ring bonded to the aromatic hydrocarbon group can be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, and hydroxyl groups.

[0064] Regarding the alkyl group used as the aforementioned substituent, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl, ethyl, propyl, n-butyl, and tert-butyl are most preferred.

[0065] Regarding the alkoxy, halogen atom, and haloalkyl groups that are the aforementioned substituents, examples can be given of substituents that replace the hydrogen atoms present in the aforementioned alicyclic hydrocarbon groups.

[0066] Regarding divalent linking groups containing heteroatoms: The heteroatoms in a divalent linker containing heteroatoms are atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0067] Among the divalent linking groups containing heteroatoms, preferred examples of such linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H can be replaced by alkyl, acyl, or other substituents); -S-, -S(=O)2-, -S(=O)2-O-, and 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 - represents a group [where Y is a group that represents ... 21 and Y 22 Each is an independent divalent hydrocarbon group that can have substituents, where O is an oxygen atom and m” is an integer from 0 to 3.

[0068] When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, its H can be replaced by substituents such as alkyl or acyl groups. The number of carbon atoms in the substituent (alkyl, acyl, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0069] 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 Each is an independent divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include the same "divalent hydrocarbon group that may have substituents" exemplified in the description of divalent linking groups above.

[0070] As Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0071] As Y 22 Preferably, the hydrocarbon group is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl.

[0072] Formula-[Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m” is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as in formula -[Y 21 -C(=O)-O] m” -Y 22 - indicates a group, particularly preferred formula -Y 21 -C(=O)-OY 22 - indicates a functional group. The preferred formulation is -(CH2). a’ -C(=O)-O-(CH2) b’ - represents a group. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1.

[0073] Among them, as R EP The epoxy group in it is preferably a glycidyl group.

[0074] Alternatively, as the (Ap) component, trifunctional epoxy compounds having three epoxy groups within the molecule are preferably selected. Examples of trifunctional epoxy compounds include trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, and trifunctional epoxy compounds represented by the following general formula (Ap-2).

[0075] [Chemical Formula 2] In equation (Ap-2), R p3 R p4 and R p5 Each is independently an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. Rm EP It is a group containing an epoxy group. Multiple Rm EP They can be the same or different. In the aforementioned equation (Ap-2), R p3 R p4 and R p5The alkyl group having 1 to 5 carbon atoms is, for example, a straight-chain, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Examples of cyclic alkyl groups include cyclobutyl, cyclopentyl, etc.

[0076] Among them, as R p3 R p4 and R p5 Each is preferably a hydrogen atom or a straight-chain or branched alkyl group, more preferably a hydrogen atom or a straight-chain alkyl group, further preferably a hydrogen atom or a methyl group, and particularly preferably methyl groups.

[0077] In the aforementioned equation (Ap-2), Rm EP It is an epoxy group, which is related to R in the aforementioned formula (Ap-1). EP Similarly, glycidyl groups are preferred.

[0078] Multiple Rm EP They can be the same or different.

[0079] The following are specific examples of trifunctional epoxy compounds represented by the aforementioned formula (Ap-2).

[0080] [Chemical Formula 3] As a trifunctional epoxy compound, it can be used alone or in combination with two or more types.

[0081] As a trifunctional epoxy compound, from the viewpoint that intramolecular crosslinking reactions are not easy to carry out, it is preferable to be a compound having a structure in which the distance between the three epoxy groups is separated within the molecule, more preferably tris(4-hydroxyphenyl)methane triglycidyl ether or a trifunctional epoxy compound represented by the above general formula (Ap-2), particularly preferably a trifunctional epoxy compound represented by the above general formula (Ap-2), and most preferably a trifunctional epoxy compound represented by the above formula (Ap-2-1).

[0082] Alternatively, as a component (Ap), resins having structural units represented by the following general formula (anv1) are also preferred.

[0083] [Chemical Formula 4] [In the formula, R] EP It is a group containing an epoxy group. R a22 and R a23 Each atom is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. In the aforementioned equation (anv1), R a22 Ra23 Alkyl groups having 1 to 5 carbon atoms and R in the aforementioned formula (Ap-1) p1 R p2 The same applies to alkyl groups with 1 to 5 carbon atoms.

[0084] R a22 R a23 The halogen atom is preferably a chlorine atom or a bromine atom.

[0085] In the aforementioned equation (anv1), R EP R in the aforementioned equation (Ap-1) EP Similarly, glycidyl groups are preferred.

[0086] The following shows a specific example of the structural unit represented by the aforementioned formula (anv1).

[0087] [Chemical Formula 5] The (Ap) component can be a resin formed solely from the aforementioned structural unit (anv1), or it can be a resin having structural unit (anv1) and other structural units.

[0088] As other structural units, examples include structural units represented by the following general formulas (anv2) to (anv3).

[0089] [Chemical Formula 6] [In the formula, R] a24 It is a hydrocarbon group that can have substituents. R a25 ~R a26 R a28 ~R a30 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. R a27 It can be an epoxy group or a hydrocarbon group that may have substituents. In the aforementioned equation (anv2), R a24 It is a hydrocarbon group that may have substituents. Examples of hydrocarbon groups that may have substituents include straight-chain or branched alkyl groups, or cyclic hydrocarbon groups.

[0090] The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, and methyl or ethyl are more preferred.

[0091] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0092] R a24 When it becomes a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, it can be a polycyclic group or a monocyclic group.

[0093] Regarding the aliphatic hydrocarbon group as a monocyclic group, it is preferable to have a group formed by removing one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc.

[0094] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferred to be a group obtained by removing one hydrogen atom from a polycyclic alkane. As for the polycyclic alkane, it is preferred to be a polycyclic alkane with 7 to 12 carbon atoms. Specifically, examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0095] R a24 When a cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0096] The aromatic ring is not particularly limited, as long as it is a cyclic conjugated system with 4n+2 π electrons, and can 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. Specifically, examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by replacing a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0097] As R a24 Specifically, the aromatic hydrocarbon group in the form of the alkyl group can be categorized as an aryl or heteroaryl group formed by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; a group formed by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); or a group formed by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups, etc.). The alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0098] In the aforementioned equations (anv2) and (anv3), R a25 ~R a26 R a28 ~R a30 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0099] Alkyl groups and halogen atoms with 1 to 5 carbon atoms respectively are associated with the aforementioned R a22 R a23 same.

[0100] In the aforementioned equation (anv3), R a27 It is a group containing an epoxy group, or a hydrocarbon group that may have substituents. R a27 The epoxy-containing group and R in the aforementioned formula (Ap-1) EP Similarly. R a27 The hydrocarbon group that may have substituents and R in the aforementioned formula (anv2) a24 same.

[0101] The following are specific examples of the structural units represented by the aforementioned equations (anv2) to (anv3).

[0102] [Chemical Formula 7] When the (Ap) component has not only structural unit (anv1) but also other structural units, the proportion of each structural unit in the (Ap) component is not particularly limited. Relative to the total of all structural units constituting the (Ap) component, the total number of structural units with epoxy groups is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%.

[0103] Commercially available products containing (Ap) include, for example, jER-152, jER-154, jER-157S70, jER-157S65 (and above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON HP5000 (and above, manufactured by DIC Corporation), and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).

[0104] If the above-mentioned commercially available products contain impurities such as low molecular weight components in addition to the (Ap) component, the (Ap) component obtained by removing such impurities from the commercially available products can also be used.

[0105] There are no particular limitations on the method for removing impurities, and any known method may be used. Examples of methods for removing impurities include, for instance, washing with commercially available products using a solvent that dissolves only the impurities, redeposition of (Ap) components, component separation based on GPC extraction, and component separation using a dialysis membrane.

[0106] The molecular weight dispersion (Mw / Mn) of the (Ap) component is preferably 2.0 or more and 4.0 or less, more preferably 2.0 or more and 3.0 or less.

[0107] The epoxy equivalent of the (Ap) component is preferably 200 g / eq. or more and 300 g / eq. or less, more preferably 200 g / eq. or more and 240 g / eq. or less.

[0108] The epoxy equivalent of the (Ap) component can be determined by potentiometric titration as described in JIS K-7236. Examples of potentiometric titration-based methods for determining epoxy equivalent include the hydrochloric acid-dioxane method, the perchloric acid-tetraethylammonium bromide method, the perchloric acid-hexadecyltrimethylammonium bromide method, the hydrochloric acid-potassium iodide method, and the Durbertaki method using a hydrobromic acid solution.

[0109] As a component (Ap), one type can be used alone, or two or more types can be used together.

[0110] <Difunctional aromatic epoxides (Am) with a molecular weight below 800> The (Am) component uses a difunctional aromatic epoxy compound with a molecular weight of less than 800.

[0111] Examples of difunctional aromatic epoxides with a molecular weight below 800 include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol Z diglycidyl ether, bisphenol S diglycidyl ether, bisphenol AD ​​diglycidyl ether, bisphenol acetophenone diglycidyl ether, bisphenol trimethylcyclohexane diglycidyl ether, bisphenol fluorene diglycidyl ether, tetramethylbisphenol A diglycidyl ether, tetramethylbisphenol F diglycidyl ether, tetra-tert-butylbisphenol A diglycidyl ether, and tetramethylbisphenol S diglycidyl ether, etc.; biphenol di... Biphenol-based diglycidyl ethers include: tetramethylbiphenol diglycidyl ether, dimethylbiphenol diglycidyl ether, tetra-tert-butylbiphenol diglycidyl ether, etc.; hydroquinone-based diglycidyl ethers include: hydroquinone diglycidyl ether, dihydroanthracene diglycidyl ether, methylhydroquinone diglycidyl ether, dibutylhydroquinone diglycidyl ether, resorcinol diglycidyl ether, methyl resorcinol diglycidyl ether, etc.; dihydroanthracene hydroquinone diglycidyl ether, dihydroxydiphenyl ether diglycidyl ether, dihydroxydiphenyl sulfide diglycidyl ether, dihydroxynaphthalene diglycidyl ether, etc.

[0112] As a difunctional aromatic epoxy compound, a difunctional epoxy compound represented by the following general formula (Am-1) is preferably cited.

[0113] [Chemical Formula 8] In formula (Am-1), R p6 and R p7 Each is independently an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. R p6 With R p7 They can be keyed and merged with each other. Together they form alicyclic groups that can have substituents. R EP It is a group containing an epoxy group. Multiple R EP They can be the same or different. In the aforementioned formula (Am-1), R p6 R p7 Alkyl groups having 1 to 5 carbon atoms and R in the aforementioned formula (Ap-1) p1 R p2 The same applies to alkyl groups with 1 to 5 carbon atoms.

[0114] R p6 With R p7 Merging and mutual keys When the alicyclic group that can have substituents is formed together, the number of carbon atoms in the aforementioned alicyclic group is preferably 3 to 11, more preferably 3 to 8, and even more preferably 3 to 6.

[0115] In the aforementioned formula (Am-1), REP R in the aforementioned equation (Ap-1) EP Similarly, glycidyl groups are preferred.

[0116] In the negative photosensitive composition of this embodiment, the total content of (Ap) component and (Am) component is preferably 70% or more by mass relative to the total mass (100% by mass) of the solid components of the negative photosensitive composition, more preferably 80 to 99% by mass, and even more preferably 85 to 95% by mass.

[0117] In the negative photosensitizing composition of this embodiment, the content of the (Am) component is 0.6 to 10% by mass relative to the total mass (100% by mass) of the (Ap) component and the (Am) component, preferably 0.7 to 8.0% by mass, and more preferably 0.8 to 2.0% by mass.

[0118] If the content of component (Am) is above the lower limit of the aforementioned preferred range, the adhesion of the photosensitive film used to form the top plate to the sidewalls of the hollow structure is easily improved when forming the hollow structure. On the other hand, if it is below the upper limit of the aforementioned preferred range, a pattern with a good shape and high rectangularity is easily formed when forming the pattern.

[0119] In the negative photosensitive composition of this embodiment, the content of the (Ap) component is 90 to 99.4% by mass, preferably 92 to 99.3% by mass, and more preferably 98 to 99.2% by mass, relative to the total mass (100% by mass) of the (Ap) component and the (Am) component.

[0120] If the content of the (Ap) component is above the lower limit of the aforementioned preferred range, it is easy to form a pattern with a good shape and high rectangularity when forming the pattern. On the other hand, if it is below the upper limit of the aforementioned preferred range, it is easy to improve the adhesion of the photosensitive film used to form the top plate to the sidewalls of the hollow structure when forming the hollow structure.

[0121] Other compounds containing epoxy groups In the negative photosensitive composition of this embodiment, in addition to the (Ap) component and the (Am) component, other epoxy-containing compounds may also be used.

[0122] Other epoxy-containing compounds include bisphenol type epoxy resins (bisphenol A type epoxy resin, bisphenol F type epoxy resin), acrylic resins, aliphatic epoxy resins, etc.

[0123] Examples of bisphenol type epoxy resins include epoxy resins represented by the following general formula (abp1).

[0124] [Chemical Formula 9] [In the formula, R] EP R is a group containing an epoxy group. a31 R a32 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, na 31 Integers from 1 to 50. In equation (abp1), R a31 R a32 Alkyl groups having 1 to 5 carbon atoms and R in the aforementioned formula (Ap-1) p1 R p2 Alkyl groups having 1 to 5 carbon atoms are similar. Among them, as R... a31 R a32 Preferably, hydrogen atoms or methyl groups are used.

[0125] R EP R in the aforementioned equation (Ap-1) EP Similarly, glycidyl groups are preferred.

[0126] As an acrylic resin, for example, a resin having an epoxy-containing unit represented by each of the following general formulas (a1-1) to (a1-2) can be cited.

[0127] [Chemical Formula 10] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Va] 41 It is a divalent hydrocarbon group that can have substituents. na 41 R is an integer between 0 and 2. a41 R a42 It is a group containing an epoxy group. na 42 It can be 0 or 1. Wa 41 for (na 43 +1) Valence aliphatic hydrocarbon group. na 43 It is an integer between 1 and 2. In the aforementioned formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms.

[0128] The alkyl group of R having 1 to 5 carbon atoms is preferably linear or branched. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0129] The alkyl halogroup R having 1 to 5 carbon atoms is a group formed by replacing some or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms with halogen atoms. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0130] R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. From the perspective of industrial availability, a hydrogen atom or a methyl group is most preferred.

[0131] In the aforementioned equation (a1-1), Va 41 For divalent hydrocarbon groups that can have substituents, examples include R in the aforementioned formula (Ap-1). EP The same group as the divalent hydrocarbon group described herein can have substituents.

[0132] In the above, Va 41 The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a straight-chain or branched aliphatic hydrocarbon group, even more preferably a straight-chain aliphatic hydrocarbon group, and particularly preferably a straight-chain alkylene group.

[0133] In formula (a1-1), na 41 It is an integer from 0 to 2, preferably 0 or 1.

[0134] In equations (a1-1) and (a1-2), R a41 R a42 It is an epoxy group, which is related to R in the aforementioned formula (Ap-1). EP same.

[0135] In formula (a1-2), Wa 41 (na) 43 +1) Aliphatic hydrocarbon groups refer to hydrocarbon groups that do not possess aromaticity. They can be saturated or unsaturated, but are usually preferred to be saturated. Examples of the aforementioned aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing rings in their structure, or groups formed by combining straight-chain or branched aliphatic hydrocarbon groups and aliphatic hydrocarbon groups containing rings in their structure.

[0136] Furthermore, regarding the acrylic resin in component (A) above, for the purpose of moderately controlling physical and chemical properties, it may have structural units derived from other polymeric compounds. Examples of such polymeric compounds include known free radical polymeric compounds and anionic polymeric compounds. Examples of such polymeric 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 with carboxyl groups and ester bonds such as 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate, and 2-methacryloyloxyethyl hexahydrophthalate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; and hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Aryl esters of methacrylates such as phenyl methacrylate and benzyl methacrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymeric compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymeric compounds such as vinyl chloride and vinylidene chloride; polymeric compounds containing amide bonds such as acrylamide and methacrylamide; and so on.

[0137] In addition, as other epoxy-containing compounds, compounds represented by the following general formula (m-01) are preferably cited (hereinafter also referred to as "(m01) component").

[0138] [Chemical Formula 11] [In the formula, R] EP It is a group containing an epoxy group. Multiple R EP They can be the same or different. In the aforementioned formula (m-01), R EP It is an epoxy group, which is related to R in the aforementioned formula (Ap-1). EP same.

[0139] Commercially available products that can be used as (m01) ingredients include, for example, the TEPIC series (manufactured by Nissan Chemical Co., Ltd.), such as TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, TEPIC-UC, etc.; MA-DGIC, DA-MGIC, TOIC (manufactured by Shikoku Chemical Co., Ltd.), etc.

[0140] As a (m01) component, one type can be used alone, or two or more types can be used together.

[0141] In the negative photosensitive composition used in this embodiment, when the total mass parts of (PO) component are taken as 100 parts by mass, the content of (m01) component is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass.

[0142] In addition, as other epoxy-containing compounds, compounds having a structure represented by the following general formula (m-O2) are preferably cited (hereinafter also referred to as "(mO2) component"). The (mO2) component can form a fused ring.

[0143] [Chemical Formula 12] [In the formula, n² is an integer from 1 to 4.] In the aforementioned formula (m-02), n2 is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 2.

[0144] As a component (m02), examples include compounds having multiple partial structures represented by the above general formula (m-02) bonded by divalent linking groups or single bonds. Among these, compounds having multiple partial structures represented by the above general formula (m-02) bonded by divalent linking groups are preferred.

[0145] There are no particular limitations on the divalent linking group used here, and preferred examples include divalent hydrocarbon groups that may have substituents and divalent linking groups that contain heteroatoms.

[0146] Regarding the divalent hydrocarbon group that may have substituents and the divalent linking group containing heteroatoms mentioned here, respectively, they are related to R in the above formula (Ap-1). EP The same applies to the divalent hydrocarbon groups (containing epoxy groups) described herein, which may have substituents, and divalent linking groups containing heteroatoms, wherein divalent linking groups containing heteroatoms are preferred, and -Y is more preferred. 21 -C(=O)-O- represents the group, -C(=O)-OY 21 - indicates a group. As Y 21Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0147] Examples of compounds represented by the following chemical formulas can be cited as components of (m02). In the following formulas, l represents an integer from 1 to 10, and m represents an integer from 1 to 30. R represents an alkylene group having 1 to 8 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms, such as methylene, ethylene, n-propylene, or isopropylene). n1 and n2 each represent an integer from 1 to 30.

[0148] [Chemical Formula 13] Commercially available products that can be used as (mO2) components include Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 8000, Celloxide 8010 (all manufactured by Daicel Co., Ltd.); EPOCHALIC THI-DE, EPOCHALIC THI-DE-102, EPOCHALIC THI-DE-103 (all manufactured by ENEOS Co., Ltd.), etc.

[0149] As a (m02) component, one type can be used alone, or two or more types can be used together.

[0150] In the negative photosensitive composition that can be used in this embodiment, when the total mass parts of the (Ap) component and the (Am) component are taken as 100 parts by mass, the content of the (mO2) component is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass.

[0151] In addition, examples of aliphatic epoxy resins include hydrogenated bisphenol A type glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,4-cyclohexanediethanol diglycidyl ether.

[0152] <Catonic Polymerization Initiators> The negative photosensitive composition of this embodiment contains a cationic polymerization initiator (hereinafter also referred to as "component (I)") which is a compound that generates a cation by being irradiated by active energy rays such as ultraviolet light, far ultraviolet light, KrF, ArF, excimer lasers, X-rays, electron beams, etc., and that the cation can become a polymerization initiator.

[0153] As a component (I) mentioned above, examples include onium borate (hereinafter also referred to as "(I1) component") and cationic polymerization initiators other than (I1) component (other cationic polymerization initiators).

[0154] ≪Onium borate≫ Onium borate (I1 component) produces a strong acid upon exposure. Therefore, by using a negative photosensitive composition containing I1 component to form patterns, sufficient sensitivity and good pattern formation can be obtained. In addition, the toxicity and risk of metal corrosion are low when using I1 component.

[0155] As a component (I1), compounds represented by the following general formula (I1) are preferably examples.

[0156] [Chemical Formula 14] [In the formula, R] b01 ~R b04 Each is an aryl group or fluorine atom that can have substituents. q is an integer greater than or equal to 1. q＋ It is a q-valent organic cation. • Anion section In the aforementioned equation (I1), R b01 ~R b04 The aryl group preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specifically, naphthyl, phenyl, anthracene, etc. can be cited as examples, and phenyl is preferred from the perspective of easy availability.

[0157] R b01 ~R b04 The aryl group may also have substituents. There are no particular limitations on the substituent, but halogen atoms, hydroxyl groups, alkyl groups (preferably straight-chain or branched alkyl groups, preferably with 1 to 5 carbon atoms), and haloalkyl groups are preferred; halogen atoms or haloalkyl groups with 1 to 5 carbon atoms are more preferred; and fluorine atoms or fluoroalkyl groups with 1 to 5 carbon atoms are particularly preferred. Having a fluorine atom in the aryl group results in a high polarity of the anionic portion, which is preferable.

[0158] Where R is the expression in equation (I1) b01 ~R b04 Fluorinated phenyl groups are preferred, with perfluorophenyl groups being particularly preferred.

[0159] As a preferred specific example of the anionic portion of the compound represented by the aforementioned formula (I1), tetra(pentafluorophenyl)borate ([B(C6F5)4]) can be cited. - Tetra[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4]) -); Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ); Trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - Tetrafluorophenyl)borate ([B(C6H3F2)4) - )wait.

[0160] Of particular preference is tetra(pentafluorophenyl)borate ([B(C6F5)4)). - ).

[0161] • Cation section In the aforementioned equation (I1), as Q q＋ Examples of preferred organic cations include sulfonium cations and iodonium cations, with particular preference given to organic cations represented by the following general formulas (ca-1) to (ca-5).

[0162] [Chemical Formula 15] [In the formula, R] 201 ~R 207 and R 211 ~R 212 Each can independently represent an aryl, heteroaryl, alkyl, or alkenyl group that may have substituents. R 201 ~R 203 R 206 ~R 207 R 211 ~R 212 They can bond with each other and form a ring together with the sulfur atoms in the formula. R 208 ~R 209 Each can independently represent an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a cyclic group containing -SO2- that may have a substituent. L 201 This represents -C (=O)- or -C (=O)-O-. Y 201 Each can independently represent an arylene, alkylene, or alkenyl group. x is 1 or 2. W 201 This indicates a (x+1) valence linkage group. As R 201 ~R 207 and R 211 ~R 212 The aryl group in the formula can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0163] As R 201 ~R 207 and R 211 ~R 212The heteroaryl group in the text can be exemplified by a group in which a portion of the carbon atom constituting the aforementioned aryl group is replaced by a heteroatom. Examples of heteroatoms include oxygen, sulfur, and nitrogen atoms. Examples of heteroaryl groups include those formed by removing one hydrogen atom from 9H-thioxanthone; examples of substituted heteroaryl groups include those formed by removing one hydrogen atom from 9H-thioxanthone-9-one.

[0164] As R 201 ~R 207 and R 211 ~R 212 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0165] As R 201 ~R 207 and R 211 ~R 212 The alkenyl group in the form of carbon atoms preferably has a carbon number of 2 to 10.

[0166] As R 201 ~R 207 and R 210 ~R 212 The substituents that may be present include, for example, alkyl, halogen atom, haloalkyl, carbonyl, cyano, amino, oxo (=O), aryl, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

[0167] [Chemical Formula 16] [In the formula, R'] 201 Each group can be an independent hydrogen atom, a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents. In the aforementioned equations (ca-r-1) to (ca-r-10), R' 201 Each can be an independent hydrogen atom, a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents.

[0168] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which can be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group can be saturated or unsaturated, but is generally preferred to be saturated.

[0169] R' 201The aromatic hydrocarbon group in the form is a hydrocarbon group having an aromatic ring. The number of carbon atoms in this aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. This number of carbon atoms does not include the number of carbon atoms in the substituents.

[0170] As R' 201 The aromatic rings contained in aromatic hydrocarbon groups can be specifically exemplified by benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles formed by replacing some carbon atoms in these aromatic rings with heteroatoms, or rings formed by replacing some hydrogen atoms in these aromatic rings or aromatic heterocycles with oxo groups, etc. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0171] As R' 201 The aromatic hydrocarbon group in the group can specifically include groups obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, anthracene, etc.), groups obtained by substituting one hydrogen atom of the aforementioned aromatic ring with an alkylene group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl), groups obtained by removing one hydrogen atom from a ring obtained by substituting a portion of the hydrogen atoms constituting the aforementioned aromatic ring with an oxo group (for example, anthraquinone, etc.), and groups obtained by removing one hydrogen atom from an aromatic heterocycle (for example, 9H-thioxanth, 9H-thioxanth-9-one, etc.). The number of carbon atoms in the aforementioned alkylene group (alkyl chain in arylalkyl) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0172] R' 201 Examples of cyclic aliphatic hydrocarbon groups in the structure include aliphatic hydrocarbon groups containing rings.

[0173] Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups in between alicyclic hydrocarbon groups that are intermediate in the form of straight-chain or branched aliphatic hydrocarbon groups.

[0174] The number of carbon atoms in the aforementioned alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0175] The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group formed by removing one or more hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms; specifically, cyclopentane and cyclohexane are examples. As a polycyclic alicyclic hydrocarbon group, it is preferably a group formed by removing one or more hydrogen atoms from a polycyclic alkane; as the polycyclic alkane, it is preferably a polycyclic alkane with 7 to 30 carbon atoms. Among these, more preferably, polycyclic alkanes with a cross-linked ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycyclic alkanes with a fused ring system such as a cyclic group possessing a steroidal skeleton are also preferred.

[0176] Among them, as R' 201 The cyclic aliphatic hydrocarbon group in the form is preferably a group formed by removing one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane, more preferably a group formed by removing one hydrogen atom from a polycyclic alkane, particularly preferably adamantyl or norbornyl, and most preferably adamantyl.

[0177] The number of carbon atoms in the alicyclic hydrocarbon group, whether linear or branched, that can be bonded to the alicyclic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3.

[0178] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0179] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include 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 1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl 1,4-butylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. As for the alkyl group in the alkyl alkylene group, a straight-chain alkyl group with 1 to 5 carbon atoms is preferred.

[0180] Chain alkyl groups that may have substituents: As R' 201 The chain alkyl group can be either straight-chain or branched.

[0181] As a straight-chain alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotriadecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, and dodecyl.

[0182] As a branched alkyl group, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0183] Chain alkenyl groups that may have substituents: As R' 201 The chain-like alkenyl group can be any of straight-chain or branched, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of straight-chain alkenyl groups include vinyl, allyl, and butenyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. As for the chain-like alkenyl group, linear alkenyl groups are preferred, vinyl and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0184] As R' 201 Substituents in cyclic groups, chain-like alkyl or alkenyl groups, such as alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, oxo groups, and the aforementioned R' groups. 201 The cyclic groups, alkyl carbonyl groups, thiophene carbonyl groups, etc.

[0185] Among them, R' 201 Preferably, it is a cyclic group that may have substituents or a chain alkyl group that may have substituents.

[0186] R 201 ~R 203 R 206 ~R 207 R 211 ~R 212When bonds are formed between atoms and together with the sulfur atom in the formula to form a ring, they can be intermediates such as sulfur atoms, oxygen atoms, nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R) atoms. N )-(the R N It is an alkyl group having 1 to 5 carbon atoms. Functional groups such as […] are bonded together. As the formed ring, one ring containing the sulfur atom in the formula, preferably a 3- to 10-membered ring, particularly preferably a 5- to 7-membered ring, has a ring skeleton containing the sulfur atom. Specific examples of the formed ring include thiophene rings, thiazole rings, benzothiophene rings, thiathanthene rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthene rings, thioxanone rings, thiathanthene rings, phenoxathia rings, tetrahydrothiophenonium rings, and tetrahydrothiaran rings.

[0187] In the aforementioned equation (ca-3), R 208 ~R 209 Each alkyl group independently represents an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, preferably an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. When they are alkyl groups, they can bond with each other to form a ring.

[0188] In the aforementioned equation (ca-3), R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a cyclic group containing -SO2- that may have a substituent.

[0189] As R 210 The aryl group in the formula can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0190] As R 210 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0191] As R 210 The alkenyl group in the form of carbon atoms preferably has a carbon number of 2 to 10.

[0192] In the aforementioned equations (ca-4) and (ca-5), Y 201 Each can be independently represented as arylene, alkylene, or alkenyl.

[0193] About Y 201 The subarylene group in R' can be cited as an example. 201 The aromatic hydrocarbon group in the example is a group formed by removing one hydrogen atom from the aryl group.

[0194] About Y 201 The alkylene and alkenylene groups in R' can be exemplified by those derived from R'. 201 The chain alkyl group or chain alkenyl group in the example group is formed by removing one hydrogen atom.

[0195] In the aforementioned equations (ca-4) and (ca-5), x is 1 or 2.

[0196] W 201 It is a (x+1) valence, that is, a divalent or trivalent linker.

[0197] As W 201 The divalent linking group in the above formula (Ap-1) is preferably a divalent hydrocarbon group that may have substituents, and is preferably related to R in the above formula (Ap-1). EP The example shown is the same group that can have substituents, specifically divalent hydrocarbon groups. 201 The divalent linking group can be any of straight-chain, branched, or cyclic, preferably cyclic. Preferably, it is a group formed by combining two carbonyl groups at both ends of the arylene group, or a group formed solely by the arylene group. Examples of arylene groups include phenylene and naphthylene, with phenylene being particularly preferred.

[0198] As W 201 The trivalent linker in the W can be cited as an example. 201 Groups formed by removing one hydrogen atom from a divalent linker, and groups formed by further bonding the aforementioned divalent linker to the aforementioned divalent linker, etc. As W 201 The trivalent linking group in the group is preferably a group formed by bonding two carbonyl groups to an arylene group.

[0199] As preferred cations represented by the aforementioned formula (ca-1), examples include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0200] [Chemical Formula 17] [Chemical Formula 18] [In the formula, R”] 201 It is a hydrogen atom or a substituent. As this substituent, it is related to the aforementioned R... 201 ~R 207 and R 210 ~R 212 The same applies to groups that may have substituents. Furthermore, as the cation represented by the aforementioned formula (ca-1), the cations represented by the following general formulas (ca-1-25) to (ca-1-35) are preferred.

[0201] [Chemical Formula 19] [Chemical Formula 20] [In the formula, R'] 211It is an alkyl group. R hal It consists of hydrogen atoms or halogen atoms. Furthermore, as the cation represented by the aforementioned formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are preferred.

[0202] [Chemical Formula 21] Furthermore, as the cation represented by the aforementioned formula (ca-1), it is also preferred to have cations represented by the following chemical formulas (ca-1-49) to (ca-1-54) having benzoylphenyl.

[0203] [Chemical Formula 22] Preferred cations represented by the aforementioned formula (ca-2) include, specifically, diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc.

[0204] As preferred cations represented by the aforementioned formula (ca-3), examples include cations represented by formulas (ca-3-1) to (ca-3-6) respectively.

[0205] [Chemical Formula 23] As preferred cations represented by the aforementioned formula (ca-4), examples include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0206] [Chemical Formula 24] Furthermore, as the cation represented by the aforementioned formula (ca-5), the cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferred.

[0207] [Chemical Formula 25] [In the formula, R'] 212 It consists of an alkyl group or a hydrogen atom. R' 211 It is an alkyl group. In the above, the cation part [(Q q＋ ) 1 / q The preferred cation is represented by the general formula (ca-1), more preferably by the cations represented by formulas (ca-1-1) to (ca-1-54), and even more preferably by the cations represented by formulas (ca-1-49) to (ca-1-54).

[0208] Other cationic polymerization initiators Examples of cationic polymerization initiators other than the above-mentioned (I1) component include compounds represented by the following general formula (I2-1) or (I2-2) (hereinafter referred to as "(I2) component"); and compounds represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "(I3) component").

[0209] Regarding the composition of (I2): (I2) is a compound represented by the following general formula (I2-1) or (I2-2).

[0210] The (I2) component produces a strong acid upon exposure, thus, when using a negative photosensitive composition containing the (I) component to form a pattern, sufficient sensitivity can be obtained and a good pattern can be formed.

[0211] [Chemical Formula 26] [In the formula, R] b05 It can be a fluoroalkyl group or a fluorine atom that may have substituents. Multiple R b05 They can be the same or different. q is an integer greater than or equal to 1. q＋ It is a q-valent organic cation. [Chemical Formula 27] [In the formula, R] b06 It can be a fluoroalkyl group or a fluorine atom that may have substituents. Multiple R b06 They can be the same or different. q is an integer greater than or equal to 1. q＋ It is a q-valent organic cation. • Anion section In the aforementioned equation (I2-1), R b05 It can be a fluoroalkyl group or a fluorine atom that may have substituents. Multiple R b05 They can be the same or different.

[0212] R b05 The fluoroalkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. Specifically, examples include groups obtained by substituting some or all of the hydrogen atoms in an alkyl group having 1 to 5 carbon atoms with fluorine atoms.

[0213] Among them, as R b05 Preferably, it is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and even more preferably a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group.

[0214] The anionic portion of the compound represented by formula (I2-1) is preferably an anion represented by the following general formula (b0-2a).

[0215] [Chemical Formula 28] [In the formula, R] bf05 It is a fluoroalkyl group that can have substituents. 1 Integers from 1 to 5. In equation (b0-2a), R is... bf05 The fluoroalkyl group that may have substituents, and the aforementioned R b05 The same applies to fluoroalkyl groups that can have substituents, as mentioned above.

[0216] In equation (b0-2a), nb 1 Preferably, it is an integer from 1 to 4, more preferably an integer from 2 to 4, and most preferably 3.

[0217] In the aforementioned equation (I2-2), R b06 It can be a fluoroalkyl group or a fluorine atom that may have substituents. Multiple R b06 They can be the same or different.

[0218] R b06 The fluoroalkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. Specifically, examples include groups obtained by substituting some or all of the hydrogen atoms in an alkyl group having 1 to 5 carbon atoms with fluorine atoms.

[0219] Among them, as R b06 Preferably, it is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and even more preferably a fluorine atom.

[0220] • Cation section In equations (I2-1) and (I2-2), q is an integer greater than or equal to 1, and Q q＋ It is a q-valent organic cation.

[0221] As the Q q＋ Examples of Q in equation (I1) above can be cited. q＋ The same cation, wherein the cation represented by the general formula (ca-1) is preferred, and the cation represented by each of the formulas (ca-1-1) to (ca-1-54) is more preferred.

[0222] Regarding the components of (I3): (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0223] [Chemical Formula 29] [In the formula, R] b11 ~Rb12 It can be a cyclic group having substituents other than halogen atoms, a chain alkyl group having substituents other than halogen atoms, or a chain alkenyl group having substituents other than halogen atoms. m is an integer greater than or equal to 1, M m ＋ Each is an m-valent organic cation. {(I3-1) ingredient} • Anion section In equation (I3-1), R b12 R' can be a cyclic group having substituents other than halogen atoms, a chain alkyl group having substituents other than halogen atoms, or a chain alkenyl group having substituents other than halogen atoms; examples of R' are mentioned above. 201 The description refers to cyclic groups, chain alkyl groups, and chain alkenyl groups that do not have substituents or groups that have substituents other than halogen atoms.

[0224] As R b12 Preferably, it is a chain alkyl group that may have substituents other than halogen atoms, or an aliphatic cyclic group that may have substituents other than halogen atoms.

[0225] As a chain alkyl group, it is preferred to have 1 to 10 carbon atoms, more preferably 3 to 10. As an aliphatic cyclic group, it is more preferably a group formed by removing one or more hydrogen atoms from adamantane, norbornane, isoboronane, tricyclodecane, tetracyclododecane, etc. (it may also have substituents other than halogen atoms); or a group formed by removing one or more hydrogen atoms from camphor, etc.

[0226] R b12 The hydrocarbon group may have substituents other than halogen atoms. Examples of such substituents include R in the aforementioned formula (I3-2). b11 The hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) can have the same substituent group as the halogen atom.

[0227] The phrase "may have substituents other than halogen atoms" here excludes not only substituents formed solely of halogen atoms, but also substituents containing even one halogen atom (e.g., fluoroalkyl substituents).

[0228] Hereinafter, preferred examples of the anionic portion of component (I3-1) are shown.

[0229] [Chemical Formula 30] • Cation section In equation (I3-1), M m＋ It is an m-valent organic cation.

[0230] As M m＋ The organic cation is preferably the same as the cation represented by each of the above general formulas (ca-1) to (ca-5), with the cation represented by the above general formula (ca-1) being more preferred. From the perspective of improving resolution and roughness characteristics, R in the above general formula (ca-1) is particularly preferred. 201 R 202 R 203 At least one of them is a sulfonium cation that is an organic group (aryl, heteroaryl, alkyl or alkenyl) with 16 or more carbon atoms that may have substituents.

[0231] As substituents that the aforementioned organic groups may have, examples include alkyl groups, halogen atoms, haloalkyl groups, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the formulas (ca-r-1) to (ca-r-10) above.

[0232] The number of carbon atoms in the aforementioned organic group (aryl, heteroaryl, alkyl, or alkenyl) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18, as the M. m＋ Organic cations, preferably, include those represented by the formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), (ca-1-46), and (ca-1-47) above, with the cation represented by formula (ca-1-29) above being particularly preferred.

[0233] {(I3-2) ingredient} • Anion section In equation (I3-2), R b11 R' can be a cyclic group having substituents other than halogen atoms, a chain alkyl group having substituents other than halogen atoms, or a chain alkenyl group having substituents other than halogen atoms; examples of R' are mentioned above. 201 The description refers to cyclic groups, chain alkyl groups, and chain alkenyl groups that do not have substituents or groups that have substituents other than halogen atoms.

[0234] Among them, as R b11 Preferably, the substituents are aromatic hydrocarbon groups that may have substituents other than halogen atoms, aliphatic cyclic groups that may have substituents other than halogen atoms, or chain alkyl groups that may have substituents other than halogen atoms. Examples of substituents that may be present in these groups include hydroxyl groups, oxo groups, alkyl groups, aryl groups, lactone-containing cyclic groups, ether bonds, ester bonds, or combinations thereof.

[0235] When the substituent includes an ether bond or an ester bond, it can be linked by an alkylene group. In this case, the linking groups represented by the following general formulas (y-al-1) to (y-al-7) are preferred as the substituents.

[0236] It should be noted that in the following general formulas (y-al-1) to (y-al-7), R is different from that in the above formula (I3-2). b11 The bond is V' in the following general formulas (y-al-1) to (y-al-7). 101 .

[0237] [Chemical Formula 31] [In the formula, V'] 101 It is a single bond or an alkylene group having 1 to 5 carbon atoms. V' 102 It is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms. V' 102 The divalent saturated hydrocarbon group is preferably an alkylene group with 1 to 30 carbon atoms, more preferably an alkylene group with 1 to 10 carbon atoms, and even more preferably an alkylene group with 1 to 5 carbon atoms.

[0238] As V' 101 and V' 102 The alkylene groups in the form can be straight-chain alkylene groups or branched alkylene groups, with straight-chain alkylene groups being preferred.

[0239] As V' 101 and V' 102 Specifically, examples of alkylene groups include methylene [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; ethylene [-CH2CH2-]; alkylmethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3)-. ) CH2- and other alkyl ethylenes; 1,3-propylene (n-propylene) [-CH2CH2CH2-]; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and other alkyl 1,3-propylenes; 1,4-butylene [-CH2CH2CH2CH2-]; -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkyl 1,4-butylenes; 1,5-pentylene [-CH2CH2CH2CH2CH2-] and so on.

[0240] Additionally, V' 101 or V'102 In the aforementioned alkylene group, a portion of the methylene group can be replaced by a divalent aliphatic cyclic group having 5 to 10 carbon atoms. This aliphatic cyclic group is preferably derived from R'. 201 The divalent group formed by further removing one hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group), more preferably a cyclohexylene, 1,5-adamantane subunit or 2,6-adamantane subunit.

[0241] As the aforementioned aromatic hydrocarbon group, phenyl or naphthyl is more preferred.

[0242] More preferably, the aliphatic cyclic group is a group formed by removing one or more hydrogen atoms from polycyclic hydrocarbons such as adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0243] As for the aforementioned chain alkyl group, it is preferred that the number of carbon atoms is 1 to 10. Specifically, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and branched-chain alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0244] As R b11 Preferably, the cyclic group may have substituents other than halogen atoms.

[0245] The following shows a preferred example of the anionic portion of component (I3-2).

[0246] [Chemical Formula 32] • Cation section In equation (I3-2), M m＋ It is an m-valent organic cation, and M in the aforementioned formula (I3-1) m＋ same.

[0247] Furthermore, considering the high elasticity of the photosensitive film and the ease with which a fine structure can be formed without residue, component (I) is preferably a cationic polymerization initiator that produces an acid with a pKa (acid dissociation constant) of -5 or less upon exposure. By using a cationic polymerization initiator that produces an acid with a more preferably pKa of -6 or less, and even more preferably a pKa of -8 or less, high sensitivity to exposure can be obtained. The lower limit of the pKa of the acid that produces component (I) is preferably -15 or more. High sensitivity is easily achieved by using a cationic polymerization initiator that produces an acid with the aforementioned preferred pKa.

[0248] Here, "pKa (acid dissociation constant)" refers to a parameter commonly used as an indicator of the acid strength of a substance. It should be noted that the pKa values ​​in this specification are values ​​at 25°C. Furthermore, pKa values ​​can be determined using known methods. Alternatively, they can be calculated using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development Corporation).

[0249] As component (I), one type can be used alone or two or more types can be used together.

[0250] In the negative photosensitivity composition used in this embodiment, component (I) is preferably selected from at least one of the group consisting of components (I1), (I2) and (I3), and component (I1) is more preferably used.

[0251] In the negative photosensitive composition used in this embodiment, when the total mass parts of the (Ap) component and the (Am) component are taken as 100 parts by mass, the content of the (I) component is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, further preferably 0.15 to 3 parts by mass, and particularly preferably 0.2 to 1 part by mass.

[0252] If the content of component (I) is above the lower limit of the aforementioned preferred range, sufficient sensitivity can be obtained, further improving the etching characteristics of the pattern. Furthermore, the strength of the photosensitive film can be further improved. On the other hand, if it is below the upper limit of the aforementioned preferred range, the sensitivity can be moderately controlled, and a pattern with a good shape can be easily obtained.

[0253] <Other Ingredients> In addition to the (Ap), (Am) and (I) components described above, the negative photosensitive composition of this embodiment may also contain other components as needed.

[0254] As desired, additives containing miscibility, such as epoxy compounds other than (Ap) and (Am) components, silane coupling agents, sensitizing agents, metal oxides (M), solvents, additional resins for improving film properties, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, anti-halo agents, etc., may be appropriately added to the negative photosensitive composition of the embodiment.

[0255] Silane coupling agents can be used as adhesive aids to improve adhesion to substrates.

[0256] Examples of silane coupling agents include those with reactive substituents such as carboxyl, methacryloyl, isocyanate, and epoxy groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0257] Silane coupling agents can be used alone or in combination with two or more.

[0258] The content of the silane coupling agent is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the (PO) component, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3 parts by mass.

[0259] If the content of the silane coupling agent is within the aforementioned preferred range, the strength of the cured film is further improved. Furthermore, the adhesion between the cured film and the substrate can be further enhanced.

[0260] There are no particular restrictions on the sensitizer component; any substance that can absorb exposure-based energy and transfer that energy to other substances is acceptable.

[0261] Specifically, the following sensitizers can be used as sensitizer components: benzophenone, p,p'-tetramethyldiaminobenzophenone and other benzophenone-based photosensitizers; carbazole-based photosensitizers; acetophenone-based photosensitizers; naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene; phenol-based photosensitizers; anthracene-based photosensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9-ethoxyanthracene; and known photosensitizers such as diacetyl, eosin, rose safflower, pyrene, phenothiazine, and anthrone.

[0262] Sensitizers can be used alone or in combination with two or more.

[0263] The content of the sensitizer component is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of component (P0), more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass.

[0264] When the content of the sensitizer component is within the aforementioned preferred range, the sensitivity and resolution are further improved.

[0265] From the perspective of easily obtaining a cured film with improved strength, the negative photosensitive composition of this embodiment may also contain a metal oxide (M) (hereinafter also referred to as "(M) component"). In addition, by using the (M) component, it is possible to form a high-resolution pattern with good shape.

[0266] As a component (M), examples include oxides of metals such as silicon (metallic silicon), titanium, zirconium, and hafnium. Among these, oxides of silicon are preferred, and silicon dioxide is particularly preferred.

[0267] In addition, the shape of component (M) is preferably particulate.

[0268] As the particulate (M) component, it is preferable to form a (M) component consisting of a group of particles with a volume average particle size of 5 to 40 nm, more preferably a (M) component consisting of a group of particles with a volume average particle size of 5 to 30 nm, and even more preferably a (M) component consisting of a group of particles with a volume average particle size of 10 to 20 nm.

[0269] When the volume average particle size of component (M) is above the lower limit of the aforementioned preferred range, the strength of the cured film will be easily improved. On the other hand, when it is below the upper limit of the aforementioned preferred range, residues will be less likely to be generated during pattern formation, and higher resolution patterns will be easier to form. In addition, the transparency of the photosensitive film is improved.

[0270] The particle size of the (M) component can be appropriately selected based on the exposure light source. Generally, it is considered that for particles with a particle size of less than 1 / 10 of the wavelength of light, the effect of light scattering can be basically ignored. Therefore, for example, when forming a fine structure using i-line (365nm) photolithography, a particle group (particularly silicon dioxide particles) with a primary particle size (volume average) of 10 to 20 nm is preferably used as the (M) component.

[0271] As component (M), one type can be used alone, or two or more types can be used together.

[0272] The content of component (M) is preferably 5 to 50 parts by mass relative to 100 parts by mass of component (P0), and more preferably 10 to 40 parts by mass.

[0273] When the content of component (M) is above the lower limit of the aforementioned preferred range, the strength of the cured film is further improved. On the other hand, when it is below the upper limit of the aforementioned preferred range, the transparency of the photosensitive film is further improved.

[0274] The negative photosensitive composition of this embodiment may also contain a solvent (hereinafter, sometimes referred to as "(S) component").

[0275] Examples of (S) components 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; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds with ester bonds such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; and compounds with ether bonds such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc., of the aforementioned polyols or compounds with ester bonds. Derivatives of polyols [among which, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethyl sulfoxide (DMSO).

[0276] (S) Component can be used alone or as a mixed solvent of two or more.

[0277] The amount of component (S) is not particularly limited, and can be appropriately set according to the coating film thickness to achieve a concentration that allows the negative photosensitive composition to be coated onto a substrate or the like without dripping.

[0278] For example, the (S) component can be used in a manner where the solid component concentration reaches 70% by mass or more, or the (S) component can be used in a manner where the solid component concentration reaches 60% by mass or more.

[0279] In addition, it is possible to adopt a scheme that does not substantially contain (S) components (i.e., a scheme with a solid component concentration of 100% by mass).

[0280] The negative photosensitive composition described above contains a multifunctional epoxy compound (Ap) with three or more functions and a difunctional aromatic epoxy compound (Am) with a molecular weight of 800 or less. The content of the (Am) component is 0.6 to 10% by mass relative to the total content (100% by mass) of the (Ap) component and the (Am) component.

[0281] The negative photosensitive composition of this embodiment contains a predetermined amount of (Ap) component, thus easily reducing solubility upon exposure. Furthermore, the presence of a predetermined amount of (Am) component facilitates improved flowability. Through these synergistic effects, the negative photosensitive composition of this embodiment can form well-shaped patterns, improving adhesion to the sidewalls of hollow structures.

[0282] (Photosensitive resist film) The photosensitive resist film involved in this embodiment is formed by sequentially stacking a photosensitive film and a cover film using the photosensitive composition of the above embodiment on a substrate film.

[0283] The photosensitive resist film involved in this embodiment can be manufactured, for example, by coating the photosensitive composition of the above embodiment onto a substrate film, drying it to form a photosensitive film, and then laminating a cover film on the photosensitive film.

[0284] For coating photosensitive compositions onto a substrate film, appropriate methods based on blade coaters, lip coaters, comma coaters, die coaters, etc., can be used.

[0285] The thickness of the photosensitive film is preferably less than 100 μm, and more preferably 5 to 50 μm.

[0286] The substrate film can be any known film, such as a thermoplastic resin film. Examples of such thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 to 150 μm.

[0287] For the cover film, known films can be used, such as polyethylene film, polypropylene film, etc. Preferably, the cover film has a lower adhesion strength to the photosensitive film than the substrate film.

[0288] The thickness of the covering film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm.

[0289] The substrate film and the cover film can be made of the same film material or different film materials.

[0290] (Manufacturing method of hollow structure) The method for manufacturing a hollow structure according to this embodiment is a method for manufacturing a hollow structure including a recess and a top plate portion that seals the opening surface of the recess, wherein the aforementioned negative photosensitive composition is used to form the aforementioned top plate portion.

[0291] Figure 1 This is a schematic diagram illustrating the manufacturing method of the hollow structure according to this embodiment.

[0292] The manufacturing method of the hollow structure shown in the figure includes a step of forming sidewalls on a substrate (step 1 (S1)); and a step of forming a top plate portion on the aforementioned sidewalls to manufacture the aforementioned hollow structure (step 2 (S2)). Details of step 1 (S1) and step 2 (S2) will be described below.

[0293] [Step 1 (S1)] In the first process, a sidewall 20 is formed on the substrate 10 to obtain a substrate 10 with a recess 15 on its surface.

[0294] Figure 1 In the [first process], a substrate 10 is shown having a recess 15 on its surface through a substrate 10 and a sidewall 20 formed on the substrate 10.

[0295] Regarding substrates with recesses on their surfaces: Examples of substrates 10 having recesses 15 on their surface include structures formed by patterning on the substrate 10 and stepped substrates. It should be noted that the recesses 15 can be made of organic or inorganic materials.

[0296] Such a substrate 10 having recesses 15 on its surface can be manufactured, for example, by a method including the following steps: a step of forming a photosensitive film on a support using a negative photosensitive composition (hereinafter referred to as the "film formation step"); a step of exposing the aforementioned photosensitive film (hereinafter referred to as the "exposure step"); and a step of developing the exposed photosensitive film using a developer containing an organic solvent to form a negative pattern that becomes the sidewall 20 of the recesses 15 (hereinafter referred to as the "development step"). The method for manufacturing such a substrate 10 having recesses 15 on its surface can be performed as follows.

[0297] Membrane formation process: First, a negative photosensitive composition is coated onto a support using known methods such as spin coating, roller coating, or screen printing. For example, a baking treatment (post-coating baking (PAB)) is performed at a temperature of 50–150°C for 2–60 minutes to form a photosensitive film.

[0298] It should be noted that this film formation process can also be performed by placing a photosensitive composition layer pre-made using a negative photosensitive composition on the support.

[0299] There are no particular limitations on the support body; any known support body can be used, such as a substrate for electronic components or a support body on which a specified wiring pattern is formed.

[0300] As substrates used for electronic components, more specifically, examples 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.

[0301] Materials such as copper, aluminum, nickel, and gold can be used as wiring patterns.

[0302] The thickness of the photosensitive film formed using the negative photosensitive composition is not particularly limited, but is preferably around 10 to 100 μm.

[0303] Exposure process: Next, the formed photosensitive film is selectively exposed using a known exposure apparatus, either by exposure through a mask (mask pattern) with a predetermined pattern formed on it, or by direct electron beam irradiation without the mask pattern on it. Then, as needed, baking (post-exposure baking (PEB)) is performed for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds, at a temperature of 80 to 150°C.

[0304] There is no particular limitation on the wavelength used for exposure; selective irradiation (exposure) can be performed using radiation, such as ultraviolet light with a wavelength of 300–500 nm, i-rays (wavelength 365 nm), or visible light. As the source of these radiations, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc., can be used.

[0305] The term "radiation" here refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and proportion of each component in the composition, the film thickness, etc. For example, when using an ultra-high pressure mercury lamp, it ranges from 100 to 2000 mJ / cm². 2 .

[0306] The exposure method for photosensitive films can be either conventional exposure (dry exposure) in inert gases such as air or nitrogen, or liquid immersion lithography.

[0307] Developing process: Next, the exposed photosensitive film is developed using a developer containing an organic solvent (organic developer). After development, rinsing is preferably performed. Baking (post-baking) may be performed as needed.

[0308] The organic solvents contained in organic-based developers can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0309] 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, acetone-based acetone, ionone, diacetone-based alcohol, acetoethanol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methylpentyl ketone (2-heptanone). Among these, methylpentyl ketone (2-heptanone) is preferred as a ketone solvent.

[0310] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy, ethyl ethoxy, 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, diethylene glycol monoethyl 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, propylene glycol monopropyl ether acetate, 2- Ethoxybutyl ester, 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, lactic acid Ethyl acetate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc. Among these, butyl acetate or PGMEA is preferred as an ester solvent.

[0311] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0312] As needed, known additives can be incorporated into organic developers. Examples of such additives include surfactants. There are no particular limitations on the surfactant; for example, ionic, nonionic fluorinated, and / or silicone surfactants can be used.

[0313] As a surfactant, a nonionic surfactant is preferred, and a nonionic fluorinated surfactant or a nonionic silicone surfactant is more preferred.

[0314] When a surfactant is used, its amount relative to the total amount of organic developer is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0315] The developing process can be carried out using known developing methods, such as: immersing the support in the developing solution for a certain time (immersion method); using surface tension to make the developing solution rise on the surface of the support and remain stationary for a certain time (spinning immersion method); spraying the developing solution onto the surface of the support (spraying method); and continuously coating the developing solution onto a support that is rotating at a certain speed while the developing solution coating nozzle is scanning at a certain speed (dynamic distribution method), etc.

[0316] The rinsing process (cleaning process) using rinsing solution can be carried out using known rinsing methods. Examples of such rinsing methods include: continuously coating the rinsing solution onto a support rotating at a certain speed (rotation coating); immersing the support in the rinsing solution for a certain time (immersion method); spraying the rinsing solution onto the surface of the support (spraying method); and so on.

[0317] The rinsing process preferably uses a rinsing solution containing organic solvents.

[0318] Through the above-described film formation process, exposure process and development process, a substrate 10 (a structure or step substrate obtained by forming a pattern on a substrate) with a recess 15 on its surface can be manufactured.

[0319] The thickness (horizontal dimension relative to the support) and height (vertical dimension relative to the support) of the sidewall 20 can be appropriately set based on the size of the hollow portion, which is determined according to the type of electronic equipment housed in the recess 15.

[0320] [Step 2 (S2)] In the second step of this embodiment, an exposure section 30A, which becomes the top plate portion, is formed on the sidewall 20 formed in the first step, and the aforementioned hollow structure is manufactured.

[0321] The second step in this embodiment includes the following steps: (i); (ii); (iii); (iv); and (v).

[0322] Step (i): A step in which a photosensitive resist film 30F is disposed such that the opening surface of the recess 15 formed by the sidewall 20 and the substrate 10 is sealed with a photosensitive resist film 30F, and a substrate film is peeled off from the photosensitive film 30 constituting the photosensitive resist film 30F. Step (ii): The step of exposing the photosensitive film 30 after the aforementioned step (i). Step (iii): A step of heat-treating the photosensitive film 30 after step (ii). Step (iv): After the aforementioned step (iii), the photosensitive film 30 is developed, and a negative pattern (exposure section 30A) is formed in the substrate 10 prepared in the first step (S1) that has recesses 15 on its surface, sealing the opening of the recesses 15 formed by the sidewalls 20 and the substrate 10. Step (v): The negative pattern (exposure section 30A) following step (iv) is further heated to cure it, thereby obtaining a hollow structure 100 formed by the cured body 40 of the aforementioned photosensitive film as the exposure section 30A of the aforementioned top plate. The hollow structure manufactured by the method described herein includes a recess 15 and a top plate portion that seals the opening of the recess 15. This hollow structure is preferably used for hollow encapsulation in SAW filters, MEMS, various sensors, and the like.

[0323] Regarding photosensitive resist films The photosensitive resist film 30F in this embodiment, for example, has a negative photosensitive film 30 formed from the above-described negative photosensitive composition.

[0324] When a photosensitive film 30 is formed using the photosensitive resist film 30F and the photosensitive film 30 is selectively exposed, the cationic part of component (I) in the exposure section 30A of the photosensitive film 30 decomposes to produce acid, and the epoxy group in component (A) undergoes ring-opening polymerization through the action of the acid.

[0325] Therefore, in the exposed portion 30A of the photosensitive film 30, the solubility of component (A) in the developer containing organic solvent decreases, while in the unexposed portion 30B of the photosensitive film 30, the solubility of component (A) in the developer containing organic solvent remains unchanged. Thus, a difference in solubility in the developer containing organic solvent arises between the exposed portion 30A and the unexposed portion 30B of the photosensitive film 30. That is, the photosensitive film 30 is negative. Therefore, if the photosensitive film 30 is developed with a developer containing organic solvent, the unexposed portion 30B can be dissolved and removed, forming a negative pattern.

[0326] Here, the negative photosensitive film 30 of the photosensitive resist film 30F is typically composed of a B-stage (semi-cured) resin material.

[0327] As a photosensitive resist film 30F, examples include resist films included in a laminated film obtained by laminating a photosensitive film 30 on a substrate film. The photosensitive resist film 30F according to this embodiment is preferably used in a laminated film obtained by laminating a photosensitive film 30 on a substrate film.

[0328] The photosensitive resist film 30F can be manufactured by coating the above-mentioned negative photosensitive composition onto a substrate film and drying it to form the photosensitive film 30.

[0329] The coating of the negative photosensitive composition onto the substrate film can be carried out using appropriate methods based on a coater, blade coater, lip coater, comma coater, die coater, etc.

[0330] The thickness of the photosensitive film 30 is preferably less than 100 μm, and more preferably 5 to 50 μm.

[0331] The substrate film can be any known film, such as a thermoplastic resin film. Examples of such thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 to 150 μm.

[0332] [[Process (i)]] In step (i), the photosensitive resist film 30F is disposed such that the surface of the photosensitive film 30 constituting the photosensitive resist film 30F seals the opening surface of the recess 15. Then, the aforementioned substrate film is peeled off from the photosensitive film 30 constituting the photosensitive resist film 30F.

[0333] Figure 1 In this process, the photosensitive film 30 constituting the photosensitive resist film 30F is arranged opposite to the substrate 10 with the sidewall 20 in between. Then, a hollow, sealed space (cavity) is formed by the substrate 10, the sidewall 20 and the photosensitive film 30.

[0334] [[Process (ii)]] In step (ii), the photosensitive film 30 is exposed.

[0335] For example, using a known exposure device, the photosensitive film 30 is selectively exposed through a photomask 60 with a prescribed pattern.

[0336] The wavelength used in the exposure is not particularly limited; selective irradiation (exposure) is performed using radiation, such as ultraviolet light (300–500 nm), GHI rays, I rays (365 nm wavelength), or visible light. Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc., can be used as the radiation source. The preferred irradiation dose during exposure is 100–1500 mJ / cm². 2 More preferably 200–900 mJ / cm 2 .

[0337] [[Process (iii)]] In step (iii), the exposed photosensitive film 30 is subjected to heat treatment, known as post-exposure baking (PEB) treatment.

[0338] PEB treatment is performed, for example, at a temperature of 80–150°C for 40–600 seconds, preferably 60–300 seconds.

[0339] Through the heat treatment in step (iii), the exposed photosensitive film 30 becomes the exposed part 30A, in which the epoxy groups in component (A) have undergone ring-opening polymerization, and the unexposed part 30B, which remains unchanged.

[0340] [[Process (iv)]] In step (iv), the photosensitive film 30 (exposed part 30A, unexposed part 30B) after PEB treatment is developed to form a negative pattern (exposed part 30A).

[0341] The development process here can be performed in the same way as the [development process] described above. After development, rinsing is preferably performed.

[0342] During development in step (iv), the unexposed portion 30B is dissolved and removed, while the exposed portion 30A remains as a negative pattern. The exposed portion 30A becomes the top plate portion (the top of the opening surface of the sealing recess).

[0343] [[Process (v)]] In step (v), the developed negative pattern (exposure section 30A) is further subjected to heat treatment (curing operation) to cure it, thereby obtaining a hollow structure 100 formed by the cured body 40 of the photosensitive film 30 in the exposure section 30A (top plate section). The heat treatment is performed, for example, at a temperature of 150 to 300°C for 10 minutes to 5 hours, preferably 1 to 3 hours. A nitrogen atmosphere is preferred as the atmosphere for the heat treatment.

[0344] Figure 1 In the solidified body 40, the photosensitive material forming the sidewall 20 and the photosensitive film 30 are solidified and integrated.

[0345] (Pattern Formation Method) The pattern forming method of this embodiment includes: a step of forming a photosensitive film on a support using the negative photosensitive composition of the above embodiment (hereinafter referred to as the "film forming step"); a step of exposing the aforementioned photosensitive film (hereinafter referred to as the "exposure step"); and a step of developing the aforementioned exposed photosensitive film with a developer containing an organic solvent to form a negative pattern (hereinafter referred to as the "development step").

[0346] The pattern forming method of this embodiment can be performed, for example, in the following manner.

[0347] [Membrane Formation Process] First, the negative photosensitive composition of the above embodiment is coated on a support using known methods such as spin coating, roller coating, screen printing, or doctor blade coating. For example, a baking treatment (post-coating baking (PAB)) is performed at a temperature of 60 to 180°C for 2 to 60 minutes to form a photosensitive film.

[0348] It should be noted that the film forming process can also be performed by placing the photosensitive composition layer of the aforementioned laminated film on a support.

[0349] There are no particular limitations on the support structure; conventionally known supports can be used, such as substrates for electronic components and supports on which a specified wiring pattern is formed. More specifically, 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, can be used. Materials used for the wiring pattern include, for example, copper, aluminum, nickel, and gold.

[0350] The pattern forming method of this embodiment is useful, for example, for lithium tantalate (LiTaO3) substrates and lithium niobate (LiNbO3) substrates used in SAW devices mounted on communication terminals.

[0351] The thickness of the photosensitive film formed using the negative photosensitive composition is not particularly limited, but is preferably around 10 to 100 μm. The negative photosensitive composition of the above embodiments also exhibits good properties when formed as a thick film.

[0352] [Exposure Process] Next, the formed photosensitive film is subjected to selective exposure using a known exposure apparatus, either by exposure through a mask with a predetermined pattern (mask pattern) or by drawing using direct electron beam irradiation without the mask pattern. Then, as needed, baking (post-exposure baking (PEB)) is performed for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds, at a temperature of 80 to 150°C.

[0353] There are no particular restrictions on the wavelength used for exposure; selective irradiation (exposure) can be performed using radiation, such as ultraviolet light with wavelengths of 300–500 nm, i-rays (wavelength 365 nm), or visible light. Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc., can be used as the source of these radiations.

[0354] The term "radiation" here refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and proportion of each component in the composition, the film thickness, etc. For example, when using an ultra-high pressure mercury lamp, it ranges from 100 to 2000 mJ / cm². 2 .

[0355] The exposure method for photosensitive films can be either conventional exposure (dry exposure) in inert gases such as air or nitrogen, or liquid immersion lithography.

[0356] The photosensitive film after the exposure process has high transparency. For example, the haze value when irradiated with i-line (wavelength 365nm) is preferably less than 3%, and more preferably 1.0 to 2.5%.

[0357] Thus, the photosensitive film formed using the negative photosensitive composition of the above embodiment has high transparency. Therefore, during exposure in pattern formation, light transmittance is increased, and negative patterns with good etching characteristics are easily obtained.

[0358] The haze value of the photosensitive film after the exposure process was determined using the method in accordance with JIS K 7136 (2000).

[0359] [Developing process] Next, the exposed photosensitive film is developed using a developer containing an organic solvent (organic developer). After development, rinsing is preferably performed. Baking (post-baking) may be performed as needed.

[0360] As for the organic solvent contained in the organic-based developer, it is only necessary to be a solvent that can dissolve the (P0) component (the (P0) component before exposure), and it can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and hydrocarbon solvents can be cited.

[0361] 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, acetone-based acetone, ionone, diacetone-based alcohol, acetoethanol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methylpentyl ketone (2-heptanone). Among these, methylpentyl ketone (2-heptanone) is preferred as a ketone solvent.

[0362] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy, ethyl ethoxy, 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, diethylene glycol monoethyl 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, propylene glycol monopropyl ether acetate, 2- Ethoxybutyl ester, 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, lactic acid Ethyl acetate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc. Among these, butyl acetate or PGMEA is preferred as an ester solvent.

[0363] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0364] As needed, known additives can be incorporated into organic developers. Examples of such additives include surfactants. There are no particular limitations on the surfactant; for example, ionic, nonionic fluorinated, and / or silicone surfactants can be used.

[0365] As a surfactant, a nonionic surfactant is preferred, and a nonionic fluorinated surfactant or a nonionic silicone surfactant is more preferred.

[0366] When a surfactant is used, the amount of surfactant used is typically 0.001 to 5% by mass relative to the total amount of organic developer, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0367] The developing process can be carried out using known developing methods, such as: immersing the support in the developing solution for a certain time (immersion method); using surface tension to make the developing solution rise on the surface of the support and remain stationary for a certain time (spinning immersion method); spraying the developing solution onto the surface of the support (spraying method); and continuously coating the developing solution onto a support that is rotating at a certain speed while the developing solution coating nozzle is scanning at a certain speed (dynamic distribution method), etc.

[0368] The rinsing process (cleaning process) using rinsing solution can be carried out using known rinsing methods. Examples of such rinsing methods include: continuously coating the rinsing solution onto a support rotating at a certain speed (rotation coating); immersing the support in the rinsing solution for a certain time (immersion method); spraying the rinsing solution onto the surface of the support (spraying method); and so on.

[0369] The rinsing process preferably uses a rinsing solution containing organic solvents.

[0370] Through the above-mentioned film formation process, exposure process and development process, negative patterns can be formed.

[0371] (cured film) The cured film of this embodiment is obtained by curing the negative photosensitive composition of the above embodiment.

[0372] (Method for manufacturing the cured film) The method for manufacturing the cured film according to this embodiment includes: a step (i) of forming a photosensitive film on a support using the negative photosensitive composition of the above embodiment; and a step (ii) of curing the aforementioned photosensitive film to obtain a cured film.

[0373] The operation of step (i) can be performed in the same way as the [film formation step] described above. The baking process can be performed, for example, at a temperature of 60 to 150°C for 40 to 600 seconds.

[0374] The curing process in step (ii) can be carried out, for example, at a temperature of 100–250°C for 0.5–2 hours.

[0375] In addition to steps (i) and (ii), the method for manufacturing the cured film according to the embodiments may also include other steps. For example, between steps (i) and (ii), there may be the above-mentioned [exposure step], in which the photosensitive film formed in step (i) is selectively exposed to cure the photosensitive film (pre-cured film) that has undergone baking (PEB) treatment as needed, thereby obtaining a cured film.

[0376] According to the method for manufacturing the cured film according to the above embodiments, it is possible to easily manufacture a cured film that faithfully reproduces the mask pattern.

[0377] Example The present invention will be described below by way of examples, but the present invention is not limited to the following examples.

[0378] <Preparation of Negative Photosensitive Compositions> (Examples 1-10, Comparative Examples 1-2) The components shown in Table 1 were mixed and dissolved in methyl ethyl ketone (MEK), and filtered using a PTFE filter (1 μm pore size, manufactured by PALL) to prepare negative photosensitive compositions (78% by mass solution of solid components) for each example.

[0379] [Table 1] In Table 1, each abbreviation has the following meaning. The value in [ ] is the amount of each component (parts by mass; converted according to solid components).

[0380] (A)-1: The following chemical formula (A1-1) represents a multifunctional epoxy compound.

[0381] [Chemical Formula 33] (A)-2: The following chemical formula (A1-2) represents a multifunctional epoxy compound.

[0382] [Chemical Formula 34] (A)-3: The following chemical formula (A1-3) represents a difunctional aromatic epoxy compound.

[0383] [Chemical Formula 35] (A)-4: The following chemical formula (A1-4) represents a difunctional alicyclic epoxy compound.

[0384] [Chemical Formula 36] (I)-1: Sulfonium salt represented by the following chemical formula (I0-1).

[0385] [Chemical Formula 37] <Pattern Formation Method> A negative pattern (residual film) is formed on a silicon wafer through the following film formation, exposure, and development processes, and the cone angle is evaluated.

[0386] Membrane formation process: The negative photosensitive compositions of each example are coated onto the substrate film using a coater, and then baked in an oven at 70°C for 10 minutes (PAB) to form a photosensitive film with a film thickness of 20 μm, thereby obtaining a laminated film.

[0387] A photosensitive resist film was laminated on a silicon wafer at 80°C, 0.3 MPa, and 0.5 m / min.

[0388] Bake on a 120°C heating plate for 5 minutes (PAB).

[0389] Exposure process: The operation of peeling the substrate film from the photosensitive film of the aforementioned laminated film is performed.

[0390] Next, the exposure unit was aligned using a SUSS MicroTec MA / BA 8 Gen4 Pro, with the gap set to 30 μm and the intensity at 400 mJ / cm². 2 The photosensitive film was irradiated with ghi rays. Then, the exposed photosensitive film was heated for 5 minutes on a heating plate at 110°C.

[0391] Developing process: Using propylene glycol monomethyl ether acetate as the developer, the heat-treated photosensitive film was developed for 120 seconds to form a negative pattern (residual film). The result was a 50μm × 50μm square pattern.

[0392] [Evaluation of the cone angle] Figure 2 A cross-sectional view of a substrate with a square pattern formed by silicon wafer 101 and residual film 501 of silicon wafer 101 is shown schematically. The square pattern was observed using a scanning electron microscope (product name: SU-5000, manufactured by Hitachi High-Tech Corporation), and the angle θ (cone angle) formed by the periphery of silicon wafer 101 and residual film 501 in contact with silicon wafer 101 was measured. The results were evaluated according to the following criteria. The evaluation results are shown in Table 2.

[0393] Judgment criteria: A: θ is above 87°.

[0394] B: θ is greater than 85° and less than 87°.

[0395] C: θ is greater than 80° and less than 85°.

[0396] D: θ is less than 80°.

[0397] Set evaluations A through C as qualified, and evaluation D as unqualified.

[0398] <Manufacturing of Hollow Structures> Using the negative photosensitive compositions of each example, a substrate with a recessed portion surrounded by sidewalls was prepared. The photosensitive film formed using the negative photosensitive compositions of each example was then adhered to the sidewalls in a manner that the opening of the recessed portion was sealed, and the adhesion was evaluated.

[0399] Membrane formation process: The negative photosensitive compositions of each example are coated onto the substrate film using a coater, and then baked in an oven at 70°C for 10 minutes (PAB) to form a photosensitive film with a film thickness of 20 μm, thereby obtaining a laminated film.

[0400] A photosensitive resist film was laminated on a silicon wafer at 80°C, 0.3 MPa, and 0.5 m / min.

[0401] Next, bake on a 120°C heating plate for 5 minutes (PAB).

[0402] Exposure process: The operation of peeling the substrate film from the photosensitive film of the aforementioned laminated film is performed.

[0403] Next, the exposure unit was aligned using a SUSS MicroTec MA / BA 8 Gen4 Pro, with the gap set to 30 μm and the intensity at 400 mJ / cm². 2 The photosensitive film was irradiated with ghi rays. Then, the exposed photosensitive film was heated for 5 minutes on a heating plate at 110°C.

[0404] Developing process: Next, PGMEA was used as the developer, and the mixture was immersion-developed at 23°C for 120 seconds. After drying, it was cured at 200°C for 1 hour under a nitrogen atmosphere.

[0405] Through the above operations, a substrate with a walled portion is obtained, in which a recessed pattern is formed on the Si substrate, with a 50 μm wide sidewall formed by a cured film surrounding a quadrilateral with a length of 1170 μm and a width of 1500 μm.

[0406] Next, using the same method as described above, a laminated film with a thickness of 20 μm was prepared using the negative photosensitive composition of each example.

[0407] Next, using a TEAM-100ARF manufactured by Takatori, the photosensitive film of the laminated film was laminated and adhered to the sidewall by sealing the opening of the aforementioned recess in the substrate with the aforementioned wall. The sidewalls (Wall) and top plate (Roof) of the hollow structure (the top of the opening sealing the aforementioned recess) were formed using the same negative photosensitive composition. The lamination conditions were: stage temperature 30°C, roller temperature 40°C, perforated plate temperature 23°C, roller speed 5.0 mm / s, roller pressure 300 kPa, and atmospheric open mode.

[0408] [Paste-based reviews] One hundred structures manufactured using the negative-type photosensitive compositions of various examples, with the top plate laminated on the sidewalls, were observed under a microscope. The number of structures with poor adhesion between the top plate and the sidewalls was counted based on the adhesion of the top plate, and the structures were evaluated according to the following criteria. The evaluation results are shown in Table 2.

[0409] Judgment criteria: A: The number of poorly pasted hollow structures is 0.

[0410] B: The number of poorly attached hollow structures is 1 to 3.

[0411] C: The number of poorly attached hollow structures is 4 to 9.

[0412] D: The number of poorly pasted hollow structures is more than 10.

[0413] Set evaluations A through C as qualified, and evaluation D as unqualified.

[0414] [Table 2] 10 Substrate, 15 Recess, 20 Sidewall, 30 Photosensitive film, 30A Exposure area (top plate), 30B Unexposed area, 30F Photosensitive resist film, 40 Cured body, 60 Photomask, 100 Hollow structure, 101 Silicon wafer, 501 Residual film.

Claims

1. A negative photosensitizing composition comprising a multifunctional epoxy compound with three or more functions, a cationic polymerization initiator, and a difunctional aromatic epoxy compound with a molecular weight of less than 800. The proportion of the difunctional aromatic epoxy compound is 0.6 to 10% by mass relative to the total content (100% by mass) of the polyfunctional epoxy compound and the difunctional aromatic epoxy compound.

2. The negative photosensitizing composition as claimed in claim 1, wherein, The proportion of the difunctional aromatic epoxy compound is 0.7 to 8% by mass relative to the total content (100% by mass) of the polyfunctional epoxy compound and the difunctional aromatic epoxy compound.

3. The negative photosensitizing composition as described in claim 1, wherein, The multifunctional epoxy compound comprises bisphenol Novolac type epoxy resin.

4. The negative photosensitizing composition as described in claim 3, wherein, The 2-functional aromatic epoxy compound contains a bisphenol epoxy monomer.

5. The negative photosensitive composition as claimed in claim 1 or 2, used for forming the top plate portion of a hollow structure comprising a recess and an opening surface of the recess.

6. A photosensitive resist film, wherein a photosensitive film formed using the negative photosensitive composition of claim 1 or 2 and a cover film are sequentially laminated on a substrate film.

7. A method for manufacturing a hollow structure, the hollow structure comprising a recess and a top plate portion that seals the opening of the recess, wherein in the manufacturing method, The top plate portion is formed using the negative photosensitive composition according to claim 1 or 2.

8. Pattern forming methods, including: The process of forming a photosensitive film on a support using the negative photosensitive composition according to claim 1 or 2; The process of exposing the photosensitive film; and A process of developing the exposed photosensitive film using a developer containing an organic solvent to form a negative pattern.

9. Pattern forming methods, including: The process of forming a photosensitive film on a support using the photosensitive resist film according to claim 5; The process of exposing the photosensitive film; and A process of developing the exposed photosensitive film using a developer containing an organic solvent to form a negative pattern.

Images