Negative photosensitive resin composition, pattern forming method, and laminated film

Abstract

This invention provides a negative photosensitive resin composition, a patterning method, and a laminated film. The negative photosensitive resin composition contains an epoxy-containing resin (A) and a cationic polymerization initiator (I), wherein the cationic polymerization initiator (I) comprises a sulfonate salt represented by the following general formula (I0). In formula (I0), R1 represents a thioxanthone group, and R2 represents an aryl group having 6 to 30 carbon atoms, wherein a portion of the hydrogen atoms of the aryl group is substituted or unsubstituted by a substituent (t), and the substituent (t) is an alkyl group having 1 to 18 carbon atoms. R3 to R5 are alkyl, hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, hydroxy(poly)alkoxy, or halogen atoms. k is 0, m is 0, and n is an integer from 1 to 4. When n is 2 or more, the plurality of R5s may be the same or different from each other. A is a group represented by -S-. X ‑ This refers to a monovalent polyatomic anion.

Description

Technical Field

[0001] This invention relates to negative photosensitive resin compositions, patterning methods, and laminated films. This application claims priority based on Japanese Patent Application No. 2020-117686, filed July 8, 2020, the contents of which are incorporated herein by reference. Background Technology

[0002] In recent years, with the miniaturization and increasing density of electronic components, the requirements for photosensitive resin compositions in electronic components with hollow, sealed structures, such as those used in surface acoustic wave (SAW) filters, have increased. In the formation of the hollow, sealed structure of these electronic components, the thinning and strength of the cured film obtained by curing the photosensitive resin composition have become essential.

[0003] Furthermore, photosensitive resin compositions are also used as spacers (wall materials) between semiconductor wafers and transparent substrates. For example, a photosensitive resin film is formed on the surface of a semiconductor wafer or the like using a negative photosensitive resin composition. This photosensitive resin film is then selectively exposed to radiation such as light or electron beams, and a development process is performed to form a pattern. Finally, it is bonded to a transparent substrate (e.g., a glass substrate) to form a spacer. In this photosensitive resin film, it is essential to form a film of the required thickness for the spacer during the development process using photolithography, and to be able to perform high-resolution patterning with good shape and no residue.

[0004] As a photosensitive material for forming the photosensitive resin film, photosensitive resin compositions containing an epoxy resin having two or more epoxy groups in one molecule, an alkali-soluble resin, and a cationic polymerization initiator have been disclosed in the past (see Patent Document 1).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2012 / 176750 Summary of the Invention

[0008] The technical problem that the invention aims to solve

[0009] As electronic components with hollow sealed structures continue to become smaller and denser, the formation of thick-film, fine-scale patterns becomes crucial in the formation of these structures.

[0010] However, in existing photosensitive resin compositions such as the composition described in Patent Document 1, poor resolution becomes a problem when attempting to miniaturize the pattern of the spacer that serves as the hollow sealing structure.

[0011] The present invention was made in view of the above circumstances, and its technical problem is to provide a negative photosensitive resin composition with further improved resolution, a pattern forming method using the negative photosensitive resin composition, and a laminated film using the negative photosensitive resin composition.

[0012] Solution to the above technical problems

[0013] To solve the above-mentioned technical problems, the present invention adopts the following structure.

[0014] That is, the first aspect of the present invention is a negative photosensitive resin composition, which is a negative photosensitive resin composition containing an epoxy resin (A) and a cationic polymerization initiator (I), characterized in that the cationic polymerization initiator (I) comprises a sulfonium salt (I0) represented by the following general formula (I0).

[0015]

Chemistry 1

[0016]

[0017] In formula (I0), R1 and R2 represent aryl groups with 6 to 30 carbon atoms, heterocyclic hydrocarbon groups with 4 to 30 carbon atoms, or alkyl groups with 1 to 30 carbon atoms, respectively. A portion of the hydrogen atoms of these aryl, heterocyclic hydrocarbon, or alkyl groups may be replaced by a substituent (t). This substituent (t) is derived from alkyl groups with 1 to 18 carbon atoms, hydroxyl groups, alkoxy groups with 1 to 18 carbon atoms, alkyl carbonyl groups with 2 to 18 carbon atoms, aryl carbonyl groups with 7 to 11 carbon atoms, acyloxy groups with 2 to 19 carbon atoms, arylthio groups with 6 to 20 carbon atoms, alkoxy groups with 1 to 18 carbon atoms, aryl groups with 6 to 10 carbon atoms, heterocyclic hydrocarbon groups with 4 to 20 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, and HO(-R) groups. A O)q-{R A O represents ethyleneoxy and / or propyleneoxy, q represents an integer from 1 to 5.} represents at least one group selected from the group consisting of hydroxyl (poly)alkoxide, and halogen atoms. R3 to R5 are respectively alkyl, hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, hydroxyl (poly)alkoxide, or halogen atoms. k, m, and n represent the number of R3, R4, and R5, where k is an integer from 0 to 4, m is an integer from 0 to 3, and n is an integer from 1 to 4. When k, m, and n are 2 or more, multiple R3, R4, and R5 can be the same or different. A is a group represented by -S-, -O-, -SO-, -SO2-, or -CO-, where O is an oxygen atom, S is a sulfur atom, X - This represents a monovalent polyatomic anion.

[0018] The second aspect of the present invention is a pattern forming method, characterized by comprising: a step of forming a photosensitive resin film on a support using the negative photosensitive resin composition of the first aspect; a step of exposing the photosensitive resin film; and a step of developing the exposed photosensitive resin film using a developer containing an organic solvent to form a negative pattern.

[0019] The third aspect of the present invention is a laminated film, which is obtained by laminating a photosensitive resin composition layer composed of the negative photosensitive resin composition of the first aspect with a support film.

[0020] Invention Effects

[0021] According to the present invention, a negative photosensitive resin composition with further improved resolution, a pattern forming method using the negative photosensitive resin composition, and a laminated film using the negative photosensitive resin composition can be provided. Detailed Implementation

[0022] In this specification and claims, "aliphatic" is a relative concept compared to aromatic, and is defined as a group or compound that does not have aromatic properties.

[0023] Unless otherwise specified, "alkyl" includes straight-chain, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups.

[0024] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0025] "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.

[0026] "Fluoroalkyl" refers to a group in which some or all of the hydrogen atoms of an alkyl group are replaced by fluorine atoms.

[0027] "Structural unit" refers to the monomer unit (monomeric unit) that constitutes a polymer compound (resin, polymer, copolymer).

[0028] When it is stated that "substituents may be present", there are two cases: replacing the hydrogen atom (-H) with a monovalent group and replacing the methylene group (-CH2-) with a divalent group.

[0029] "Exposure" is a concept that includes exposure to all types of radiation.

[0030] (Negative photosensitive resin)

[0031] The negative photosensitive resin composition of this embodiment (hereinafter sometimes simply referred to as the "photosensitive composition") contains an epoxy-containing resin (A) and a cationic polymerization initiator (I). Hereinafter, these components will also be referred to as component (A) and component (I), respectively.

[0032] If a photosensitive resin film is formed using the above-described photosensitive composition and then selectively exposed, the cationic portion of component (I) in the exposed portion of the photosensitive resin film decomposes to produce acid. Through the action of this acid, the epoxy groups in component (A) undergo ring-opening polymerization, reducing the solubility of component (A) in the developer containing organic solvents. Conversely, in the unexposed portion of the photosensitive resin film, the solubility of component (A) in the developer containing organic solvents remains unchanged. Therefore, a difference in solubility of the photosensitive resin film in the developer containing organic solvents arises between the exposed and unexposed portions. Consequently, if the photosensitive resin film is developed using a developer containing organic solvents, the unexposed portions are dissolved and removed, forming a negative pattern.

[0033] <Epoxy-containing resin (A)>

[0034] There are no particular limitations on epoxy-containing resins (component (A)), as long as they are resins that have enough epoxy groups in one molecule to form a pattern by exposure.

[0035] As component (A), for example, a resin having a glycidyl ether group in its structure can be used.

[0036] In addition, as component (A), examples include phenolic varnish epoxy resin (Anv), bisphenol A type epoxy resin (Abp), bisphenol F type epoxy resin, aliphatic epoxy resin, and acrylic resin (Aac).

[0037] Phenolic varnish-type epoxy resin (Anv)

[0038] As a phenolic varnish-type epoxy resin (Anv), a resin (A1) represented by the following general formula (A1) (hereinafter also referred to as "(A1) component") is preferably exemplified.

[0039]

Chemistry 2

[0040]

[0041] [In the formula, R] p1 and R p2 Each is independently a hydrogen atom or an alkyl group having 1 to 5 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 REP They can be the same or different.

[0042] In the formula (A1), R p1 R p2 The 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.

[0043] Among them, as R p1 R p2 Preferably, hydrogen atoms or straight-chain or branched alkyl groups are used, more preferably hydrogen atoms or straight-chain alkyl groups, and particularly preferably hydrogen atoms or methyl groups.

[0044] In equation (A1), multiple R p1 They can be the same or different. Multiple Rs p2 They can be the same or different.

[0045] In formula (A1), n1 is an integer from 1 to 5, preferably 2 or 3, and more preferably 2.

[0046] In equation (A1), R EP It is a group containing an epoxy group.

[0047] As R EP The group containing an epoxy group is not particularly limited, and examples include groups consisting only of epoxy groups; groups consisting only of alicyclic epoxy groups; and groups having an epoxy group or an alicyclic epoxy group and a divalent linking group.

[0048] Alicyclic epoxy groups refer to alicyclic groups that have a three-membered cyclic ether, i.e., an oxacyclopropane structure. Specifically, they are groups that have both an alicyclic group and an oxacyclopropane structure.

[0049] 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 of these alicyclic groups can be replaced by alkyl, alkoxy, or hydroxyl groups.

[0050] In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable to bond the epoxy group or the alicyclic epoxy group via a divalent linking group bonded to the oxygen atom (-O-) in the formula.

[0051] Here, the divalent linking group is not particularly limited, and examples such as divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms are preferred.

[0052] Regarding divalent hydrocarbon groups that can have substituents:

[0053] The divalent hydrocarbon group mentioned above can be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0054] As an aliphatic hydrocarbon group in a divalent hydrocarbon group, it can be saturated or unsaturated, but is usually preferred to be saturated.

[0055] 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.

[0056] The 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-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0057] The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, 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-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene 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.

[0058] Examples of aliphatic hydrocarbon groups containing a ring in the structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups where the alicyclic hydrocarbon group is intermediate between a straight-chain or branched aliphatic hydrocarbon groups. Examples of straight-chain or branched aliphatic hydrocarbon groups are the same aliphatic hydrocarbon groups as described above.

[0059] The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12.

[0060] The alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, and examples include cyclopentane and cyclohexane.

[0061] The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms, and examples include adamantane, norbornene, isoboronane, tricyclodecane, tetracyclododecane, etc.

[0062] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. There is no particular limitation on whether the aromatic ring is a cyclic conjugated system with (4n+2) π electrons; it 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 obtained by replacing some carbon atoms of the aromatic hydrocarbon ring 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.

[0063] Specifically, examples of aromatic hydrocarbon groups include groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group obtained by removing one hydrogen atom from an aryl group (e.g., a group obtained 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 alkylene group bonded to the aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0064] Divalent hydrocarbon groups can have substituents.

[0065] As a divalent hydrocarbon group, a straight-chain or branched aliphatic hydrocarbon group may or may not have substituents. Examples of such substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms substituted by fluorine atoms, and carbonyl groups.

[0066] Alicyclic hydrocarbon groups, which are divalent hydrocarbon groups and contain rings in their structure, may or may not have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and carbonyl groups.

[0067] The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0068] The alkoxy group used as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and most preferably methoxy or ethoxy.

[0069] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0070] The alkyl halogroup that serves as the substituent can be exemplified by groups obtained by replacing some or all of the hydrogen atoms of the alkyl group with the halogen atom.

[0071] In alicyclic hydrocarbon groups, a portion of the carbon atoms constituting the ring structure can be replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0072] In aromatic hydrocarbon groups that are divalent hydrocarbon groups, the hydrogen atoms in the aromatic hydrocarbon group can also be replaced by substituents. For example, the hydrogen atoms in the aromatic hydrocarbon group that are bonded to the aromatic ring can be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, and hydroxyl groups.

[0073] The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0074] The alkoxy, halogen atom, and haloalkyl groups that serve as substituents can be exemplified as substituents replacing hydrogen atoms in the alicyclic hydrocarbon group.

[0075] Regarding divalent linking groups containing heteroatoms:

[0076] In a divalent linker containing heteroatoms, heteroatoms refer to atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0077] Among the divalent linking groups containing heteroatoms, 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 substituted by alkyl, acyl, or other substituents); -S-, -S(=O)2-, -S(=O)2-O-, and those with the general formula -Y 21 -OY 22 -、-Y 21 -O-、-Y 21 -C(=O)-O-、-C(=O)-OY 21 -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 - represents a group [where Y is a group that represents ... 21 and Y 22 Preferred groups include divalent hydrocarbon groups that can be independently substituted, where O is an oxygen atom and m" is an integer from 0 to 3.

[0078] When the 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.

[0079] 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 are the same as those "divalent hydrocarbon groups that may have substituents" mentioned in the description of the divalent linking groups above.

[0080] As Y21 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.

[0081] As Y 22 Preferably, the alkyl 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.

[0082] With 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 a group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 - represents a group, particularly preferably represented by the formula -Y 21 -C(=O)-OY 22 - represents a group. Preferably, it is represented by the formula -(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.

[0083] Among them, as R EP The epoxy group in it is preferably a glycidyl group.

[0084] Furthermore, resins having structural units represented by the following general formula (anv1) are also preferably cited as phenolic varnish-type epoxy resins (Anv).

[0085]

Transformation 3

[0086]

[0087] [In the formula, R] EP R is a group containing an epoxy group. a22 R a23 Each of these can be independently composed of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0088] In equation (anv1), R a22 R a23An alkyl group having 1 to 5 carbon atoms and R in formula (A1) p1 R p2 The alkyl groups with 1 to 5 carbon atoms are the same. R a22 R a23 The halogen atom is preferably a chlorine atom or a bromine atom.

[0089] In equation (anv1), R EP With R in the above formula (A1) EP Similarly, glycidyl group is preferred.

[0090] The following shows a specific example of a structural unit represented by the formula (anv1).

[0091]

Chemistry 4

[0092]

[0093] The phenolic varnish-type epoxy resin (Anv) can be a resin composed solely of the aforementioned structural unit (anv1), or it can be a resin having structural unit (anv1) and other structural units. Examples of these other structural units include those represented by the following general formulas (anv2) to (anv3).

[0094]

Transformation 5

[0095]

[0096] [In the formula, R] a24 It is a hydrocarbon group that can have substituents. R a25 ~R a26 R a28 ~R a30 Each of the following can be independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. R a27 It is a group containing an epoxy group or a hydrocarbon group that may have substituents.

[0097] In the formula (anv2), R a24 It is a hydrocarbon group that can have substituents. Examples of hydrocarbon groups that can have substituents include straight-chain or branched alkyl groups or cyclic hydrocarbon groups.

[0098] 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, more preferably methyl or ethyl.

[0099] 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.

[0100] In R a24 In the case of 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.

[0101] The aliphatic hydrocarbon group that is a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms, and examples include cyclopentane and cyclohexane.

[0102] The aliphatic hydrocarbon group that is the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms. Examples of such polycyclic alkane include adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0103] In R a24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0104] The aromatic ring is not particularly limited to a cyclic conjugated system having 4n+2 π electrons; it 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 aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles obtained by replacing some carbon atoms in the aromatic hydrocarbon ring 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.

[0105] As R a24 The aromatic hydrocarbon group in the compound can specifically include, for example, a group (aryl or heteroaryl) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle; a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group obtained by substituting one hydrogen atom of the 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 aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0106] In equations (anv2) and (anv3), Ra25 ~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, and the alkyl group having 1 to 5 carbon atoms or the halogen atom are respectively associated with the R. a22 R a23 same.

[0107] In 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 formula (A1) EP Similarly, R a27 Hydrocarbon groups that may have substituents and R a24 same.

[0108] The following are specific examples of structural units represented by the formulas (anv2) to (anv3).

[0109]

Transformation 6

[0110]

[0111] When the phenolic varnish-type epoxy resin (Anv) has other structural units besides the structural unit (anv1), the proportion of each structural unit in the resin (Anv) is not particularly limited, but the total number of structural units with epoxy groups is preferably 10 to 90 mol% relative to the total number of all constituent units constituting the resin (Anv), more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%.

[0112] Bisphenol A type epoxy resin (Abp)

[0113] Examples of bisphenol A type epoxy resins (Abp) can be exemplified by epoxy resins represented by the following general formula (abp1).

[0114]

Transformation 7

[0115]

[0116] [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.

[0117] In equation (abp1), R a31 R a32 An alkyl group having 1 to 5 carbon atoms and R in formula (A1) p1 Rp2 The alkyl groups having 1 to 5 carbon atoms are the same. Among them, as R a31 R a32 Preferably, hydrogen atoms or methyl groups are used.

[0118] R EP With R in the above formula (A1) EP Similarly, glycidyl groups are preferred.

[0119] Aliphatic epoxy resins and acrylic resins (Aac)

[0120] Examples of aliphatic epoxy resins and acrylic resins (Aac) include resins having epoxy-containing units represented by the following general formulas (a1-1) to (a1-2).

[0121]

Transformation 8

[0122]

[0123] [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 [Integers from 1 to 3.]

[0124] In the 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.

[0125] The alkyl group of R having 1 to 5 carbon atoms is preferably straight-chain or branched. Examples of such groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0126] The alkyl halogroup R having 1 to 5 carbon atoms is a group obtained by substituting some or all of the hydrogen atoms of the alkyl halogroup 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.

[0127] 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 viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.

[0128] In the formula (a1-1), Va 41It is a divalent hydrocarbon group that can have substituents, such as R in formula (A1). EP The same group as the divalent hydrocarbon group described herein, which may have substituents.

[0129] 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.

[0130] In equation (a1-1), na 41 It is an integer from 0 to 2, preferably 0 or 1.

[0131] In equations (a1-1) and (a1-2), R a41 R a42 It is an epoxy group, and it is related to R in formula (A1). EP same.

[0132] In formula (a1-2), Wa 41 (na) 43 +1) The aliphatic hydrocarbon group represents a hydrocarbon group that does not possess aromaticity. It can be saturated or unsaturated, but is generally preferred to be saturated. Examples of the aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in their structure, or groups obtained by combining straight-chain or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in their structure.

[0133] In equation (a1-2), na 43 It is an integer from 1 to 3, preferably 1 or 2.

[0134] The following are specific examples of structural units represented by the formula (a1-1) or (a1-2).

[0135]

Chemistry 9

[0136]

[0137]

Chemistry 10

[0138]

[0139]

Chemistry 11

[0140]

[0141]

Chemistry 12

[0142]

[0143] In the above formula, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0144] R a51 R represents a divalent hydrocarbon group with 1 to 8 carbon atoms. a52 R represents a divalent hydrocarbon group with 1 to 20 carbon atoms. a53 This indicates a hydrogen atom or a methyl group. (na) 51 Integers from 0 to 10.

[0145] R a51 R a52 R a53 They can be the same or different.

[0146] Furthermore, for the purpose of moderately controlling physical and chemical properties, acrylic resins (Aac) can also have structural units derived from other polymeric compounds. Examples of such polymeric compounds include known free radical polymers and anionic polymers. 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 and ester bonds such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; and hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. (Meth)acrylate aryl esters 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; and polymeric compounds containing amide bonds such as acrylamide and methacrylamide.

[0147] When aliphatic epoxy resins and acrylic resins (Aac) have other structural units, the content ratio of epoxy-containing units in the resin is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and most preferably 15 to 25 mol%.

[0148] Furthermore, as an aliphatic epoxy resin, it is also preferable to include compounds containing a local structure represented by the following general formula (m1) (hereinafter also referred to as "(m1) component").

[0149]

Chemistry 13

[0150]

[0151] [In the formula, n2 is an integer from 1 to 4. * represents a chemical bond.]

[0152] In formula (m1), n2 is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 2.

[0153] As component (m1), examples include compounds in which multiple local structures represented by the above general formula (m1) are bonded via divalent linking groups or single bonds. Among these, compounds in which multiple local structures represented by the above general formula (m1) are preferably bonded via divalent linking groups.

[0154] The divalent linking group here is not particularly limited, but examples such as divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms are preferred. For divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms, and R in the above formula (A1)... EP The divalent hydrocarbon group (containing an epoxy group) described in the section on substituents and the divalent linking group containing heteroatoms are the same, wherein the divalent linking group containing heteroatoms is preferred, and the -Y group is more preferred. 21 Groups represented by -C(=O)-O-, and those represented by -C(=O)-OY 21 - indicates a group. 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.

[0155] Furthermore, as an aliphatic epoxy resin, a compound represented by the following general formula (m2) (hereinafter also referred to as "(m2) component") may preferably be cited.

[0156]

Chemistry 14

[0157]

[0158] [In the formula, R] EP It is a group containing an epoxy group. Multiple R EP They can be the same or different.

[0159] In formula (m2), R EP It is an epoxy group, and it is related to R in formula (A1). EP same.

[0160] As component (A), one type can be used alone or two or more types can be used together.

[0161] In component (A), it is preferred to use a resin having a glycidyl ether group in its structure.

[0162] (A) The component preferably includes at least one resin selected from the group consisting of phenolic varnish epoxy resin (Anv), bisphenol A type epoxy resin (Abp), bisphenol F type epoxy resin, aliphatic epoxy resin, and acrylic resin (Aac).

[0163] Of which, component (A) more preferably includes at least one resin selected from the group consisting of phenolic varnish-type epoxy resin (Anv) and bisphenol A type resin (Abp).

[0164] Component (A) is further preferably a combination of phenolic varnish-type epoxy resin (Anv) and bisphenol A type resin (Abp), and particularly preferably a combination of resin (A1) represented by the general formula (A1) and epoxy resin represented by the general formula (abp1).

[0165] In the case where both phenolic varnish-type epoxy resin (Anv) and bisphenol A type resin (Abp) are present, the ratio of phenolic varnish-type epoxy resin (Anv) to bisphenol A type resin (Abp), expressed as a mass ratio of (Anv) component / (Abp) component, is preferably 5 / 95 to 50 / 50, more preferably 10 / 90 to 40 / 60, and even more preferably 10 / 90 to 30 / 70.

[0166] If the mass ratio is within the preferred range described above, the resolution is further improved, and the adhesion to the substrate becomes excellent.

[0167] When component (A) contains at least one resin selected from the group consisting of phenolic varnish-type epoxy resin (Anv) and bisphenol A type resin (Abp), from the viewpoint of balancing the strength and flexibility of the cured film, the proportion of phenolic varnish-type epoxy resin (Anv) in component (A) relative to the total mass (100% by mass) of component (A) is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.

[0168] The proportion of bisphenol A type resin (Abp) in component (A) is preferably 50 to 95% by mass relative to the total mass (100% by mass) of component (A), more preferably 70 to 90% by mass.

[0169] The total content of phenolic varnish-type epoxy resin (Anv) and bisphenol A type resin (Abp) relative to the total mass (100% by mass) of component (A) is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may also be 100% by mass.

[0170] (A) The equivalent mass-average molecular weight of the polystyrene in component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and even more preferably 300 to 200,000. By setting such a mass-average molecular weight, it is difficult for peeling from the support to occur, and the strength of the formed cured film is sufficiently improved.

[0171] Furthermore, the molecular weight distribution coefficient of component (A) is preferably 1.05 or higher. By setting such a molecular weight distribution coefficient, the photolithographic properties during pattern formation are further improved.

[0172] The molecular weight distribution coefficient mentioned here refers to the value obtained by dividing the mass-average molecular weight by the number-average molecular weight.

[0173] Commercially available products as component (A), such as phenolic varnish-type epoxy resins (Anv), include JER-152, JER-154, JER-157S70, JER-157S65 (all manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON NHP5000 (all manufactured by DIC Corporation), EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0174] Examples of bisphenol A type epoxy resins (Abp) include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (all manufactured by DIC Corporation).

[0175] Examples of bisphenol F type epoxy resins include JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (all manufactured by DIC Corporation), LCE-21, and RE-602S (all manufactured by Nippon Kayaku Co., Ltd.).

[0176] Examples of aliphatic epoxy resins include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (manufactured by ADEKA Corporation), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EHPE-3150, EPOLEAD PPB 3600, EPOLEAD PB 4700 (manufactured by Daicel Corporation), DENACOL EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase Chemical). (Made by Chemtex Corporation), TEPIC-VL (Made by Nissan Chemical Corporation), etc.

[0177] The content of component (A) in the photosensitive composition of the embodiment can be adjusted according to the desired thickness of the photosensitive resin film.

[0178] <Catonic Polymerization Initiator (I)>

[0179] In the cationic polymerization initiator ((I) component), a cationic polymerization initiator containing a sulfonium salt (I0) represented by the following general formula (I0) (hereinafter referred to as "(I0) component") is used.

[0180]

Chemistry 15

[0181]

[0182] In formula (I0), R1 and R2 represent aryl groups with 6 to 30 carbon atoms, heterocyclic hydrocarbon groups with 4 to 30 carbon atoms, or alkyl groups with 1 to 30 carbon atoms, respectively. A portion of the hydrogen atoms of these aryl, heterocyclic hydrocarbon, or alkyl groups may be replaced by a substituent (t). This substituent (t) is derived from alkyl groups with 1 to 18 carbon atoms, hydroxyl groups, alkoxy groups with 1 to 18 carbon atoms, alkyl carbonyl groups with 2 to 18 carbon atoms, aryl carbonyl groups with 7 to 11 carbon atoms, acyloxy groups with 2 to 19 carbon atoms, arylthio groups with 6 to 20 carbon atoms, alkoxy groups with 1 to 18 carbon atoms, aryl groups with 6 to 10 carbon atoms, heterocyclic hydrocarbon groups with 4 to 20 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, and HO(-R) groups. A O)q-{R AO represents ethyleneoxy and / or propyleneoxy, q represents an integer from 1 to 5.} represents at least one group selected from the group consisting of hydroxyl (poly)alkoxide, and halogen atoms. R3 to R5 are respectively alkyl, hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, hydroxyl (poly)alkoxide, or halogen atoms. k, m, and n represent the number of R3, R4, and R5, where k is an integer from 0 to 4, m is an integer from 0 to 3, and n is an integer from 1 to 4. When k, m, and n are 2 or more, multiple R3, R4, and R5 can be the same or different. A is a group represented by -S-, -O-, -SO-, -SO2-, or -CO-, where O is an oxygen atom, S is a sulfur atom, X - This represents a monovalent polyatomic anion.

[0183] 《(I0)Component》

[0184] In the formula (I0), examples of alkyl groups among R3 to R5 include straight-chain alkyl groups with 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl, etc.), branched-chain alkyl groups with 1 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and isooctadecyl), and cycloalkyl groups with 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and 4-decylcyclohexyl, etc.).

[0185] Among R3 to R5, examples of alkoxy groups that are straight-chain or branched with 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexoxy, decoxy, dodecyloxy, and octadecyloxy, etc.

[0186] Among R3 to R5, examples of alkyl carbonyl groups that are straight-chain or branched and have 2 to 18 carbon atoms include acetyl, propionyl, butyryl, 2-methylpropionyl, heptanoyl, 2-methylbutyryl, 3-methylbutyryl, octanoyl, decanoyl, dodecanoyl, and octadecanoyl, etc.

[0187] Among R3 to R5, examples of aryl carbonyl groups with 7 to 11 carbon atoms include aryl carbonyl groups (such as benzoyl and naphthyl).

[0188] Among R3 to R5, examples of acyloxy groups that are straight-chain or branched with 2 to 19 carbon atoms include acetoxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, octyl carbonyloxy, tetradecyl carbonyloxy, and octadecyl carbonyloxy, etc.

[0189] Among R3 to R5, examples of arylthio groups with 6 to 20 carbon atoms include phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthio, 2-naphthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio. Thioyl, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl)phenylthio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio, etc.

[0190] Among R3 to R5, examples of alkylthio groups with 1 to 18 carbon atoms, whether linear or branched (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio, etc.), can be cited.

[0191] Among R3 to R5, examples of aryl groups with 6 to 10 carbon atoms include phenyl, tolyl, dimethylphenyl, and naphthyl groups.

[0192] Among R3 to R5, heterocyclic hydrocarbon groups with 4 to 20 carbon atoms can be exemplified as thiophene, furanyl, pyranyl, pyrrole, oxazolyl, thiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, indolyl, benzofuranyl, benzothiophene, quinolinyl, isoquinolinyl, quinoxolinyl, quinazolinyl, carbazoline, acridineyl, phenothiazinyl, phenothiazinyl, xanthonyl, thianyl, phenothiazinyl, phenothiazinyl, benzodihydropyranyl, isobenzodihydropyranyl, dibenzothiophene, xanthonone, thioxanthonone, and dibenzofuranyl, etc.

[0193] Among R3 to R5, examples of aryloxy groups with 6 to 10 carbon atoms include aryloxy groups (such as phenoxy and naphthoxy groups).

[0194] Among R3 to R5, examples of hydroxyl (poly)alkoxy groups, such as those represented by formula (2), can be cited as hydroxyl (poly)alkoxy groups.

[0195] HO(-R A O)q-(2)

[0196] R A O represents ethyleneoxy and / or propyleneoxy, and q represents an integer from 1 to 5.

[0197] Among R3 to R5, examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0198] R3 through R5 can be all the same, different, or partially different. When k, m, and n are all 2 or higher (described later), multiple R3s can be the same or different from each other. Multiple R4s can be the same or different from each other. Multiple R5s can be the same or different from each other.

[0199] k represents the number of R3, which is an integer from 0 to 4, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0200] In addition, m represents the number of R4, which is an integer from 0 to 3, preferably 0 or 1, and particularly preferably 0.

[0201] Furthermore, n represents the number of R5, which is an integer from 1 to 4. From the viewpoint of obtaining industrial raw materials, it is preferably 1 or 2, and from the viewpoint of solubility, it is particularly preferably 2.

[0202] There are no restrictions on the bonding position of R5, but if it is relative to CS + If the bond is adjacent, the photosensitivity of the sulfonium salt becomes even better.

[0203] In the above formula (I0), A is a group represented by -O-, -S-, -SO-, -SO2- or -CO-, preferably -S-.

[0204] In the formula (I0), R1 and R2 are selected from aryl groups having 6 to 30 carbon atoms, heterocyclic hydrocarbon groups having 4 to 30 carbon atoms, and alkyl groups having 1 to 30 carbon atoms, respectively, and a portion of the hydrogen atoms of these aryl, heterocyclic hydrocarbon, and alkyl groups may be substituted by substituents (t).

[0205] The substituent (t) is selected from at least one group consisting of an alkyl group having 1 to 18 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, an alkyl carbonyl group having 2 to 18 carbon atoms, an aryl carbonyl group having 7 to 11 carbon atoms, an acyloxy group having 2 to 19 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic hydrocarbon group having 4 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a hydroxyl (poly)alkeneoxy group, and a halogen atom. The substituent (t) is the same as that described for R3 to R5.

[0206] In R1 and R2, the aryl groups having 6 to 30 carbon atoms include monocyclic aryl groups and fused polycyclic aryl groups.

[0207] Examples of monocyclic aryl groups include phenyl, hydroxyphenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, n-propoxyphenyl, isopropoxyphenyl, n-butoxyphenyl, isobutoxyphenyl, sec-butoxyphenyl, tert-butoxyphenyl, acetylphenyl, benzoylphenyl, naphthoylphenyl, phenylthiophenyl, naphthoylphenyl, biphenyl, phenoxyphenyl, naphthophenyl, nitrophenyl, fluorophenyl, chlorophenyl, and bromophenyl.

[0208] Examples of fused polycyclic aryl groups include naphthyl, anthraceneyl, phenanthryl, pyrene, etc. The compounds include benzo[a]triphenyl, benzo[a]anthrayl, anthraquinoline, fluorenyl, naphthylquinoline, hydroxynaphthyl, methylnaphthyl, ethylnaphthyl, methoxynaphthyl, ethoxynaphthyl, acetylnaphthyl, benzoylnaphthyl, phenylthionaphthyl, phenoxynaphthyl, nitronaphthyl, fluoronaphthyl, chloronaphthyl, bromonaphthyl, hydroxyanthrayl, methylanthrayl, ethylanthrayl, methoxyanthrayl, ethoxyanthrayl, acetylanthrayl, benzoylanthrayl, phenylthioanthrayl, phenoxyanthrayl, nitroanthrayl, fluoroanthrayl, chloroanthrayl, and bromoanthrayl, etc.

[0209] R1 and R2 are heterocyclic hydrocarbon groups with 4 to 30 carbon atoms, including cyclic hydrocarbon groups containing 1 to 3 heteroatoms (oxygen atoms, nitrogen atoms, and sulfur atoms, etc.) within the ring, including monocyclic heterocyclic hydrocarbon groups and fused polycyclic heterocyclic hydrocarbon groups.

[0210] Examples of monocyclic and heterocyclic hydrocarbon groups include thienyl, furanyl, pyranyl, pyrroleyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, hydroxythienyl, methylthienyl, ethylthienyl, methoxythienyl, acetylthienyl, benzoylthienyl, phenylthiothienyl, phenoxythienyl, nitrothienyl, fluorothienyl, chlorothienyl, bromothienyl, hydroxyfuranyl, methylfuranyl, ethylfuranyl, methoxyfuranyl, acetylfuranyl, benzoylfuranyl, phenylthiothienyl, phenoxyfuranyl, nitrofuranyl, fluorofuranyl, chlorofuranyl, and bromofuranyl.

[0211] Examples of fused polycyclic heterocyclic hydrocarbon groups include indolyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, isobenzothiophenyl, quinolinyl, isoquinolinyl, quinoxolinyl, quinazolinyl, carbazoline, acridineyl, phenothiazinyl, phenothiazinyl, xanthoneyl, thianthenyl, phenothiazinyl, phenothiazinyl, benzodihydropyranyl, isobenzodihydropyranyl, dibenzothiophenyl, xanthoneyl, and thioxanthoneyl. Dibenzofuranyl, hydroxyxanthonyl, methylxanthonyl, ethylxanthonyl, methoxyxanthonyl, acetylxanthonyl, benzoylxanthonyl, phenylthioxanthonyl, phenoxyxanthonyl, nitroxanthonyl, fluoroxanthonyl, chloroxanthonyl, bromoxanthonyl, hydroxythiaanthonyl, methylthiaanthonyl, ethylthiaanthonyl, methoxythiaanthonyl, benzoylthiaanthonyl, phenylthiothiaanthonyl, phenoxythiaanthonyl, nitrothiaanthonyl alkyl, fluorothiaxanthrayl, chlorothiaxanthrayl, bromothiaxanthrayl, hydroxyxanthoxanone, methylxanthoxanone, dimethylxanthoxanone, ethylxanthoxanone, diethylxanthoxanone, n-propylxanthoxanone, isopropylxanthoxanone, methoxyxanthoxanone, acetylxanthoxanone, benzoylxanthoxanone, phenylthioxanthoxanone, phenoxyxanthoxanone, acetoxyxanthoxanone, nitroxanthoxanone, fluoroxanthoxanone, chloro Thioxanone, hydroxythioxanone, methylthioxanone, dimethylthioxanone, ethylthioxanone, diethylthioxanone, n-propylthioxanone, isopropylthioxanone, methoxythioxanone, acetylthioxanone, benzoylthioxanone, phenylthioxanone, phenoxythioxanone, acetoxythioxanone, nitrothioxanone, fluorothioxanone, chlorothioxanone, and bromothioxanone, etc.

[0212] In R1 and R2, examples of alkyl groups having 1 to 30 carbon atoms include straight-chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, benzyl, diphenylmethyl, naphthylmethyl, anthracene methyl, benzoylmethyl (-CH2COC6H5), naphthylmethyl, anthracene methyl, etc.), branched-chain alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl, etc.), and cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, etc.).

[0213] R1 and R2 are preferably aryl groups with 6 to 30 carbon atoms in which a portion of the hydrogen atom can be replaced by a substituent (t), and heterocyclic hydrocarbon groups with 4 to 30 carbon atoms in which a portion of the hydrogen atom can be replaced by a substituent (t). More preferably, at least one of R1 or R2 is a heterocyclic hydrocarbon group with 4 to 30 carbon atoms. From the viewpoint of photosensitivity and solubility, it is particularly preferred that R1 is a thioxanthone group and R2 is an aryl group with 6 to 30 carbon atoms in which a substituent (t) can be replaced.

[0214] As substituents (t), preferably alkyl, hydroxyl, alkoxy, alkyl carbonyl, or aryl carbonyl with 1 to 18 carbon atoms, preferably alkyl or alkoxy, and particularly preferably methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl), methoxy, or ethoxy.

[0215] As the cationic part of the (I0) component, it is preferable that A in the general formula (I0) is a group represented by -S- or -O-, and k and m are 0 and n is an integer from 1 to 4.

[0216] Alternatively, as the cationic portion of the (I0) component, R1 or R2 in the general formula (I0) is preferably a cation of an aryl group having 6 to 30 carbon atoms or a heterocyclic hydrocarbon group having 4 to 30 carbon atoms (part of the hydrogen atoms of these aryl or heterocyclic hydrocarbon groups may be replaced by the substituent (t)).

[0217] Alternatively, as the cationic part of the (I0) component, it is preferred that R1 or R2 in the general formula (I0) is a thioxanone group in which part of the hydrogen atom can be replaced by the substituent (t), k and m are 0, n is 1 or 2, and A is a cationic group represented by -S-.

[0218] Specifically, examples of cations in the (I0) component include the following cations.

[0219]

Chemistry 16

[0220]

[0221]

Chemistry 17

[0222]

[0223] In the above formula (I0), X - There are no restrictions as long as it is a monovalent polyatomic anion, which is the anion corresponding to the acid (HX) produced by irradiating sulfonium salt (I0) with active energy lines (visible light, ultraviolet light, electron beams and X-rays, etc.).

[0224] As X - Examples can be given using MY a - (Rf) b PF 6-b - R 6 c BY 4-c - R 6 c GaY 4-c- R 7 SO3 - 、(R 7 SO2)3C - or (R) 7 SO2)2N - The anion is represented.

[0225] M represents a phosphorus atom, a boron atom, or an antimony atom.

[0226] Y represents a halogen atom, preferably a fluorine atom.

[0227] Rf indicates an alkyl group in which more than 80 mol% of hydrogen atoms are replaced by fluorine atoms.

[0228] As an alkyl group that becomes Rf through fluorine substitution, an alkyl group having 1 to 8 carbon atoms is preferred, and examples include straight-chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl and octyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl and tert-butyl, etc.), and cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, etc.).

[0229] In Rf, the proportion of hydrogen atoms in these alkyl groups replaced by fluorine atoms is preferably 80 mol% or more, more preferably 90% or more, and particularly preferably 100%, based on the original molar number of hydrogen atoms in the alkyl group. If the substitution ratio of fluorine atoms is within these preferred ranges, the photosensitivity of the sulfonium salt becomes better.

[0230] Examples of particularly preferred Rfs include CF3-, CF3CF2-, (CF3)2CF-, CF3CF2CF2-, CF3CF2CF2CF2-, (CF3)2CFCF2-, CF3CF2(CF3)CF-, and (CF3)3C-.

[0231] The b Rfs are independent of each other and can be the same or different from each other.

[0232] P represents a phosphorus atom, and F represents a fluorine atom.

[0233] R 6 A phenyl group is defined as a phenyl obtained by substituting one hydrogen atom with at least one element or by substituting it with an electron-withdrawing group. Examples of such one element include halogen atoms, such as fluorine, chlorine, and bromine atoms. Examples of electron-withdrawing groups include trifluoromethyl, nitro, and cyano groups. Preferably, a phenyl group is obtained by substituting one hydrogen atom with a fluorine atom or a trifluoromethyl group.

[0234] c R 6 They are independent of each other; they can be the same as each other or different from each other.

[0235] B represents boron atoms, and Ga represents gallium atoms.

[0236] R 7 It refers to an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The alkyl and perfluoroalkyl groups can be straight-chain, branched, or cyclic. The alkyl or aryl group can be unsubstituted or have substituents.

[0237] S represents sulfur, O represents oxygen, C represents carbon, and N represents nitrogen.

[0238] a represents an integer from 4 to 6.

[0239] b is preferably an integer from 1 to 5, more preferably from 2 to 4, and particularly preferably 2 or 3.

[0240] c is preferably an integer from 1 to 4, and more preferably 4.

[0241] As MY a - The anion represented can be exemplified by SbF6. - PF6 - and BF4 - The anions represented, etc.

[0242] As for (Rf) b PF 6-b - An anion can be represented by (CF3CF2)2PF4. - (CF3CF2)3PF3 - 、((CF3)2CF)2PF4 - 、((CF3)2CF)3PF3 - (CF3CF2CF2)2PF4 - (CF3CF2CF2)3PF3 - 、((CF3)2CFCF2)2PF4 - 、((CF3)2CFCF2)3PF3 - (CF3CF2CF2CF2)2PF4 - and (CF3CF2CF2CF2)3PF3 - Anions, etc., are represented by these. Among these, (CF3CF2)3PF3 is preferred. - (CF3CF2CF2)3PF3 - 、((CF3)2CF)3PF3 - 、((CF3)2CF)2PF4 - 、((CF3)2CFCF2)3PF3 - and ((CF3)2CFCF2)2PF4 -The anion is represented.

[0243] As R 6 c BY 4-c - An anion can be represented by (C6F5)4B. - 、(CF3)2C6H3)4B - (CF3C6H4)4B - (C6F5)2BF2 - C6F5BF3 - and (C6H3F2)4B - Anions, etc., are represented. Among these, (C6F5)4B is preferred. - and ((CF3)2C6H3)4B - The anion is represented.

[0244] As R 6 c GaY 4-c - An anion can be represented by (C6F5)4Ga. - 、(CF3)2C6H3)4Ga - (CF3C6H4)4Ga - (C6F5)2GaF2 - C6F5GaF3 - and (C6H3F2)4Ga - Anions, etc., are represented. Among these, (C6F5)4Ga is preferred. - and ((CF3)2C6H3)4Ga - The anion is represented.

[0245] As R 7 SO3 - Examples of anions that can be represented include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutyric acid anion, pentafluorophenylsulfonic acid anion, p-toluenesulfonic acid anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion, and butyric acid anion. Among these, trifluoromethanesulfonic acid anion, nonafluorobutyric acid anion, methanesulfonic acid anion, butyric acid anion, camphorsulfonic acid anion, benzenesulfonic acid anion, and p-toluenesulfonic acid anion are preferred.

[0246] As with (R) 7 SO2)3C - Anions that can be represented by (CF3SO2)3C can be cited as an example. - (C2F5SO2)3C - (C3F7SO2)3C- and (C4F9SO2)3C - The anions represented, etc.

[0247] As with (R) 7 SO2)2N - Anions that can be represented by (CF3SO2)2N can be cited as an example. - (C2F5SO2)2N - (C3F7SO2)2N - and (C4F9SO2)2N - The anions represented, etc.

[0248] As a monovalent polyatomic anion, besides MY a - (Rf) b PF 6-b - R 6 c BY 4-c - R 6 c GaY 4-c - R 7 SO3 - 、(R 7 SO2)3C - or (R) 7 SO2)2N - In addition to the anions indicated, perhalate ions (ClO4) can also be used. - BrO4 - etc.), halosulfonic acid ions (FSO3) - ClSO3 - (etc.), sulfate ions (CH3SO4) - CF3SO4 - HSO4 - (etc.), carbonate ions (HCO3) - CH3CO3 - (etc.), aluminate ions (AlCl4) - AlF4 - etc.), bismuth hexafluorobismuthate ion (BiF6) - ), carboxylic acid ions (CH3COO) - CF3COO - C6H5COO - CH3C6H4COO - C6F5COO - CF3C6H4COO - etc.), arylboronic acid ion (B(C6H5)4 -, CH3CH2CH2CH2B(C6H5)3-, etc.), thiocyanate ions (SCN-) and nitrate ions (NO3-) - )wait.

[0249] These X - Among them, MY is preferred. a - (Rf) b PF 6-b - R 6 c BY 4-c - R 6 c GaY 4-c - R 7 SO3 - 、(R 7 SO2)3C - or (R) 7 SO2)2N - The anion is represented.

[0250] For example, from the viewpoint of high cationic polymerizability, SbF6 is preferred. - PF6 - (CF3CF2)3PF3 - (C6F5)4B - 、(CF3)2C6H3)4B - (C6F5)4Ga - 、(CF3)2C6H3)4Ga - .

[0251] Furthermore, from the viewpoint of achieving better resist resolution and pattern shape, (CF3CF2)3PF3 is preferred. - (C6F5)4B - 、(CF3)2C6H3)4B - (C6F5)4Ga - 、(CF3)2C6H3)4Ga - Trifluoromethanesulfonic acid anion, nonafluorobutyric acid anion, methanesulfonic acid anion, butyric acid anion, camphor sulfonic acid anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, (CF3SO2)3C - and (CF3SO2)2N - .

[0252] Furthermore, from the viewpoint of good compatibility with cationic polymeric compounds and resist compositions, (CF3CF2)3PF3 is particularly preferred. -Nonafluorobutyric acid anion, (C6F5)4B - and ((CF3)2C6H3)4B - (CF3SO2)3C - .

[0253] Furthermore, from the perspective of excellent heat resistance and transparency, (C6F5)4Ga is further preferred. - .

[0254] In particular, in the negative photosensitive resin composition of this embodiment, from the viewpoint that the anionic portion of the (I0) component is preferably (Rf), which easily improves the resolution of the pattern. b PF 6-b - R 6 c BY 4-c - .

[0255] The following are specific examples of the preferred (I0) components.

[0256] [Chemistry 18]

[0257]

[0258]

Chemistry 19

[0259]

[0260]

Chemistry 20

[0261]

[0262]

Chemistry 21

[0263]

[0264]

Chemistry 22

[0265]

[0266]

Chemistry 23

[0267]

[0268]

Chemistry 24

[0269]

[0270]

Chemistry 25

[0271]

[0272]

Chemistry 26

[0273]

[0274]

Chemistry 27

[0275]

[0276]

Chemistry 28

[0277]

[0278]

Chemistry 29

[0279]

[0280] As a component (I0), one type can be used alone, or two or more types can be used together.

[0281] As component (I0), it is preferred to select at least one from the group consisting of compounds (I0-01) to (I0-48), more preferably at least one from the group consisting of compounds (I0-25) to (I0-48), and even more preferably at least one from the group consisting of compounds (I0-41) to (I0-48).

[0282] In the photosensitive composition of this embodiment, the content of component (I0) is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of component (A), more preferably 0.3 to 4.5 parts by mass, and even more preferably 0.5 to 4 parts by mass.

[0283] If the content of component (I0) is above the lower limit of the preferred range, sufficient sensitivity can be obtained, and the resolution of the pattern is further improved. Furthermore, the strength of the cured film is further improved. On the other hand, if it is below the upper limit of the preferred range, the sensitivity is moderately controlled, and it becomes easier to obtain patterns with good shapes.

[0284] [Method for manufacturing matte salt (I0)]

[0285] The sulfonium salt (I0) in this embodiment can be manufactured by the following manufacturing method.

[0286] The methods shown in the following reaction formulas (e.g., the methods described in the 4th edition of Lectures on Experimental Chemistry, Vol. 24, published by Maruzen Co., Ltd. in 1992, page 376; Japanese Patent Application Publication No. 7-329399; Japanese Patent Application Publication No. 8-165290; Japanese Patent Application Publication No. 10-212286 or Japanese Patent Application Publication No. 10-7680, etc.).

[0287]

Transformation 30

[0288]

[0289] In the above reaction formula, R1~R5, A, S, O, X - k, m, and n are the same as R1~R5, A, S, O, and X in the above general formula (I0). - The definitions of k, m, and n are the same. H represents a hydrogen atom.

[0290] HX' represents the conjugate acid of a monovalent polyatomic anion. From the viewpoints of ease of acquisition, acid stability, and reaction yield, methanesulfonic acid, perfluoromethanesulfonic acid, and sulfuric acid are preferred as HX'.

[0291] Dehydrating agents include, for example, phosphoric anhydride, acetic anhydride, or concentrated sulfuric acid.

[0292] Monovalent polyatomic anion (X' - For example, it can be replaced by other anions (X) through the double displacement reaction described above. - ).

[0293] MX represents an alkali metal (lithium, sodium, and potassium, etc.) cation and other anions {e.g., MY} a - (Rf) b PF 6-b - R 6 c BY 4-c - R 6 c GaY 4-c - R 7 SO3 - 、(R 7 SO2)3C - or (R) 7 SO2)2N - Salts of anions such as}.

[0294] In the above reaction formula, the first stage reaction can be carried out in a solvent-free environment or in an organic solvent (acetonitrile, tetrahydrofuran, dioxane, ethanol, acetone, etc.) as needed. The reaction temperature is approximately 20–105℃.

[0295] The second stage reaction can be carried out immediately after the first stage reaction, or it can be carried out after isolating (purifying as needed) the reaction intermediate (G2).

[0296] The reaction intermediate (G2) and an aqueous solution of an alkali metal cation and other anion salt (MX) are mixed and stirred to carry out a metathesis reaction. The precipitated solid is filtered out, or the separated oily substance is extracted with an organic solvent and the organic solvent is removed, thereby obtaining a sulfonium salt (I0) as a solid or viscous liquid. The obtained solid or viscous liquid can be washed with a suitable organic solvent as needed, or purified by recrystallization or column chromatography.

[0297] The chemical structure of sulfonium salts (I0) can be determined by common analytical methods (e.g., 1 H-、 11 B-、 13 C-、 19 F-、 31 Identification is performed using P-NMR spectroscopy, infrared absorption spectroscopy, and / or elemental analysis, etc.

[0298] (I0) Cationic polymerization initiators other than the components

[0299] In the photosensitive composition of this embodiment, as component (I), in addition to component (I0), a cationic polymerization initiator other than component (I0) may also be used.

[0300] There are no particular limitations on cationic polymerization initiators other than the (I0) component; for example, cationic polymerization initiators that are different from the cationic portion in the (I0) component can be cited.

[0301] As a cation different from the cation portion in the above-mentioned (I0) component, examples of sulfonium cation and iodonium cation are preferred, and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0302]

Chemistry 31

[0303]

[0304] [In the formula, R] 201 ~R 207 and R 211 ~R 212 Each can be independently represented as an aryl group that may have substituents, a heteroaryl group that may have substituents, an alkyl group that may have substituents, or an 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 be independently represented by a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 210It can be an aryl group that may have substituents, an alkyl group that may have substituents, an alkenyl group that may have substituents, or a -SO2- cyclic group that may have substituents. L 201 This represents -C(=O)- or -C(=O)-O-. Y 201 Each can be independently represented as arylene, alkylene, or alkenyl. x is 1 or 2. W 201 [This represents a linking group with a valence of (x+1).]

[0305] As R 201 ~R 207 and R 211 ~R 212 The aryl group in the aryl group can be substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0306] As R 201 ~R 207 and R 211 ~R 212 The heteroaryl group in the text can be exemplified by heteroaryl groups obtained by replacing a portion of the carbon atoms constituting the aryl group with heteroatoms.

[0307] Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroaryl groups include those obtained by removing one hydrogen atom from 9H-thioxanthone; examples of substituted heteroaryl groups include those obtained by removing one hydrogen atom from 9H-thioxanthone-9-one.

[0308] As R 201 ~R 207 and R 211 ~R 212 The alkyl group in the alkyl group is preferably a chain-like or cyclic alkyl group with 1 to 30 carbon atoms.

[0309] As R 201 ~R 207 and R 211 ~R 212 The alkenyl group in the alkenyl group preferably has 2 to 10 carbon atoms.

[0310] 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).

[0311]

Chemistry 32

[0312]

[0313] [In the formula, R']201 Each of the following 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.

[0314] In the formulas (ca-r-1) to (ca-r-10), R' 201 Each can be a 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.

[0315] Cyclic groups that may have substituents:

[0316] 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 indicates a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group can be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, with saturated aliphatic hydrocarbon groups generally preferred.

[0317] R' 201 The 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.

[0318] 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 the substitution of some carbon atoms in these aromatic rings with heteroatoms, or rings formed by the substitution of 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.

[0319] As R' 201 The aromatic hydrocarbon group in the aromatic ring can specifically include groups obtained by removing one hydrogen atom from the aromatic ring (aryl: for example, phenyl, naphthyl, anthracene, etc.), groups obtained by substituting one hydrogen atom of the 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 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 alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0320] R' 201 Examples of cyclic aliphatic hydrocarbon groups in the structure include aliphatic hydrocarbon groups containing rings.

[0321] Examples of alicyclic hydrocarbon groups containing a ring in the structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an alicyclic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched alicyclic hydrocarbon group, and groups in which the alicyclic hydrocarbon group is intermediate between a straight-chain or branched alicyclic hydrocarbon group.

[0322] The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12.

[0323] The alicyclic hydrocarbon group can be either a polycyclic or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, a monocyclic alkane with 3 to 6 carbon atoms is preferred; examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane; as the polycyclic alkane, a polycyclic alkane with 7 to 30 carbon atoms is preferred. More preferably, as the polycyclic alkane, are polycyclic alkanes with a cross-linked ring structure such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycyclic alkanes with a fused ring structure such as a cyclic group with a steroidal skeleton.

[0324] Among them, as R' 201 The cyclic aliphatic hydrocarbon group in the form is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane or a polycyclic alkane, more preferably a group obtained by removing one hydrogen atom from a polycyclic alkane, particularly preferably adamantyl or norbornyl, and most preferably adamantyl.

[0325] The linear or branched aliphatic hydrocarbon group that can be bonded to the alicyclic 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.

[0326] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0327] 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-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene 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.

[0328] Chain alkyl groups that may have substituents:

[0329] As R' 201 The chain alkyl group can be either straight-chain or branched.

[0330] As a straight-chain alkyl group, it is preferred to have 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotriadecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, dodecyl, etc.

[0331] As a branched alkyl group, it is preferably composed of 3 to 20 carbon atoms, 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.

[0332] Chain alkenyl groups that may have substituents:

[0333] As R' 201 The chain-like alkenyl group can be either straight-chain or branched, preferably with 2 to 10 carbon atoms, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of straight-chain alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0334] As a chain-like alkenyl group, linear alkenyl groups are preferred, vinyl and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0335] As R' 201 Substituents in the cyclic group, chain alkyl group, or chain alkenyl group, for example, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, amino, oxo, and the above R' 201 The group includes cyclic groups, alkyl carbonyl groups, thiophene carbonyl groups, etc.

[0336] Among these, R' 201 Preferably, it is a cyclic group that may have substituents or a chain alkyl group that may have substituents.

[0337] In R 201 ~R 203 R 206 ~R 207 R 211 ~R 212 When they bond together and form a ring with the sulfur atom in the formula, they can be linked via heteroatoms such as sulfur, oxygen, and nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R) N )-(the R N The ring is bonded to functional groups such as alkyl groups having 1 to 5 carbon atoms. Preferably, the ring skeleton containing the sulfur atom in the formula is a three- to ten-membered ring, and particularly preferably a five- to seven-membered ring. Specific examples of the formed ring include thiophene rings, thiazole rings, benzothiophene rings, thiathracene rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthium rings, thioxanone rings, thiathracene rings, phenoxathiin rings, tetrahydrothiophenonium rings, and tetrahydrothiaranonium rings.

[0338] In the formula (ca-3), R 208 ~R 209 Each of the above independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, in R 208 ~R 209 When they are alkyl groups, they can bond with each other to form a ring.

[0339] In the formula (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 -SO2- cyclic group that may have a substituent.

[0340] As R 210 The aryl group in the aryl group can be exemplified by unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred.

[0341] As R210 The alkyl group in the formula is preferably a chain-like or cyclic alkyl group with 1 to 30 carbon atoms.

[0342] As R 210 The alkenyl group in the alkenyl group preferably has 2 to 10 carbon atoms.

[0343] In equations (ca-4) and (ca-5), Y 201 Each can be independently represented as arylene, alkylene, or alkenyl.

[0344] Y 201 The aryl group in R' can be exemplified by... 201 The aromatic hydrocarbon group in the example is a group obtained by removing one hydrogen atom from the aryl group.

[0345] Y 201 The alkylene and alkenylene groups in R' can be exemplified by those derived from R'. 201 The group obtained by removing one hydrogen atom from the chain alkyl or chain alkenyl groups exemplified in the text.

[0346] In equations (ca-4) and (ca-5), x is 1 or 2.

[0347] W 201 It is a (x+1) valence, that is, a divalent or trivalent linker.

[0348] As W 201 The divalent linking group in the above formula (A1) is preferably a divalent hydrocarbon group that may have substituents, and is preferably associated with R in the above formula (A1). EP The examples shown are groups that can have substituents and are identical to divalent hydrocarbon groups. 201 The divalent linking group can be any of the following: linear, branched, or cyclic, preferably cyclic. Preferably, it is a group obtained by combining two carbonyl groups at both ends of the arylene group, or a group composed solely of arylene groups. Examples of arylene groups include phenylene and naphthylene, with phenylene being particularly preferred.

[0349] As W 201 The trivalent linker group in the W can be exemplified by the W 201 Groups obtained by removing one hydrogen atom from a divalent linking group, and groups obtained by bonding another divalent linking group to the divalent linking group, etc. As W 201 The trivalent linking group in the group is preferably a group obtained by bonding two carbonyl groups to an arylene group.

[0350] As the anionic portion of the cationic polymerization initiator other than component (I0), a sulfonic acid anion is preferred. Examples of such sulfonic acid anions include those described above using R... 7 SO3 -The anion represented is camphor sulfonic acid anion, which is particularly preferred.

[0351] In the photosensitive composition of this embodiment, when a cationic polymerization initiator other than component (I0) is used, its content is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of component (A), more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 2 parts by mass.

[0352] <Other Ingredients>

[0353] In addition to components (A) and (I) described above, the photosensitive composition of this embodiment may also contain other components as needed.

[0354] In the photosensitive resin composition of the embodiments, additives with mixed properties can be added as desired, such as metal oxides (M), silane coupling agents, sensitizer components, solvents, additional resins for improving the performance of the film, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, anti-halo agents, etc.

[0355] Metal Oxides (M)

[0356] Starting from the premise that a cured film with improved strength can be easily obtained, the photosensitive resin composition of this embodiment may further contain metal oxide (M) (hereinafter also referred to as "(M) component") in addition to components (A) and (I). Furthermore, by including component (M), high-resolution patterns can be formed with good shape.

[0357] As a component (M), examples include oxides of metals such as silicon (metallic silicon), titanium, zirconium, and hafnium. Among the above, oxides of silicon are preferred, and silicon dioxide is particularly preferred.

[0358] Furthermore, the shape of component (M) is preferably particulate.

[0359] As the aforementioned particulate (M) component, it is preferable to be a substance composed of a group of particles with a volume average particle size of 5 to 40 nm, more preferably a substance composed of a group of particles with a volume average particle size of 5 to 30 nm, and even more preferably a substance composed of a group of particles with a volume average particle size of 10 to 20 nm.

[0360] If the volume average particle size of component (M) is above the lower limit of the above-mentioned preferred range, the strength of the cured film can be easily improved. On the other hand, if it is below the upper limit of the above-mentioned preferred range, it is difficult to generate residues during pattern formation, and it is easier to form patterns with higher resolution. In addition, the transparency of the resin film is improved.

[0361] The particle size of the (M) component can be appropriately selected based on the exposure light source. Generally, particles with a particle size of less than 1 / 10 of the wavelength of light can be used with negligible light scattering effects. Therefore, for example, when forming a fine structure using i-line (365 nm) 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.

[0362] As component (M), one type can be used alone, or two or more types can be used together.

[0363] When the component (M) is included, its content relative to 100 parts by mass of component (A) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass.

[0364] If the content of component (M) is above the lower limit of the above-mentioned preferred range, the strength of the cured film is further improved. On the other hand, if it is below the lower limit of the above-mentioned preferred range, the transparency of the resin film is further improved.

[0365] Silane coupling agents

[0366] To improve adhesion to the substrate, the photosensitive resin composition of this embodiment may further contain an adhesive aid. A silane coupling agent is preferably used as this adhesive aid.

[0367] 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.

[0368] Silane coupling agents can be used alone or in combination with two or more.

[0369] When the silane coupling agent is included, its content relative to 100 parts by weight of component (A) is preferably 2.5 to 20 parts by weight, more preferably 3 to 15 parts by weight, and even more preferably 3 to 10 parts by weight.

[0370] If the content of the silane coupling agent is within the above-mentioned preferred range, the strength of the cured film is further improved. Furthermore, the adhesion between the cured film and the substrate is further enhanced.

[0371] Sensitizer Ingredients

[0372] The photosensitive resin composition of this embodiment may further contain a sensitizer component.

[0373] As a sensitizer component, there are no particular limitations as long as it can absorb the energy generated by exposure and transfer that energy to other substances.

[0374] Specifically, as a sensitizing agent, known photosensitizers such as benzophenone, p,p'-tetramethyldiaminobenzophenone, carbazole, acetophenone, naphthalene, phenol, anthracene, 9-ethoxyanthracene, and diacetyl, eosin, rose red, pyrene, phenothiazine, and anthrone can be used.

[0375] Sensitizers can be used alone or in combination with two or more.

[0376] When the sensitizer component is included, its content relative to 100 parts by weight of component (A) is preferably 0.1 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight.

[0377] If the content of the sensitizer component is within the above-mentioned preferred range, the sensitivity and resolution will be further improved.

[0378] Solvent

[0379] The photosensitive resin composition of this embodiment may further contain a solvent (hereinafter sometimes referred to as "(S) component").

[0380] Examples of components (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; 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 monoalkyl ethers or monophenyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., of the polyols or the compounds with ester bonds. Derivatives of polyols such as compounds [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, methyl toluene, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylene, cumene, toluene, xylene, isopropyl toluene, and mesitylene; and dimethyl sulfoxide (DMSO).

[0381] (S) Component can be used alone or as a mixed solvent of two or more components.

[0382] The amount of component (S) is not particularly limited, and is appropriately set according to the coating film thickness to achieve a concentration that allows the photosensitive composition to be coated onto a substrate or the like without dripping.

[0383] For example, component (S) can be used in a manner where the solid component concentration is 50% by mass or more, and component (S) can also be used in a manner where the solid component concentration is 60% by mass or more.

[0384] In addition, it is possible to use a scheme that is substantially free of (S) components (i.e., a scheme with a solid component concentration of 100% by mass).

[0385] In the negative photosensitive resin composition of this embodiment described above, since it contains a sulfonium salt (I0) represented by the general formula (I0), its compatibility with the epoxy-containing resin (A) is improved, and high sensitivity is achieved relative to the g-line and h-line (it is possible to form patterns with low exposure compared to the prior art). As a result, the resolution during pattern formation can be further improved.

[0386] The negative photosensitive resin composition according to the above embodiments can form a film of the required thickness for the spacer during the formation of a hollow sealing structure, and can be patterned at high resolution with good shape and no residue.

[0387] Furthermore, the negative photosensitive resin composition of this embodiment can also be patterned when forming a film as a thick film, resulting in excellent properties. Therefore, the negative photosensitive resin composition of this embodiment is also useful as a photosensitive dry film resist.

[0388] (Laminated thin film)

[0389] The laminated film of this embodiment is obtained by laminating a photosensitive resin composition layer composed of the negative photosensitive resin composition of the above embodiment with a support film.

[0390] Alternatively, the laminated film may also have a covering film disposed on the opposite side of the side of the support film of the photosensitive resin composition layer formed using a negative photosensitive resin composition.

[0391] The laminated film of this embodiment can be manufactured, for example, by coating a negative photosensitive resin composition of the above embodiment onto a support film, drying it to form a photosensitive resin composition layer, and then laminating a cover film on the photosensitive resin composition layer.

[0392] The negative photosensitive resin composition can be coated onto a substrate film using appropriate methods such as a doctor blade coater, lip coater, comma roller coater, or coating machine.

[0393] The thickness of the photosensitive resin composition layer is preferably less than 100 μm, more preferably 5 to 50 μm.

[0394] For the support film, known films can be used, such as thermoplastic resin films. Examples of such thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 to 150 μm.

[0395] For the cover film, known cover films can be used, such as polyethylene film, polypropylene film, etc. As the cover film, it is preferable that the adhesion to the photosensitive resin composition layer is less than that of the supporting film. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm.

[0396] The supporting film and the covering film can be made of the same film material or different film materials.

[0397] (Pattern Formation Method)

[0398] The pattern forming method of this embodiment includes: a step of forming a photosensitive resin film on a support using the negative photosensitive resin composition of the above embodiment (hereinafter referred to as the "film forming step"), a step of exposing the photosensitive resin film (hereinafter referred to as the "exposure step"), and a step of developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern (hereinafter referred to as the "development step").

[0399] The pattern forming method of this embodiment can be performed, for example, in the following manner.

[0400] [Membrane Formation Process]

[0401] First, the negative photosensitive resin composition of the above embodiment is coated on the support using known methods such as spin coating, roller coating, or screen printing. For example, a baking (post apply bake, PAB) treatment is performed at a temperature of 50 to 150°C for 2 to 60 minutes to form a photosensitive resin film.

[0402] Alternatively, this film forming process can also be performed by placing the photosensitive resin composition layer of the aforementioned laminated film onto a support.

[0403] 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, examples include metal substrates made of silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium tungsten, copper, chromium, iron, aluminum, and glass substrates. Materials used for the wiring pattern include, for example, copper, aluminum, nickel, and gold.

[0404] The patterning method of this embodiment is particularly useful for lithium tantalate (LiTaO3) substrates and lithium niobate (LiNbO3) substrates used in SAW devices mounted in communication terminals.

[0405] The thickness of the photosensitive resin film formed from the negative photosensitive resin composition is not particularly limited, but is preferably about 10 to 100 μm. The negative photosensitive resin composition of the above embodiments exhibits good properties even when formed as a thick film.

[0406] [Exposure Process]

[0407] Next, the formed photosensitive resin film is selectively exposed using a known exposure apparatus by exposure through a mask with a predetermined pattern (mask pattern) or by drawing based on direct irradiation with electron beams without a mask. Then, a baking (post-exposure baking (PEB)) process is performed as needed, for example at a temperature of 80 to 150°C for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds.

[0408] There is no particular limitation on the wavelength used for exposure; selective irradiation (exposure) is 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.

[0409] Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the film thickness, etc. For example, when using an ultra-high pressure mercury lamp, it ranges from 100 to 2000 mJ / cm². 2 .

[0410] The exposure method for photosensitive resin films can be either conventional exposure (dry exposure) in air or an inert gas such as nitrogen, or liquid immersion lithography.

[0411] The photosensitive resin film after the exposure process has high transparency; for example, the haze value when irradiated with i-ray (wavelength 365nm) is preferably less than 3%, and more preferably 1.0 to 2.7%.

[0412] Thus, the photosensitive resin film formed using the negative photosensitive resin composition described above has high transparency. Therefore, during exposure in pattern formation, light transmittance is improved, and negative patterns with good photolithographic properties are easily obtained.

[0413] The haze value of the photosensitive resin film after the above exposure process was measured according to the method of JIS K7136 (2000).

[0414] [Developing process]

[0415] Next, the exposed photosensitive resin film is developed using a developer containing an organic solvent (organic developer). After development, rinsing is preferably performed. Alternatively, baking (post-baking) may be performed as needed.

[0416] As for the organic solvent contained in an organic developer, any organic solvent that can dissolve component (A) (the component (A) before exposure) is acceptable, and it 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, ether solvents, and hydrocarbon solvents.

[0417] 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 alcohol, acetylmethanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methylpentyl ketone (2-heptanone). Among these, methylpentyl ketone (2-heptanone) is preferred as a ketone solvent.

[0418] Examples of ester 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 monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate. Acetates, 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, ethyl lactate, butyl lactate Esters, 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.

[0419] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0420] Organic developers can be mixed with known additives as needed. Examples of such additives include surfactants. There are no particular limitations on the surfactants used; for example, ionic and nonionic fluorinated and / or silicone surfactants can be used.

[0421] As a surfactant, a nonionic surfactant is preferred, and a nonionic fluorinated surfactant or a nonionic silicone surfactant is more preferred.

[0422] When a surfactant is added, the amount added is typically 0.001 to 5% by mass relative to the total amount of the organic developer, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0423] The developing process can be carried out by known developing methods, such as immersing the support in the developing solution for a certain time (immersion method), bearing the developing solution on the surface of the support by surface tension and keeping it still for a certain time (puddle method), spraying the developing solution onto the surface of the support (spraying method), and continuously dispensing the developing solution onto the support rotating at a certain speed while scanning the nozzle at a certain speed (dynamic distribution method), etc.

[0424] Rinsing treatment (cleaning treatment) using rinsing solution can be carried out using known rinsing methods. Examples of such rinsing methods include continuously dispensing rinsing solution onto a support rotating at a certain speed (spin coating), immersing the support in rinsing solution for a certain time (immersion method), and spraying rinsing solution onto the surface of the support (spraying method).

[0425] The rinsing process preferably uses a rinsing solution containing organic solvents.

[0426] Patterns can be formed through the above-mentioned film formation process, exposure process, and development process.

[0427] In the pattern forming method of the above embodiments, since the negative photosensitive resin composition as described in the first aspect is used, it is possible to form a pattern with improved resolution. Furthermore, the pattern forming method according to the embodiments can form patterns that achieve high sensitivity, reduce residue, and have good shape.

[0428] (cured film)

[0429] The cured film in this embodiment is a cured film obtained by curing the negative photosensitive resin composition of the above embodiment.

[0430] (Method for manufacturing cured film)

[0431] The method for manufacturing the cured film according to this embodiment includes: step (i), forming a photosensitive resin film on a support using the negative photosensitive resin composition of the above embodiment; and step (ii), curing the photosensitive resin film to obtain a cured film.

[0432] 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 80 to 150°C for 40 to 600 seconds.

[0433] The curing process in step (ii) can be carried out, for example, at a temperature of 100 to 250°C for 0.5 to 2 hours.

[0434] In addition to steps (i) and (ii), the method for manufacturing the cured film according to the embodiments may include other steps. For example, the above-mentioned [exposure step] may be included between steps (i) and (ii) to selectively expose the photosensitive resin film formed in step (i), or the photosensitive resin film (pre-cured film) that has undergone baking (PEB) treatment may be cured as needed to obtain a cured film.

[0435] According to the method for manufacturing the cured film of the above embodiments, it is possible to easily manufacture a cured film that faithfully reproduces the mask pattern.

[0436] Example

[0437] The present invention will be further described in detail below by way of examples, but the present invention is not limited to these examples. In the description of each manufacturing example, "parts" refers to parts by mass.

[0438] <The manufacture of sulfonium salt>

[0439] (Manufacturing Example 1)

[0440] Synthesis of [2-tert-butyl-5-methyl-4-(2-thioxanthonethio)phenyl](5-tert-butyl-2-methylphenyl)(2-thioxanthone)sulfonate (compound (I0-41))

[0441]

Transformation 33

[0442]

[0443] 1.0 part of 2-[(5-tert-butyl-2-methylphenyl)sulfinyl]thioxanthone, 1.0 part of 2-[(5-tert-butyl-2-methylphenyl)thio]thioxanthone, 5.0 part of acetic anhydride, and 1.9 part of methanesulfonic acid were uniformly mixed and reacted at 65°C for 6 hours. The reaction solution was cooled to room temperature and added to 10 parts of deion-exchanged water for extraction with 10 parts of dichloromethane. The aqueous layer was removed, and the organic layer was washed again with 10 parts of deion-exchanged water. This washing operation was repeated until the pH of the aqueous layer became neutral. Then, 15 parts of cyclohexane were added to the organic layer three times, stirred, and allowed to stand for 30 minutes before removing the upper layer to remove unreacted raw materials. The lower layer was transferred to a rotary evaporator to distill off the solvent, yielding 1.5 parts of compound (I0-41).

[0444] The obtained compound (I0-41) was derived from 1 Identification by H-NMR and LC-MS.

[0445] 1¹H-NMR: d6-dimethyl sulfoxide, δ (ppm) 8.7 (1H, s), 8.2–8.5 (4H, m), 7.7–8.0 (8H, m), 7.5–7.6 (3H, m), 7.2 (2H, d), 7.0 (1H, s), 2.4 (3H, s), 2.3 (3H, s), 2.2 (3H, s), 1.3 (9H, s), 1.1 (9H, s)

[0446] LC-MS: (positive)m / z=779.00, (negative)m / z=94.98

[0447] (Manufacturing Example 2)

[0448] Synthesis of [2-tert-butyl-5-methyl-4-(2-thioxanthonethio)phenyl](5-tert-butyl-2-methylphenyl)(2-thioxanthone)sulfonium tri(pentafluoroethyl)trifluorophosphate (compound (I0-46))

[0449]

Transformation 34

[0450]

[0451] 1.0 part of compound (I0-41) synthesized in Manufacturing Example 1 was dissolved in 5.8 parts of dichloromethane, and 0.59 parts of potassium tris(pentafluoroethyl)trifluorophosphate and 5.1 parts of deionized water were added. The mixture was stirred at room temperature for 1 hour. The organic layer was washed 5 times with 5 parts of deionized water and then transferred to a rotary evaporator to distill off the solvent, yielding 1.26 parts of compound (I0-46).

[0452] The obtained compound (I0-46) was derived from 1 H-NMR, 19 F-NMR identification.

[0453] 1 ¹H-NMR: d6-dimethyl sulfoxide, δ (ppm) 8.7 (1H, s), 8.2–8.5 (4H, m), 7.7–8.0 (8H, m), 7.5–7.6 (3H, m), 7.2 (2H, d), 7.0 (1H, s), 2.4 (3H, s), 2.2 (3H, s), 1.3 (9H, s), 1.1 (9H, s)

[0454] 19 1 / 2F-NMR: d6-dimethyl sulfoxide, δ (ppm) -42.0 (1F, d), -79.9 (3F, s), -81.2 (6F, s), -87.9 (2F, d), -115.0~-116.2 (6F, m)

[0455] (Manufacturing Example 3)

[0456] Synthesis of [2-tert-butyl-5-methyl-4-(2-thioxanthonethio)phenyl](5-tert-butyl-2-methylphenyl)(2-thioxanthone)sulfonium tetra(pentafluorophenyl)borate (compound (I0-45))

[0457]

Chemistry 35

[0458]

[0459] Except for changing "0.59 parts of potassium tri(pentafluoroethyl)trifluorophosphate" to "0.85 parts of sodium tetra(pentafluorophenyl)borate" in Manufacturing Example 2, 1.5 parts of compound (I0-45) were obtained by operating in the same manner as in Manufacturing Example 2.

[0460] The obtained compound (I0-45) was obtained from 1 H-NMR, 19 F-NMR identification.

[0461] 1 ¹H-NMR: d6-dimethyl sulfoxide, δ (ppm) 8.7 (1H, s), 8.2–8.5 (4H, m), 7.7–8.0 (8H, m), 7.5–7.6 (3H, m), 7.2 (2H, d), 7.0 (1H, s), 2.4 (3H, s), 2.2 (3H, s), 1.3 (9H, s), 1.1 (9H, s)

[0462] 19 1 / 2 ppm F-NMR: d6-dimethyl sulfoxide, δ (ppm) -132.1 (8F, s), -161.8 (4F, s), -166.0 (8F, s)

[0463] (Manufacturing Example 4)

[0464] Synthesis of compound (H1-TF)

[0465]

Transformation 36

[0466]

[0467] While stirring at 40°C, 4.3 parts of 2-(phenylthio)thioxanthone, 4.5 parts of 2-[(phenyl)sulfinyl]thioxanthone, 4.1 parts of acetic anhydride, and 110 parts of acetonitrile were added dropwise with 2.4 parts of trifluoromethanesulfonic acid. The reaction was carried out at 40–45°C for 1 hour. The reaction solution was then cooled to room temperature (approximately 25°C) and added to 150 parts of distilled water. Extraction was performed with chloroform, followed by washing with water until the pH of the aqueous phase became neutral. The chloroform phase was transferred to a rotary evaporator to remove the solvent. This process was repeated three times, adding 50 parts of toluene and dispersing the solid in the toluene using an ultrasonic cleaner. After standing for approximately 15 minutes, the supernatant was removed to clean the solid. The solid was then transferred to a rotary evaporator to remove the solvent, yielding compound (H1-TF).

[0468] (Manufacturing Example 5)

[0469] Synthesis of compound (H1-FP)

[0470]

Chemistry 37

[0471]

[0472] 1.0 part of compound (H1-TF) was dissolved in 6.4 parts of dichloromethane, and 0.60 parts of potassium tris(pentafluoroethyl)trifluorophosphate and 5.7 parts of deionized water were added. The mixture was stirred at room temperature for 1 hour. The organic layer was washed five times with 6 parts of deionized water, and the solvent was removed by distillation in a rotary evaporator to obtain 1.2 parts of compound (H1-FP). The obtained compound (H1-FP) was... 1 H-NMR, 19 F-NMR identification.

[0473] 1 ¹H-NMR: d6-dimethyl sulfoxide, δ (ppm) 8.7 (¹H, d), 8.5 (¹H, d), 8.4 (2H, m), 8.2 (¹H, d), 8.1 (¹H, dd), 8.0 (¹H, d), 7.7–7.9 (¹²H, m), 7.6 (2H, m), 7.5 (2H, d)

[0474] 19 1 / 2F-NMR: d6-dimethyl sulfoxide, δ (ppm) -42.0 (1F, d), -79.9 (3F, s), -81.2 (6F, s), -87.9 (2F, d), -115.0~-116.2 (6F, m)

[0475] (Manufacturing Example 6)

[0476] Synthesis of compound (H1-B)

[0477]

Transformation 38

[0478]

[0479] Except for changing "0.60 parts of potassium tri(pentafluoroethyl)trifluorophosphate" to "0.93 parts of sodium tetra(pentafluorophenyl)borate" in Manufacturing Example 5, 1.5 parts of compound (H1-B) were obtained by operating in the same manner as in Manufacturing Example 5.

[0480] The obtained compound (H1-B) was derived from 1 H-NMR, 19 F-NMR identification.

[0481] 1 ¹H-NMR: d6-dimethyl sulfoxide, δ (ppm) 8.7 (¹H, d), 8.5 (¹H, d), 8.4 (2H, m), 8.2 (¹H, d), 8.1 (¹H, dd), 8.0 (¹H, d), 7.7–7.9 (¹²H, m), 7.6 (2H, m), 7.5 (2H, d)

[0482] 19 1 / 2 ppm F-NMR: d6-dimethyl sulfoxide, δ (ppm) -132.1 (8F, s), -161.8 (4F, s), -166.0 (8F, s)

[0483] <Preparation of Negative Photosensitive Resin Compositions>

[0484] (Examples 1-2, Comparative Examples 1-2)

[0485] The components shown in Table 1 were mixed and dissolved, and filtered using a PTFE filter (1 μm pore size, manufactured by PALL Corporation) to prepare negative photosensitive resin compositions (solutions of 65% by mass of solid components) for each example.

[0486] [Table 1]

[0487]

[0488] In Table 1, each abbreviation has the following meaning. The value in [] is the amount of each component blended (parts by mass; converted to solid content).

[0489] (A)-1: A phenolic varnish-type epoxy resin represented by the following general formula (A11). Trade name "JER157S70", manufactured by Mitsubishi Chemical Corporation.

[0490]

Chemistry 39

[0491]

[0492] (A)-2: Bisphenol A type epoxy resin represented by the following general formula (A21). Trade name "EPICLON1055", manufactured by DIC Corporation. In formula (A21), n ​​is the number of repetitions of the structure in parentheses.

[0493]

Chemistry 40

[0494]

[0495] (I)-1: The above compound (I0-46).

[0496] (I)-2: The above compound (I0-45).

[0497] (I)-3: The above compound (H1-B). That is, the cationic polymerization initiator represented by the following chemical formula (I1-1).

[0498] (I)-4: The above compound (H1-FP). That is, the cationic polymerization initiator represented by the following chemical formula (I2-1).

[0499]

Chemistry 41

[0500]

[0501] (I)-5: A cationic polymerization initiator represented by the following chemical formula (I3-1).

[0502]

Chemistry 42

[0503]

[0504] (S)-1: Methoxybutyl acetate

[0505] <Pattern Formation (1)>

[0506] Membrane formation process:

[0507] Each example of a negative photosensitive resin composition was coated onto a lithium tantalate (LiTaO3) substrate with a thickness of 0.35 mm using a spin coater. The mixture was then pre-baked (PAB) at 115°C for 5 minutes on a hot plate and dried to form a photosensitive resin film with a thickness of 20 μm.

[0508] Exposure process:

[0509] Next, at 350mJ / cm 2 The photosensitive resin film was irradiated with ghi rays at a certain irradiation level. Subsequently, it was exposed to a heating plate at 90°C for 15 minutes followed by heating.

[0510] Developing process:

[0511] Next, propylene glycol monomethyl ether acetate (PGMEA) was used for development for 180 seconds to attempt to form a negative pattern.

[0512] <Pattern Formation (2)>

[0513] Membrane formation process:

[0514] Each example of a negative photosensitive resin composition was coated onto a lithium niobate (LiNbO3) substrate with a thickness of 0.35 mm using a spin coater. The mixture was then pre-baked (PAB) at 115°C for 5 minutes on a heated plate and dried to form a photosensitive resin film with a thickness of 20 μm.

[0515] Exposure process:

[0516] Next, the photosensitive resin film was exposed using a GHz broadband exposure machine via a photomask, and the i-line value was converted to 350 mJ / cm. 2 The exposure.

[0517] Subsequently, it was exposed to a heating plate at 90°C for 15 minutes and then heated.

[0518] Developing process:

[0519] Next, propylene glycol monomethyl ether acetate (PGMEA) was used for 30 seconds of development in an attempt to form a negative pattern.

[0520] [Mask Reproducibility]

[0521] Through the above pattern formation (1) and pattern formation (2), with an exposure of 350 mJ / cm 2 A contact hole (C / H) pattern with a target size of 20 μm diameter was formed. The results are as follows.

[0522] Pattern formation (1): Lithium tantalate (LiTaO3) substrate

[0523] Example 1: A C / H pattern with a hole diameter of 19.418 μm was formed.

[0524] Example 2: A C / H pattern with a hole diameter of 17.887 μm was formed.

[0525] Comparative Example 1: No image formed (poor resolution).

[0526] Comparative Example 2: No image formed (poor resolution).

[0527] Pattern formation (2): Lithium niobate (LiNbO3) substrate

[0528] Example 1: A C / H pattern with a hole diameter of 20.356 μm was formed.

[0529] Example 2: A C / H pattern with a hole diameter of 19.944 μm was formed.

[0530] Comparative Example 1: A C / H pattern with a hole diameter of 17.540 μm was formed.

[0531] Comparative Example 2: A C / H pattern with a hole diameter of 16.582 μm was formed.

[0532] [Extreme Resolution]

[0533] In each exposure step of the above-mentioned pattern formation (1) and pattern formation (2), the exposure amount is made to be between 250 and 600 mJ / cm. 2 Within the range, each change is 50 mJ / cm 2 To form the C / H pattern, a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Co., Ltd.) was used to determine the smallest pattern size that could be resolved at each exposure.

[0534] Exposure 350mJ / cm 2 The results are shown below.

[0535] Pattern formation (1): Lithium tantalate (LiTaO3) substrate

[0536] Example 1: C / H patterns with hole diameters up to 10 μm were formed.

[0537] Example 2: C / H patterns with hole diameters up to 15 μm were formed.

[0538] Comparative Example 1: No image formed (poor resolution).

[0539] Comparative Example 2: C / H patterns with aperture diameters up to 40 μm were formed.

[0540] Furthermore, the negative photosensitive resin composition of Example 1 is capable of operating at an exposure level of 350–450 mJ / cm. 2 C / H patterns with aperture diameters up to 10 μm are formed within the specified range.

[0541] The negative photosensitive resin composition of Example 2 is capable of operating at an exposure level of 300–400 mJ / cm. 2 C / H patterns with aperture diameters up to 15 μm are formed within the specified range.

[0542] Therefore, it can be confirmed that the negative photosensitive resin compositions of Examples 1 and 2 have excellent exposure latitude.

[0543] Pattern formation (2): Lithium niobate (LiNbO3) substrate

[0544] Example 2: C / H patterns with hole diameters up to 10 μm were formed.

[0545] Comparative Example 1: C / H patterns with aperture diameters up to 20 μm were formed.

[0546] Furthermore, the negative photosensitive resin composition of Example 2 is capable of operating at an exposure level of 250–300 mJ / cm. 2 C / H patterns with hole diameters up to 5 μm are formed within the range.

[0547] Therefore, it can be confirmed that the negative photosensitive resin composition of Example 2 is particularly excellent in terms of resolution.

[0548] Based on the above evaluation results, it was confirmed that the negative photosensitive resin compositions of Examples 1 and 2 of the present invention, which were applied to this invention, had a higher resolution compared to the negative photosensitive resin compositions of Comparative Examples 1 and 2, which were outside the scope of the present invention.

Claims

1. A negative photosensitive resin composition, comprising an epoxy-containing resin (A) and a cationic polymerization initiator (I), characterized in that, The cationic polymerization initiator (I) comprises a sulfonium salt (I0) represented by the following general formula (I0). In equation (I0), R1 represents a thioxanthone group, and R2 represents an aryl group with 6 to 30 carbon atoms, wherein a portion of the hydrogen atoms of the aryl group is substituted or unsubstituted by a substituent (t), which is an alkyl group with 1 to 18 carbon atoms. R3 to R5 are alkyl, hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, hydroxy(poly)alkeneoxy, or halogen atoms, respectively. k, m, and n represent the number of R3, R4, and R5, where k is 0, m is 0, and n is an integer from 1 to 4. When n is 2 to 4, multiple R5s may be the same or different from each other. A is a group represented by -S-, O is an oxygen atom, S is a sulfur atom, and X is a sulfur atom. - This refers to a monovalent polyatomic anion.

2. The negative photosensitive resin composition according to claim 1, characterized in that, X in the general formula (I0) - Therefore (Rf) b PF 6-b - or R 6 c BY 4-c - The anion is represented by Rf, which represents an alkyl group in which more than 80 mol% of hydrogen atoms are replaced by fluorine atoms. 6 This indicates a phenyl group obtained by replacing a portion of a hydrogen atom with at least one halogen atom or with an electron-withdrawing group, where Y represents a halogen atom, b is an integer from 1 to 5, and c is an integer from 1 to 4.

3. The negative photosensitive resin composition according to claim 1, characterized in that, The content of the sulfonium salt (I0) is 0.1 to 5 parts by mass relative to 100 parts by mass of the epoxy-containing resin (A).

4. The negative photosensitive resin composition according to claim 1, characterized in that, The epoxy-containing resin (A) comprises resins having glycidyl ether groups in their structure.

5. The negative photosensitive resin composition according to claim 1, characterized in that, The epoxy-containing resin (A) combines the properties of phenolic varnish-type epoxy resin and bisphenol A-type epoxy resin.

6. A pattern forming method, characterized in that, The device comprises: a step of forming a photosensitive resin film on a support using the negative photosensitive resin composition according to any one of claims 1 to 5; a step of exposing the photosensitive resin film; and a step of developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern.

7. A laminated thin film, characterized in that, It is obtained by laminating a photosensitive resin composition layer made of the negative photosensitive resin composition according to any one of claims 1 to 5 with a support film.

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