Negative-type photosensitive resin composition, method for producing hollow structures, and polymer compounds

Abstract

To provide a negative type photosensitive resin composition suppressed in deformation of a top board part by heat treatment, a production method of a hollow structure, and a macromolecular compound.SOLUTION: A negative type photosensitive resin composition includes: a resin component (A) having a constitutional unit (a01) represented by a general formula (a0-1), a constitutional unit (a00) represented by a general formula (a0-0), and a constitutional unit (a02) represented by a general formula (a0-2); a cationic polymerization initiator; and a photoradical polymerization initiator. In the formulae, Rx1a and Rx1b are groups having cationic polymerizable groups, Rx2a and Rx2b are groups having radical polymerizable groups, and one of Rx0a and Rx0b is a group having a cationic polymerizable group, and the other is a group having a radical polymerizable group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative-type photosensitive resin composition, a method for producing a hollow structure, and a polymer compound. [Background technology]

[0002] In recent years, the development of micro-electronic devices such as surface acoustic wave (SAW) filters has progressed. Packages containing such electronic devices have a hollow structure to ensure the propagation of surface acoustic waves and the mobility of the movable components of the electronic device. A photosensitive resin composition is used to form the aforementioned hollow structure, and the package is manufactured by molding while maintaining the hollow structure on the wiring substrate on which the electrodes are formed.

[0003] For example, Patent Document 1 discloses a method for manufacturing a hollow package, comprising the steps of forming a cavity to cover Micro Electro Mechanical Systems (MEMS) formed on a substrate to create a hollow structure, and sealing the entire hollow structure with a sealing layer by transfer molding. Patent Document 1 also discloses a negative-type photosensitive resin composition containing an epoxy group-containing compound and a cationic polymerization initiator.

[0004] The cavity securing portion is formed as follows. After applying a photosensitive resin composition around the MEMS, exposure, post-exposure baking (PEB), and development are performed via a photomask to create the sidewalls. Next, the cover film is peeled off from the dry film resist, which is formed by laminating a base film, a photosensitive resin composition layer, and a cover film in that order, and laminated onto the upper part of the side wall to form the top plate. Exposure, PEB, and development are performed again through a photomask, and unnecessary parts are removed to create the top plate, thereby forming the cavity securing portion. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2009 / 151050 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] When fabricating hollow structures, a high-temperature heat treatment (curing operation) of, for example, 200°C or higher is generally performed on the cavity-securing portion after development in order to increase the strength of the cured film of the photosensitive resin composition layer. During the heat treatment of the PEB when fabricating hollow structures and the high-temperature heat treatment of the curing operation, a phenomenon called doming may occur, in which the air inside the hollow structure expands and the top plate portion bulges. When conventional negative-type photosensitive resin compositions, such as the negative-type photosensitive resin composition described in Patent Document 1, are used as the top plate portion of a hollow structure, a doming phenomenon occurs depending on the blending balance, making it difficult to reduce the height of electronic components having a hollow structure.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a negative-type photosensitive resin composition, a method for manufacturing a hollow structure, and a polymer compound that suppress deformation of the top plate portion due to heat treatment. [Means for solving the problem]

[0008] The present invention includes the following embodiments. In other words, a first aspect of the present invention is a negative-type photosensitive resin composition comprising a resin component (A), a cationic polymerization initiator, and a photoradical polymerization initiator, wherein the resin component (A) has a constituent unit (a01) represented by the following general formula (a0-1), a constituent unit (a00) represented by the following general formula (a0-0), and a constituent unit (a02) represented by the following general formula (a0-2).

[0009] [ka] [In the formula, R11 , R 12 , R 21 , R 22 , R 01 and R 02 is, independently of one another, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R x1a and R x1b is a group containing a cationically polymerizable group. R x2a and R x2b is a group containing a radically polymerizable group. R x0a and R x0b is such that one is a group containing a cationically polymerizable group and the other is a group containing a radically polymerizable group. R x1a and R x1b may be the same as or different from each other. R x2a and R x2b may be the same as or different from each other. l, m and n represent the proportions of the respective structural units in the resin component (A). l + m + n ≤ 1. 0 < l + m. 0 < m + n.

[0010] A second aspect of the present invention is a method for producing a hollow structure including a recess and a top plate portion closing an opening surface of the recess, the method including forming the top plate portion using the negative-type photosensitive resin composition according to the first aspect.

[0011] A third aspect of the present invention is a polymer compound having a structural unit (a01) represented by the following general formula (a0-1), a structural unit (a00) represented by the following general formula (a0-0), and a structural unit (a02) represented by the following general formula (a0-2).

[0012] [Chemical formula] [In the formula, R 11 , R 12 , R 21 , R 22 , R 01 and R 02Each of these is independently either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R x1a and R x1b R is a group containing a cationic polymerizable group. x2a and R x2b R is a group containing a radical polymerizable group. x0a and R x0b One of these groups contains a cationic polymerizable group, and the other contains a radical polymerizable group. R x1a and R x1b They may be identical or different from each other. x2a and R x2b They may be identical or different from one another. l, m, and n represent the proportions of each constituent unit in the polymer compound. l+m+n≦1. <l+mである。0<m+nである。] [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a negative-type photosensitive resin composition, a method for manufacturing a hollow structure, and a polymer compound that suppress deformation of the top plate portion due to heat treatment. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic diagram illustrating a method for manufacturing a hollow structure according to an embodiment of the present invention. [Modes for carrying out the invention]

[0015] In this specification and in the claims, "aliphatic" is defined as a concept relative to aromatic, meaning a group that does not possess aromaticity, a compound that does not possess aromaticity, etc. Unless otherwise specified, "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups within alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group are replaced by halogen atoms, and examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. A "fluorinated alkyl group" refers to a group in which some or all of the hydrogen atoms of an alkyl group are replaced with fluorine atoms. "Constituent unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer). When it is stated that a group "may have substituents," this includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and cases where a methylene group (-CH2-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation exposure.

[0016] (Negative-type photosensitive resin composition) The negative-type photosensitive resin composition according to this embodiment (hereinafter sometimes simply referred to as "photosensitive resin composition") contains a resin component (A) (hereinafter also referred to as "component (A)"), a cationic polymerization initiator (I) (hereinafter also referred to as "component (I)"), and a photoradical polymerization initiator (C) (hereinafter also referred to as "component (C)"). When a photosensitive resin film is formed using such a photosensitive resin composition and selectively exposed to light, the cation portion of component (I) decomposes in the exposed area of ​​the photosensitive resin film to generate acid, and cations derived from the cationic polymerizable group in component (A) are generated by the action of this acid, and the cationic polymerizable group in component (A) polymerizes by the action of these cations. In the exposed portion of the photosensitive resin film, along with this cationic polymerization reaction, radical polymerizable groups in component (A) polymerize due to the action of radicals generated from component (C) by exposure. As a result, the solubility of component (A) in the developer containing an organic solvent decreases in the exposed areas of the photosensitive resin film, while the solubility of component (A) in the developer containing an organic solvent remains unchanged in the unexposed areas of the photosensitive resin film. Therefore, a difference in solubility in the developer containing an organic solvent occurs between the exposed and unexposed areas of the photosensitive resin film. Consequently, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed areas are dissolved and removed, forming a negative-type pattern.

[0017] <Resin component (A)> The resin component (A) has a constituent unit (a01) represented by the following general formula (a0-1), a constituent unit (a00) represented by the following general formula (a0-0), and a constituent unit (a02) represented by the following general formula (a0-2).

[0018] [ka] [In the formula, R 11 , R 12 , R 21 , R 22 , R 01 and R 02 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R x1a and R x1b R is a group containing a cationic polymerizable group. x2a and R x2b R is a group containing a radical polymerizable group. x0a and R x0b One of these groups contains a cationic polymerizable group, and the other contains a radical polymerizable group. R x1a and R x1b They may be identical or different from each other. x2a and R x2b They may be identical or different from one another. l, m, and n represent the proportions of each constituent unit in the resin component (A). l+m+n≦1. <l+mである。0<m+nである。]

[0019] In the above general formulas (a0-0) to (a0-2), R 11 , R 12 , R 21 , R 22 , R 01 and R 02 In this context, the alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. Examples of cyclic alkyl groups include cyclobutyl and cyclopentyl groups. Among the alkyl groups having 1 to 5 carbon atoms, hydrogen atoms or linear or branched alkyl groups are preferred, hydrogen atoms or linear alkyl groups are more preferred, and hydrogen atoms or methyl groups are particularly preferred. R 11 and R 12 They may be identical or different from each other. 21 and R 22 They may be identical or different from each other. 01 and R 02 They may be identical or different from one another.

[0020] ≪Cationic polymerizable group≫ R x1a , R x1b , and also, R x0a and R x0b Either one of these groups contains a cationic polymerizable group. A "cationic polymerizable group" is a group that enables cationic polymerization when a cation-providing initiator is used, such as an epoxy group.

[0021] R x1a , R x1b , R x0a and R x0b The cationic polymerizable group in either of these is not particularly limited, and examples include cyclic ether groups. Examples of cyclic ether groups include epoxy groups and oxetane groups.

[0022] When the cationic polymerizable group is an epoxy group, R contains the cationic polymerizable group. x1a , R x1b , and also, R x0a and R x0b Either of these groups is not particularly limited and may include a group consisting solely of an epoxy group; a group consisting solely of an alicyclic epoxy group; or a group having an epoxy group or an alicyclic epoxy group and a divalent linking group. An alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure, which is a three-membered ring ether. Specifically, it is a group having both an alicyclic group and an oxacyclopropane structure. The alicyclic group forming the basic skeleton of an alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups. Furthermore, the hydrogen atoms of these alicyclic groups may be substituted with alkyl groups, alkoxy groups, hydroxyl groups, etc. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or alicyclic epoxy group is bonded via the divalent linking group bonded to the oxygen atom (-O-) in the formula.

[0023] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have substituents, a divalent linking group which contains a heteroatom, and so on.

[0024] Regarding divalent hydrocarbon groups that may have substituents: Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated. More specifically, examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0025] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically including methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], and the like. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6, even more preferably 2 to 4, and most preferably 2 or 3. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically 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-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0026] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is one obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, and the like. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0027] In divalent hydrocarbon groups, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system with (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group or heteroaryl group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (e.g., groups obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0028] The divalent hydrocarbon group may have substituents. The divalent hydrocarbon group, a linear or branched aliphatic hydrocarbon group, may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0029] Alicyclic hydrocarbon groups in aliphatic hydrocarbon groups containing a ring in their structure, as divalent hydrocarbon groups, may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and the like. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. The alkoxy group used as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being preferred, and methoxy and ethoxy groups being the most preferred. Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like, with fluorine atoms being preferred. Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. The alicyclic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0030] As a divalent hydrocarbon group, the aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the alkoxy group, halogen atom, and alkyl halogenated group used as substituents include those that substitute for the hydrogen atoms of the alicyclic hydrocarbon group.

[0031] Regarding divalent linking groups containing heteroatoms: In a divalent linking group containing a heteroatom, the heteroatom is an atom other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0032] In the divalent linking group containing a heteroatom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group); -S-, -S(=O)2-, -S(=O)2-O-, general formula -Y 21 -O-Y 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-O-Y 21 , -[Y 21 -C(=O)-O] m” -Y 22 - or -Y 21 -O-C(=O)-Y 22 - represented groups [wherein, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m” is an integer of 0 to 3.], etc. may be mentioned. When the divalent linking group containing the heteroatom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)-, the H thereof may be substituted with a substituent such as an alkyl group or an acyl group. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Formula -Y 21 -O-Y 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-O-Y 21 -, -[Y 21 -C(=O)-O] m” -Y 22 - or -Y 21 -O-C(=O)-Y 22 - in, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as those of the “divalent hydrocarbon group which may have a substituent” mentioned in the description of the divalent linking group above. Y 21 is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. In the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 -, m” is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 -, the group represented by the formula -Y 21 -C(=O)-O-Y 22 - is particularly preferred. Among them, the group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ - is preferred. In the formula, a’ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b’ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0033] R x1a 、R x1b 、and x0a R x0b any one of and R The cationic polymerizable group is preferably an epoxy group. R x1a 、R x1b 、and x0a R x0b ​​A glycidyl group is preferred as one of the two.

[0034] <<Radical Polymerizable Group>> R x2a and R x2b , and also, R x0a and R x0b Either one of these groups contains a radical polymerizable group. A "radical polymerizable group" is a group that enables a polymerizable compound to be polymerized by radical polymerization, and refers to a group that includes multiple bonds between carbon atoms, such as an ethylenic double bond.

[0035] R x2a and R x2b , and also, R x0a and R x0b Either one of them is W 01 -L 01 - is a base represented by W. 01 L is a radical polymerizable group. 01 It is a linking group. Examples of radical polymerizable groups include vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, fluorovinyl groups, difluorovinyl groups, trifluorovinyl groups, difluorotrifluoromethylvinyl groups, trifluoroallyl groups, perfluoroallyl groups, trifluoromethylacryloyl groups, nonylfluorobutylacryloyl groups, vinyl ether groups, fluorinated vinyl ether groups, allyl ether groups, fluorinated allyl ether groups, styryl groups, vinylnaphthyl groups, fluorinated styryl groups, fluorinated vinylnaphthyl groups, norbornyl groups, fluorinated norbornyl groups, and silyl groups, with acryloyl groups or methacryloyl groups being preferred.

[0036] W 01 Examples of polymerizable groups in this context include, for example, the chemical formula: C(R X11 )(R X12 )=C(R X13 Groups represented by )- are preferred examples. In this chemical formula, R X11 , R X12 and R X13These are, respectively, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms.

[0037] L 01 It is a single bond or a divalent linking group. L 01 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. L 01 Preferably, the group is a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof. More preferably, the group is a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], or -C(=O)-O-CH2-CH(OH)-CH2-, and even more preferably -C(=O)-O-CH2-CH(OH)-CH2-.

[0038] In the general formulas (a0-0) to (a0-2) above, l, m, and n represent the proportion of each constituent unit in the resin component (A). Here, the proportion refers to the ratio of the number of repetitions of each constituent unit to the total number of repetitions of all constituent units constituting component (A) (which is set to 1). l+m+n≦1. <l+mである。0<m+nである。 It is preferable that 0.3 ≤ l + m + n, more preferably that 0.5 ≤ l + m + n, even more preferably that 0.7 ≤ l + m + n, particularly preferably that 0.8 ≤ l + m + n, and most preferably that 0.9 ≤ l + m + n.

[0039] In resin component (A), l + m + n = 1. In this case, resin component (A) consists of constituent unit (a01), constituent unit (a00), and constituent unit (a02).

[0040] Alternatively, in resin component (A), l + m ≤ 1 and n = 0. In this case, resin component (A) has constituent units (a01) and (a00).

[0041] Alternatively, in resin component (A), m+n≦1 and l=0. In this case, resin component (A) has constituent units (a00) and (a02).

[0042] Alternatively, in resin component (A), m ≤ 1 and l = n = 0. In this case, resin component (A) has constituent units (a00).

[0043] Among these, the resin component (A) is preferably composed of constituent unit (a01), constituent unit (a00), and constituent unit (a02).

[0044] The ratio of constituent unit (a01), constituent unit (a02), and constituent unit (a00) preferably satisfies the relationship 1 ≤ (2l + m) / (m + 2n). The ratio of constituent units (a01), (a02), and (a00) preferably satisfies (2l+m) / (m+2n)≦9, more preferably (2l+m) / (m+2n)≦6, and even more preferably (2l+m) / (m+2n)≦4. Among these, it is preferable that (2l+m) / (m+2n)≦3, more preferably (2l+m) / (m+2n)≦2, and even more preferably (2l+m) / (m+2n)≦1.5. In resin component (A), when l, m, and n satisfy the above relationship, doming due to heating during curing is more easily suppressed in the top plate portion of the hollow structure formed from the negative-type photosensitive resin composition.

[0045] ≪Epoxy Equivalent≫ Epoxy equivalent is the mass of resin containing one equivalent of epoxy groups. The unit is g / eq. The epoxy equivalent can be measured by the method described in JIS K-7236. Specifically, it can be measured by the following method: First, the sample is dissolved in chloroform, and acetic acid and tetraethylammonium bromide acetic acid solution are added. Next, potentiometric titration is performed using a 0.1 mol / L perchloric acid acetic acid standard solution. Then, a titration curve is created from the measurement results, and the epoxy equivalent is determined using the inflection point on the titration curve as the endpoint.

[0046] In the photosensitive resin composition according to this embodiment, the epoxy equivalent of resin component (A) is preferably 300 to 750 g / eq., more preferably 400 to 750 g / eq., even more preferably 500 to 750 g / eq., particularly preferably 600 to 750 g / eq., and most preferably 650 to 750 g / eq. Because the epoxy equivalent of resin component (A) is within the above range, doming due to heating during curing is more easily suppressed in the top plate portion of the hollow structure formed from the negative-type photosensitive resin composition.

[0047] Acid Value The acid value is the number of milligrams (mg) of potassium hydroxide required to neutralize all acidic components in 1 g of sample. The unit is KOH mg / g. The acid value can be measured by the method described in JIS K2501. Specifically, it can be measured by the following method: First, the sample is dissolved in a titration solvent containing toluene, 2-propanol, and a small amount of water. Next, the glass electrode and reference electrode are immersed in the titration solvent, and potentiometric titration is performed using a 2-propanol standard solution of potassium hydroxide. Then, a titration curve is created from the measurement results, and the acid value is determined by setting the inflection point on the titration curve as the neutralization point.

[0048] In the photosensitive resin composition according to this embodiment, the acid value of resin component (A) is preferably 0.03 to 0.50 KOH mg / g, preferably 0.05 to 0.30 KOH mg / g, and more preferably 0.05 to 0.20 KOH mg / g.

[0049] The resin component (A) may be used alone or in combination of two or more types. The resin component (A) preferably contains a polymer compound consisting of constituent units (a01), (a00), and (a02), and more preferably consists only of a polymer compound consisting of constituent units (a01), (a00), and (a02). In a polymer compound consisting of constituent units (a01), (a00), and (a02), it is preferable that the ratio of constituent units (a01), (a02), and (a00) satisfies the relationship 1 ≤ (2l + m) / (m + 2n). In a polymer compound consisting of constituent units (a01), (a00), and (a02), the ratio of constituent units (a01), (a02), and (a00) preferably satisfies (2l+m) / (m+2n)≦9, more preferably (2l+m) / (m+2n)≦6, and even more preferably (2l+m) / (m+2n)≦4. Among these, it is preferable that (2l+m) / (m+2n)≦3, more preferably (2l+m) / (m+2n)≦2, and even more preferably (2l+m) / (m+2n)≦1.5.

[0050] The negative-type photosensitive resin composition according to this embodiment may contain, in addition to the resin consisting of constituent units (a01), (a00), and (a02), other materials such as novolac-type epoxy resin, bisphenol-type epoxy resin, aliphatic epoxy resin, or acrylic resin.

[0051] The content of component (A) in the photosensitive resin composition according to the embodiment may be adjusted according to the thickness of the photosensitive resin film to be formed. Furthermore, in the photosensitive resin composition according to this embodiment, the content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on the total amount (100% by mass) of the negative-type photosensitive resin composition. (A) When the content of component is above the lower limit, doming due to heating during curing is more easily suppressed in the top plate portion of the hollow structure formed from the negative-type photosensitive resin composition.

[0052] For example, in the photosensitive resin composition according to this embodiment, the content of component (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total content of components (A), (I), and (C) of 100% by mass. (A) When the content of component is above the lower limit, doming due to heating during curing is more easily suppressed in the top plate portion of the hollow structure formed from the negative-type photosensitive resin composition.

[0053] <Cationic polymerization initiator (I)> The cationic polymerization initiator (component (I)) is a compound that generates cations derived from cationic polymerizable groups through the action of acids generated by irradiation with active energy rays such as ultraviolet light, far ultraviolet light, excimer laser light such as KrF and ArF, X-rays, and electron beams, and these cations initiate or promote the polymerization of component (A).

[0054] Examples of component (I) used in the photosensitive resin composition according to this embodiment include onium salts, onium borate salts, sulfonates, and carboxylates containing phosphorus anions.

[0055] ≪Onium salts containing phosphorus anions≫ Examples of onium salts containing phosphorus anions include compounds represented by the following general formula (I2) (hereinafter referred to as "component (I2)").

[0056] Regarding compounds represented by the general formula (I2) (component (I2): Component (I2) is a compound represented by the following general formula (I2). Since component (I2) generates a relatively strong acid upon exposure, sufficient sensitivity is obtained and a good pattern is formed when a pattern is formed using a photosensitive resin composition containing component (I).

[0057] [ka] [In the formula, R b05 R is a fluorinated alkyl group which may have substituents, or a fluorine atom. b05 They may be identical or different from each other. q is an integer greater than or equal to 1, and Q q+ This is a q-valent organic cation.

[0058] · Anion Club In the above formula (I2), R b05 R is a fluorinated alkyl group which may have substituents, or a fluorine atom. b05 They may be identical or different from one another. R b05 The fluorinated alkyl group in this context preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. Specifically, this includes alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms. Among them, R b05 Preferably, the group is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms; more preferably, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms; and even more preferably, a fluorine atom, a trifluoromethyl group, or a pentafluoroethyl group.

[0059] The anionic portion of the compound represented by formula (I2) is preferably represented by the following general formula (b0-2a).

[0060] [ka] [In the formula, R bf05 nb is a fluorinated alkyl group which may have substituents. 1[This is an integer between 1 and 5.]

[0061] In formula (b0-2a), R bf05 The fluorinated alkyl group which may have substituents in the above is R b05 This is similar to the fluorinated alkyl groups that may have substituents, as mentioned above. In formula (b0-2a), nb 1 The integer is preferably between 1 and 4, more preferably between 2 and 4, and most preferably 3.

[0062] • Cation section In equation (I2), q is an integer greater than or equal to 1, and Q q+ This is a q-valent organic cation. Q q+ Sulfonium cations and iodonium cations are preferred, and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0063] [ka] [In the formula, R 201 ~R 207 , and R 211 ~R 212 Each of these independently represents an optionally substituted aryl group, heteroaryl group, alkyl group, or alkenyl group. 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 These atoms may bond to each other to form a ring with the sulfur atom in the formula. 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 This represents -C(=O)- or -C(=O)-O-. 201Each of these independently represents an arylene group, an alkylene group, or an alkenylene group. x is either 1 or 2. W 201 This represents a linking group with (x+1) valence.

[0064] R 201 ~R 207 , and R 211 ~R 212 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 201 ~R 207 , and R 211 ~R 212 Examples of heteroaryl groups include those in which some of the carbon atoms constituting the aryl group are replaced by heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Examples of such heteroaryl groups include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and examples of substituted heteroaryl groups include a group obtained by removing one hydrogen atom from 9H-thioxanthene-9-one. R 201 ~R 207 , and R 211 ~R 212 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212 Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

[0065] [ka] [In the formula, R' 201 Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0066] In the above equations (ca-r-1) to (ca-r-10), R' 201 Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0067] Cyclic groups which may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0068] R' 201 The aromatic hydrocarbon group in this context is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R' 201 Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R' 201Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, anthracenyl groups, etc.), groups in which one of the hydrogen atoms of the aromatic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl groups, etc.), groups obtained by removing one hydrogen atom from a ring in which some of the hydrogen atoms constituting the aromatic ring are substituted with oxo groups, etc. (for example, anthraquinones, etc.), and groups obtained by removing one hydrogen atom from an aromatic heterocycle (for example, 9H-thioxanthene, 9H-thioxanthene-9-one, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0069] R' 201 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, polycycloalkanes having a bridging ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0070] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, with adamantyl and norbornyl groups being particularly preferred, and the adamantyl group being the most preferred.

[0071] The linear or branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically 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-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0072] Chain-like alkyl groups which may have substituents: R' 201 The chain-like alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, and the like. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0073] A chain-like alkenyl group which may have substituents: R' 201 The linear alkenyl group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0074] R' 201 Examples of substituents in the cyclic group, linear alkyl group, or alkenyl group include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, oxo groups, and the above R' 201 Examples include cyclic groups, alkylcarbonyl groups, and thienylcarbonyl groups in this material.

[0075] Among them, R' 201 The preferably substituted cyclic group and the preferably substituted linear alkyl group are both cyclic and linear alkyl groups.

[0076] R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When these atoms bond to each other and form a ring with the sulfur atom in the formula, they may be heteroatoms such as sulfur, oxygen, or nitrogen atoms, or carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(applicable R Nis an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring is preferably a 3 to 10-membered ring, and particularly preferably a 5 to 7-membered ring, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthene ring, a phenoxatiyne ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, and the like.

[0077] In the above formula (ca-3), R 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. If an alkyl group is formed, it may bond with other elements to form a ring.

[0078] In the above formula (ca-3), R 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 210 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in this compound preferably has 2 to 10 carbon atoms.

[0079] In the above equations (ca-4) and (ca-5), Y 201 Each of these independently represents an arylene group, an alkylene group, or an alkenylene group. Y 201 The arylene group in this case is R' 201An example of an aromatic hydrocarbon group in this context is the aryl group exemplified above, with one hydrogen atom removed. Y 201 In this context, the alkylene group and alkenylene group are R' 201 Examples of the chain-like alkyl groups and chain-like alkenyl groups mentioned above include groups obtained by removing one hydrogen atom from the exemplified groups.

[0080] In equations (ca-4) and (ca-5) above, x is either 1 or 2. W 201 This is a (x+1) valence, i.e., a divalent or trivalent linking group. W 201 In the above formula (A1), the divalent linking group is preferably a divalent hydrocarbon group which may have substituents, and R EP A group similar to the divalent hydrocarbon group which may have substituents as exemplified is preferred. 201 The divalent linking group in this compound may be linear, branched, or cyclic, with cyclic being preferred. Among these, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting only of an arylene group, is preferred. Examples of arylene groups include phenylene groups and naphthylene groups, with phenylene groups being particularly preferred. W 201 The trivalent linking group in is the aforementioned W 201 Examples include a group obtained by removing one hydrogen atom from a divalent linking group, and a group in which another divalent linking group is bonded to the aforementioned divalent linking group. 201 In this compound, a trivalent linking group is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0081] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0082] [ka]

[0083] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent. The substituent is R 201 ~R 207 and R 210 ~R 212 These are the same as those listed as substituents that may be present.

[0084] Furthermore, as the cation represented by the formula (ca-1), cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferred.

[0085] [ka]

[0086] [ka] [In the formula, R' 211 R is an alkyl group. hal This is a hydrogen atom or a halogen atom.

[0087] Furthermore, as the cation represented by the formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are also preferred.

[0088] [ka]

[0089] Suitable cations represented by the formula (ca-2) include, specifically, diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0090] Specific examples of suitable cations represented by the above formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0091] [ka]

[0092] Specific examples of suitable cations represented by the above formula (ca-4) include the cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0093] [ka]

[0094] Furthermore, as the cation represented by the above formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferred.

[0095] [ka] [In the formula, R' 212 R' is an alkyl group or a hydrogen atom. 211 It is an alkyl group.

[0096] Among the above, the cation part [(Q q+ ) 1 / q The cation represented by the general formula (ca-1) is preferred, the cations represented by formulas (ca-1-1) to (ca-1-48) are more preferred, and the cation represented by formula (ca-1-25), formula (ca-1-29), formula (ca-1-35), and formula (ca-1-47) are even more preferred.

[0097] The following are specific examples of suitable (I2) components. Among the specific examples shown below, the (I2) component represented by the following general formula (I2-1-2) is more preferred.

[0098] [ka]

[0099] (I2) One component may be used alone, or two or more components may be used in combination. In the photosensitive resin composite according to this embodiment, the content of component (I2) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6.0 parts by mass, and even more preferably 1.0 to 5.0 parts by mass, based on the content of resin component (A) per 100 parts by mass. If the content of component (I2) is above the lower limit of the preferred range described above, sufficient sensitivity is obtained, and the lithography characteristics of the pattern are further improved. In addition, the strength of the cured film is further increased. On the other hand, if it is below the upper limit of the preferred range described above, the sensitivity is moderately controlled, and it becomes easier to obtain a pattern with a good shape.

[0100] Onium borate salt Onium borate salt (hereinafter also referred to as "component (I1)") generates a relatively strong acid upon exposure. Therefore, by forming a pattern using a photosensitive resin composition containing component (I1), sufficient sensitivity can be obtained and a good pattern can be formed. Furthermore, the use of component (I1) poses a low risk of toxicity and metal corrosion. Suitable examples of component (I1) include compounds represented by the following general formula (I1).

[0101] [ka] [In the formula, R b01 ~R b04 Each is independently an aryl group which may have substituents, or a fluorine atom. q is an integer of 1 or more, where Q q+ This is a q-valent organic cation.

[0102] · Anion Club In the above equation (I1), R b01 ~R b04The aryl group in this compound preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specifically, examples include naphthyl, phenyl, and anthracenyl groups, with the phenyl group being preferred because it is readily available. R b01 ~R b04 The aryl group in this compound may have substituents. These substituents are not particularly limited, but are preferably halogen atoms, hydroxyl groups, alkyl groups (linear or branched alkyl groups, preferably with 1 to 5 carbon atoms), and alkyl halides; more preferably halogen atoms or alkyl halides with 1 to 5 carbon atoms; and particularly preferably fluorine atoms or alkyl fluorides with 1 to 5 carbon atoms. The presence of a fluorine atom in the aryl group is preferable because it increases the polarity of the anionic moiety. In particular, R in equation (I1) b01 ~R b04 As for the groups, fluorinated phenyl groups are preferred, and perfluorophenyl groups are particularly preferred.

[0103] A preferred specific example of the anionic moiety of the compound represented by formula (I1) is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ); Tetrakis[(trifluoromethyl)phenyl]borate([B(C6H4CF3)4] - ); difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ); Trifluoro(pentafluorophenyl)borate([(C6F5)BF3] - ); Tetrakis(difluorophenyl)borate([B(C6H3F2)4] - Examples include: Among them, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferable.

[0104] • Cation section In equation (I1), q is an integer greater than or equal to 1, and Q q+This is a q-valent organic cation. This Q q+ As for Q in the above equation (I2) q+ Similar examples can be given, among which the cation represented by the general formula (ca-1) is preferred, the cations represented by formulas (ca-1-1) to (ca-1-48) are more preferred, and the cation represented by formula (ca-1-25), formula (ca-1-29), formula (ca-1-35), formula (ca-1-47), and formula (ca-1-48) are even more preferred.

[0105] The following are specific examples of suitable (I1) components. Among the specific examples shown below, the (I1) components represented by the following general formulas (I1-1) and (I1-2) are more preferred.

[0106] [ka]

[0107] (I1) One component may be used alone, or two or more components may be used in combination.

[0108] <<Sulfonates, carboxylates>> Examples of sulfonates include compounds represented by the following general formula (I3-1). Examples of carboxylate salts include compounds represented by the following general formula (I3-2). Hereinafter, compounds represented by general formula (I3-1) or (I3-2) will also be collectively referred to as "(I3) components".

[0109] [ka] [In the formula, R b11 ~R b12 m is a cyclic group which may have substituents other than halogen atoms, a linear alkyl group which may have substituents other than halogen atoms, or a linear alkenyl group which may have substituents other than halogen atoms. m is an integer of 1 or more, and Mm+ These are, independently, m-valent organic cations.

[0110] {(I3-1) component} · Anion Club In formula (I3-1), R b12 R' is a cyclic group which may have substituents other than halogen atoms, a linear alkyl group which may have substituents other than halogen atoms, or a linear alkenyl group which may have substituents other than halogen atoms, as described above. 201 Examples of cyclic groups, linear alkyl groups, and linear alkenyl groups mentioned in the description include those without substituents and those with substituents other than halogen atoms. R b12 Preferably, the group is a linear alkyl group which may have substituents other than halogen atoms, or an aliphatic cyclic group which may have substituents other than halogen atoms. The linear alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents other than halogen atoms); or a group obtained by removing one or more hydrogen atoms from camphor, etc. R b12 The hydrocarbon group may have substituents other than halogen atoms, and such substituents may be R of formula (I3-2) above. b11 Examples include substituents other than halogen atoms that a hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above may have. The phrase "may have substituents other than halogen atoms" here excludes not only cases where the substituent consists solely of halogen atoms, but also cases where the substituent contains at least one halogen atom (for example, when the substituent is a fluorinated alkyl group).

[0111] The following are preferred specific examples of the anionic portion of component (I3-1).

[0112] [ka]

[0113] • Cation section In formula (I3-1), M m+ This is an m-valent organic cation. M m+ Suitable organic cations include those similar to those represented by the general formulas (ca-1) to (ca-5) above, and among these, the cation represented by the general formula (ca-1) above is more preferred. Among these, the R in the general formula (ca-1) above is preferred. 201 , R 202 , R 203 Sulfonium cations in which at least one of the components is an organic group having 16 or more carbon atoms (aryl group, heteroaryl group, alkyl group, or alkenyl group), which may have substituents, are particularly preferred because they improve resolution and roughness characteristics. The substituents that the aforementioned organic group may have are the same as above, and include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the above formulas (ca-r-1) to (ca-r-10). The number of carbon atoms in the aforementioned organic group (aryl group, heteroaryl group, alkyl group, or alkenyl group) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18. m+ Suitable organic cations include, for example, the cations represented by the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), (ca-1-46), and (ca-1-47), respectively, and among these, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0114] {(I3-2) component} · Anion Club In formula (I3-2), R b11is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and is the cyclic group, the chain alkyl group, or the chain alkenyl group described in the above description of R’ 201 Among the cyclic group, the chain alkyl group, and the chain alkenyl group in the description of 201 , those having no substituent or having a substituent other than a halogen atom are exemplified.

[0115] Among these, as R b11 it is preferably an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a chain alkyl group which may have a substituent other than a halogen atom. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is included as a substituent, it may be via an alkylene group. In this case, as the substituent, a linking group represented by the following general formulas (y-al-1) to (y-al-7) is preferable. In the following general formulas (y-al-1) to (y-al-7), what binds to R b11 in the above formula (I3-2) is V’ 101 in the following general formulas (y-al-1) to (y-al-7).

[0116] [Chemical formula] [In the formula, V’ 101 is a single bond or an alkylene group having 1 to 5 carbon atoms. V’ 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.]

[0117] V’ 102 The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0118] V' 101 and V' 102 The alkylene group in this product may be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. V' 101 and V' 102 Specifically, the alkylene groups in these include: methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2 Examples include alkylethylene groups such as -CH2CH2CH2-; trimethylene groups (n-propylene groups) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene groups [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and pentamethylene groups [-CH2CH2CH2CH2CH2-]. Also, oshiV' 101 or V' 102 Some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is R' 201 A divalent group is preferred, which is obtained by removing one more hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group), and a cyclohexylene group, a 1,5-adamantilene group, or a 2,6-adamantilene group is more preferred.

[0119] A phenyl group or a naphthyl group is more preferred as the aromatic hydrocarbon group. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The linear alkyl group is preferably one with 1 to 10 carbon atoms, and specifically includes linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0120] R b11 As such, a cyclic group which may have substituents other than halogen atoms is preferred. The following are some preferred specific examples of the anionic portion of component (I3-2).

[0121] [ka]

[0122] • Cation section In formula (I3-2), M m+ is an m-valent organic cation, and M in formula (I3-1) above. m+ It is similar to that.

[0123] Furthermore, component (I) is preferably a cationic polymerization initiator that generates an acid with a pKa (acid dissociation constant) of -5 or less upon exposure, in order to increase the elasticity of the resin film and facilitate the formation of a fine structure without residue. More preferably, a cationic polymerization initiator that generates an acid with a pKa of -6 or less, and even more preferably, an acid with a pKa of -8 or less, can be used to obtain high sensitivity to exposure. The lower limit of the pKa of the acid generated by component (I) is preferably -15 or higher. By using a cationic polymerization initiator that generates an acid with such a suitable pKa, it becomes easier to achieve high sensitivity. Here, "pKa (acid dissociation constant)" refers to the commonly used indicator of the acid strength of the substance in question. Note that the pKa values ​​used herein are those obtained at a temperature of 25°C. Furthermore, pKa values ​​can be determined by known measurement methods. Alternatively, calculated values ​​using known software such as "ACD / Labs" (product name, manufactured by Advanced Chemistry Development) can also be used.

[0124] The following are specific examples of suitable (I3) components.

[0125] [ka]

[0126] In the photosensitive resin composition according to this embodiment, component (I) preferably contains component (I2), and more preferably consists only of component (I2).

[0127] <Photoradical polymerization initiator (C)> Component (C) is a photopolymerization initiator. Component (C) is a compound that initiates or promotes the radical polymerization of the radical polymerizable groups in component (A) upon exposure. A photoradical polymerization initiator is preferred as component (C).

[0128] (C) Examples of components include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl) ketone, 2- Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate 4-Dimethylaminobenzoate butyl, 4-Dimethylamino-2-ethylhexylbenzoic acid, 4-Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-methyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl Thioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-Bisdimethylaminobenzophenone, 4,4'-Bisdiethylaminobenzophenone, 4,4'-Dichlorobenzophenone, 3,3-Dimethyl-4-methoxybenzophenone, Benzoyl, Benzoin, Benzoin methyl ether, Benzoin ethyl ether, Benzoin isopropyl ether, Benzoin-n-butyl ether, Benzoin isobutyl ether, Benzoin butyl ether, Acetophenone, 2,2-Diethoxyacetophenone, p-Dimethylacetophenone, p-Dimethylaminopropiophenone, Dichloroacetophenone Phenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenylacridin, 1,7-bis-(9-acridinyl)heptane , 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]- 4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxystyryl)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxystyryl)phenyl-s-triazine; ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide; diacyl peroxides such as isobutyryl peroxide, bis(3,5,5-trimethylhexanoyl) peroxide; hydroperoxides such as p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxides such as 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane; peroxyketals such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane; peroxy esters such as t-butyl peroxy neodecanoate, 1,1,3,3-tetramethyl peroxy neodecanoate; peroxydicarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate; azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyrate; acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, etc. are mentioned.,

[0129] Among them, initiators containing no nitrogen atom such as benzophenone initiators such as 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone; acylphosphine oxide initiators such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide are preferred.

[0130] For component (C), commercially available products can be obtained and used. (C) Commercially available products containing this component include those manufactured by IGM Resins BV, such as "Omnirad 184," "Omnirad 651," "Omnirad 819," and "Omnirad TPO."

[0131] In the photosensitive resin composition according to this embodiment, component (C) may be used alone or in combination of two or more types.

[0132] The content of component (C) is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 15 parts by mass, based on the content of component (A) per 100 parts by mass. When the content of component (C) is within the above preferred range, the photocurability of the photosensitive resin composition is good.

[0133] <Other ingredients> The photosensitive resin composition according to this embodiment may contain other components as needed, in addition to the components (A), (I), and (C) described above. The photosensitive resin composition of this embodiment may also contain epoxy group-containing compounds other than component (A) described above.

[0134] Examples of epoxy group-containing compounds other than component (A) above include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, inositol hexaglycidyl ether, etc.

[0135] Furthermore, the photosensitive resin composition of this embodiment may optionally contain miscible additives, such as metal oxides (M), silane coupling agents, sensitizer components, solvents, additional resins for improving film performance, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and anti-halation agents.

[0136] ≪Metal Oxides (M)≫ The photosensitive resin composition according to this embodiment may also contain a metal oxide (M) (hereinafter also referred to as "component (M)") in addition to components (A), (C), and (I), as it is easier to obtain a cured film with increased strength. Furthermore, by including component (M), it is possible to form a high-resolution pattern with a good shape. Examples of component (M) include metal oxides such as silicon (metallic silicon), titanium, zirconium, and hafnium. Among these, silicon oxide is preferred, and among these, silica is particularly preferred.

[0137] Furthermore, the shape of component (M) is preferably particulate. The particulate (M) component is preferably composed of a group of particles with a volume-average particle diameter of 5 to 40 nm, more preferably composed of a group of particles with a volume-average particle diameter of 5 to 30 nm, and even more preferably composed of a group of particles with a volume-average particle diameter of 10 to 20 nm. If the volume-average particle size of component (M) is above the lower limit of the preferred range mentioned above, the strength of the cured film is more easily increased. On the other hand, if it is below the upper limit of the preferred range mentioned above, less residue is generated during pattern formation, and a higher-resolution pattern is more easily formed. In addition, the transparency of the resin film is improved. The particle size of component (M) can be appropriately selected depending on the exposure light source. Generally, particles with a particle size of 1 / 10 or less of the wavelength of light are considered to have virtually no effect on light scattering. For this reason, when forming a microstructure by photolithography using the i-line (365 nm), for example, it is preferable to use a group of particles with a primary particle size (volume mean) of 10 to 20 nm (particularly preferably a group of silica particles) as component (M).

[0138] Examples of commercially available products containing component (M) include the product names "MEK-EC-2130Y" and "MEK-AC-2140-Z," manufactured by Nissan Chemical Corporation.

[0139] (M) Component may be used alone or in combination of two or more types. If component (M) is included, its content is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and particularly preferably 20 to 30 parts by mass, based on 100 parts by mass of the total content of component (A) and component (B). If the content of component (M) is above the lower limit of the preferred range described above, the strength of the cured film is further increased. On the other hand, if it is below the upper limit of the preferred range described above, the transparency of the resin film is further increased.

[0140] ≪Silane coupling agents≫ The photosensitive resin composition according to this embodiment may further contain an adhesion aid to improve adhesion to the substrate. A silane coupling agent is preferred as this adhesion aid. Examples of silane coupling agents include those having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Silane coupling agents may be used individually or in combination of two or more types. When a silane coupling agent is included, its content is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total content of component (A) and component (B). When the silane coupling agent content is within the preferred range described above, the strength of the cured film is further enhanced. In addition, the adhesion between the cured film and the substrate is further strengthened.

[0141] ≪Sensitizing ingredients≫ The photosensitive resin composition according to this embodiment may further contain a sensitizer component. The sensitizing agent component is not particularly limited as long as it can absorb the energy from exposure and transfer that energy to other substances. Specifically, known photosensitizers such as benzophenone, p,p'-tetramethyldiaminobenzophenone, benzophenone-based photosensitizers, carbazole-based photosensitizers, acetophene-based photosensitizers, naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone can be used as sensitizer components. The sensitizing agent component may be used alone or in combination of two or more types. If a sensitizer component is included, the content is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A). When the content of the sensitizer component is within the aforementioned preferred range, sensitivity and resolution are further enhanced.

[0142] Solvents The photosensitive resin composition according to this embodiment may further contain a solvent (hereinafter sometimes referred to as "component (S)"). (S) Component may include, for example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having 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; monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the polyhydric alcohols or compounds having ester bonds; or Examples include derivatives of polyhydric alcohols such as compounds having ether bonds, such as nophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, and dimethyl sulfoxide (DMSO).

[0143] Component (S) may be used alone or as a mixture of two or more solvents.

[0144] The amount of component (S) used is not particularly limited and is set appropriately according to the coating thickness, at a concentration that allows the photosensitive resin composition to be applied to a substrate or the like without dripping. For example, component (S) can be used so that the solid content concentration is 50% by mass or more, or so that the solid content concentration is 60% by mass or more. Furthermore, embodiments that substantially do not contain component (S) (i.e., embodiments in which the solid content concentration is 100% by mass) can also be adopted.

[0145] The negative-type photosensitive resin composition according to this embodiment described above contains a resin component (A), a cationic polymerization initiator (I), and a photoradical polymerization initiator (C). Conventional negative-type photosensitive resin compositions for forming the top plate portion of hollow structures, consisting of an epoxy group-containing compound and a cationic polymerization initiator (I), have the problem that the film-like top plate portion is easily deformed by heat treatment of PEB or high-temperature heat treatment during curing operations.

[0146] In the negative-type photosensitive resin composition according to this embodiment, the resin component (A) has a constituent unit (a01) represented by the general formula (a0-1), a constituent unit (a00) represented by the general formula (a0-0), and a constituent unit (a02) represented by the general formula (a0-2). The constituent unit (a01) contains a cationic polymerizable group, the constituent unit (a00) contains a cationic polymerizable group and a radical polymerizable group, and the constituent unit (a02) contains a radical polymerizable group. Furthermore, the negative-type photosensitive resin composition according to this embodiment contains a cationic polymerization initiator (I) and a photoradical polymerization initiator (C).

[0147] Upon irradiation with active energy rays, acid is generated from the cationic portion of the cationic polymerization initiator (I). This acid generates cations derived from the cationic polymerizable group, and these cations act on constituent units (a01) and (a00) to induce cationic polymerization. Furthermore, upon irradiation with active energy rays, the radical polymerization initiator (C) acts on constituent units (a00) and (a02) to induce radical polymerization. Each reaction complicates the framework of the hardened material that makes up the top plate, forming a dense structure. This increases the strength of the hardened material, making it less susceptible to thermal deformation and suppressing doming caused by heating during hardening.

[0148] The negative-type photosensitive resin composition of this embodiment is useful as a material for forming the top plate portion of a hollow structure in an electronic component. Examples of hollow structures in electronic components include hollow structures consisting of a recess and a top plate that closes the opening of the recess, as illustrated in the description of the (method of manufacturing hollow structures) below.

[0149] (Photosensitive resist film) The photosensitive resist film according to this embodiment is formed by laminating a photosensitive resin film, which is formed using the photosensitive resin composition of the above-described embodiment, and a cover film on a base film in that order.

[0150] The photosensitive resist film according to this embodiment can be manufactured, for example, by applying the photosensitive resin composition of the above embodiment onto a substrate film, drying it to form a photosensitive resin film, and then laminating a cover film on the photosensitive resin film. The photosensitive resin composition can be applied to the substrate film using an appropriate method such as a blade coater, lip coater, comma coater, or film coater. The thickness of the photosensitive resin film is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0151] The base film can be any known type, such as a thermoplastic resin film. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm.

[0152] A known cover film can be used, such as polyethylene film or polypropylene film. A cover film with a lower adhesive strength to the photosensitive resin film than the base film is preferred. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm. The base film and the cover film may be made of the same film material, or different film materials may be used.

[0153] (Method of manufacturing hollow structures) The method for manufacturing a hollow structure according to this embodiment is a method for manufacturing a hollow structure comprising a recess and a top plate portion that closes the opening surface of the recess, wherein the top plate portion is formed using the negative-type photosensitive resin composition. Figure 1 is a schematic diagram illustrating the manufacturing method of the hollow structure according to this embodiment. The illustrated method for manufacturing the hollow structure comprises the steps of forming side walls on a substrate (first step (S1)) and forming a top plate on the side walls to manufacture the hollow structure (second step (S2)). The details of the first step (S1) and the second step (S2) will be described below.

[0154] [First step (S1)] In the first step, side walls 20 are formed on the substrate 10 to obtain a substrate 10 having recesses 15 on its surface. Figure 1, in the [First Step], shows a substrate 10 having a recess 15 on its surface, formed by the substrate 10 and a side wall 20 formed on the substrate 10.

[0155] Regarding substrates with recesses on their surface: Examples of a substrate 10 having recesses 15 on its surface include a structure with a pattern formed on the substrate 10, a stepped substrate, and the like. The recesses 15 may be made of organic or inorganic materials. Such a substrate 10 having recesses 15 on its surface can be manufactured by a method comprising, for example, the steps of: forming a photosensitive resin film on a support using a negative-type photosensitive resin composition (hereinafter referred to as the "film formation step"); exposing the photosensitive resin film to light (hereinafter referred to as the "exposure step"); and developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative-type pattern that will become the side walls 20 of the recesses 15 (hereinafter referred to as the "development step"). A method for manufacturing such a substrate 10 having recesses 15 on its surface can be carried out as follows.

[0156] Film formation process: First, a negative-type photosensitive resin composition is applied to a support by known methods such as spin coating, roll coating, or screen printing, and then a bake (post-application bake (PAB)) treatment is performed for 2 to 60 minutes at a temperature of, for example, 50 to 150°C to form a photosensitive resin film. This film formation process can also be carried out by placing a photosensitive resin composition layer, which has been prepared in advance using a negative-type photosensitive resin composition, onto the support.

[0157] The support material is not particularly limited and conventionally known materials can be used, such as circuit boards for electronic components or those on which a predetermined wiring pattern is formed. More specifically, substrates for electronic components include metal substrates such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. Suitable materials for wiring patterns include, for example, copper, aluminum, nickel, and gold.

[0158] The thickness of the photosensitive resin film formed by the negative-type photosensitive resin composition is not particularly limited, but is preferably about 10 to 100 μm.

[0159] Exposure process: Next, the formed photosensitive resin film is subjected to selective exposure using a known exposure apparatus, either through exposure via a mask (mask pattern) with a predetermined pattern formed on it, or by drawing by direct irradiation with an electron beam without using a mask pattern. Then, if necessary, a bake (post-exposure bake (PEB)) treatment is performed for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds, at a temperature of, for example, 80 to 150°C.

[0160] The wavelength used for exposure is not particularly limited; radiation, such as ultraviolet light with a wavelength of 300-500 nm, i-rays (wavelength 365 nm), or visible light, is selectively irradiated (exposed). Suitable radiation sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc., but for example, when using an ultra-high pressure mercury lamp, it is 100 to 2000 mJ / cm². 2 That is the case.

[0161] The exposure method for the photosensitive resin film may be conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or it may be liquid immersion lithography.

[0162] Development process: Next, the photosensitive resin film after exposure is developed with a developer containing an organic solvent (organic developer). After development, a rinsing treatment is preferably performed. A bake treatment (post-bake) may be performed if necessary.

[0163] The organic solvent contained in the organic developer can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0164] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0165] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, pro Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples include ethyl acid, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like.Among these, butyl acetate or PGMEA is preferred as the ester solvent.

[0166] Examples of nitrile solvents include acetonitrile, propionitol, valeronitrile, and butyronitrile.

[0167] Organic developers may contain known additives as needed. Examples of such additives include surfactants. While not particularly limited, surfactants such as ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. As the surfactant, a nonionic surfactant is preferred, and a nonionic fluorine-based surfactant or a nonionic silicone-based surfactant is more preferred. When a surfactant is added, the amount added is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the organic developer.

[0168] The development process can be carried out by known development methods, such as the dipping method, which involves immersing the support in a developer solution for a certain period of time; the paddle method, which involves piling the developer solution onto the surface of the support using surface tension and leaving it still for a certain period of time; the spray method, which involves spraying the developer solution onto the surface of the support; and the dynamic dispensing method, which involves continuously dispensing the developer solution onto a support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed.

[0169] Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method). For the rinsing process, it is preferable to use a rinsing solution containing an organic solvent.

[0170] Through the film formation process, exposure process, and development process described above, a substrate 10 having recesses 15 on its surface (a structure with a pattern formed on the substrate, a stepped substrate) can be manufactured. The thickness (horizontal dimension relative to the support) and height (vertical dimension relative to the support) of the side wall 20 can be appropriately set based on the size of the hollow portion, which is determined according to the type of electronic device to be housed in the recess 15.

[0171] [Second process (S2)] In the second step of this embodiment, the hollow structure is manufactured by forming an exposure section 30A, which will be the top plate, on the side wall 20 formed in the first step. The second step in this embodiment includes the following steps (i), (ii), (iii), (iv), and (v).

[0172] Step (i): A step in which the photosensitive resist film 30F is positioned such that it closes the opening surface of the recess 15 formed by the side wall 20 and the substrate 10, and the substrate film is peeled off from the photosensitive resin film 30 that constitutes the photosensitive resist film 30F. Step (ii): A step of exposing the photosensitive resin film 30 after step (i). Step (iii): A step of performing a heat treatment on the photosensitive resin film 30 after step (ii). Step (iv): After step (iii), develop the photosensitive resin film 30 to form a negative pattern (exposed area 30A) that closes the opening of the recess 15 formed by the side wall 20 and the substrate 10 on the substrate 10 having a recess 15 on its surface, which was prepared in step (S1). Step (v): A step in which the negative pattern (exposure area 30A) after step (iv) is further hardened by heat treatment to obtain a hollow structure 100 in which the exposure area 30A that will become the top plate is made of the hardened photosensitive resin film 40.

[0173] The hollow structure manufactured by the manufacturing method according to this embodiment consists of a recess 15 and a top plate portion that closes the opening surface of the recess 15. This hollow structure can be suitably used in hollow packages used in SAW filters, MEMS, various sensors, and the like.

[0174] ≪About Photosensitive Resist Film≫ The photosensitive resist film 30F in this embodiment has, for example, a negative-type photosensitive resin film 30 formed from the negative-type photosensitive resin composition described above.

[0175] When a photosensitive resin film 30 is formed using such a photosensitive resist film 30F, and the photosensitive resin film 30 is selectively exposed, in the exposed area 30A of the photosensitive resin film 30, the cation portion of component (I) decomposes to generate acid, and the cationic polymerizable groups in component (A) polymerize due to the action of this acid, and the radical polymerizable groups in component (A) polymerize due to the action of radicals generated from component (C). As a result, the solubility of component (A) in the developer containing an organic solvent decreases in the exposed portion 30A of the photosensitive resin film 30, while the solubility of component (A) in the developer containing an organic solvent remains unchanged in the unexposed portion 30B of the photosensitive resin film 30. Therefore, a difference in solubility in the developer containing an organic solvent occurs between the exposed portion 30A and the unexposed portion 30B of the photosensitive resin film 30. In other words, the photosensitive resin film 30 is negative-type. Therefore, when the photosensitive resin film 30 is developed with a developer containing an organic solvent, the unexposed portion 30B is dissolved and removed, forming a negative-type pattern.

[0176] Here, the negative-type photosensitive resin film 30 of the photosensitive resist film 30F is typically composed of a B-stage (semi-cured) resin material. The photosensitive resist film 30F can be a laminated film in which a photosensitive resin film 30 is laminated on a base film. In this embodiment, it is preferable to use a laminated film in which a photosensitive resin film 30 is laminated on a base film for the photosensitive resist film 30F.

[0177] Such a photosensitive resist film 30F can be manufactured by applying the above-mentioned negative-type photosensitive resin composition onto a substrate film and drying it to form a photosensitive resin film 30. The negative-type photosensitive resin composition can be applied to the substrate film using an appropriate method such as an applicator, blade coater, lip coater, comma coater, or film coater. The thickness of the photosensitive resin film 30 is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0178] A known base film can be used, such as a thermoplastic resin film. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm.

[0179] [[Process (i)]] In step (i), the photosensitive resist film 30F is positioned such that the surface of the photosensitive resin film 30 constituting the photosensitive resist film 30F closes the opening of the recess 15. Subsequently, the base film is peeled off from the photosensitive resin film 30 constituting the photosensitive resist film 30F. In Figure 1, the photosensitive resin film 30 constituting the photosensitive resist film 30F is positioned to face the substrate 10 via the side wall 20. A hollow, sealed space (cavity) is formed, enclosed by the substrate 10, the side wall 20, and the photosensitive resin film 30.

[0180] [[Step (ii)]] In step (ii), the photosensitive resin film 30 is exposed to light. For example, selective exposure is performed on the photosensitive resin film 30 using a known exposure apparatus via a photomask 60 on which a predetermined pattern has been formed.

[0181] The wavelength used for exposure is not particularly limited; radiation, such as ultraviolet light with a wavelength of 300-500 nm, GHI rays, I rays (wavelength 365 nm), or visible light, is selectively irradiated (exposed). Suitable radiation sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. The irradiation dose during exposure is 100-1500 mJ / cm². 2 Preferably, 200-900 mJ / cm² 2 This is preferable.

[0182] [[Step (iii)]] In step (iii), the photosensitive resin film 30 after exposure is subjected to a heat treatment, also known as post-exposure baking (PEB) treatment. The PEB treatment is performed, for example, at a temperature of 80 to 150°C for 40 to 600 seconds, preferably 60 to 300 seconds. As a result of the heat treatment in step (iii), the photosensitive resin film 30 after exposure becomes an exposed portion 30A in which the cationic polymerizable groups and radical polymerizable groups in component (A) are polymerized, and an unexposed portion 30B that remains unchanged.

[0183] [[Step (iv)]] In step (iv), the photosensitive resin film 30 (exposed area 30A, unexposed area 30B) after PEB treatment is developed to form a negative type pattern (exposed area 30A). The development process here can be carried out in the same manner as described in the [development process] above. After development, a rinsing treatment is preferably performed. During development in step (iv), the unexposed area 30B is dissolved and removed, leaving the exposed area 30A as a negative pattern. The exposed area 30A becomes the top plate (a roof that covers the opening surface of the recess).

[0184] [[Process (v)]] In step (v), the developed negative pattern (exposure area 30A) is further cured by heat treatment (curing operation) to obtain a hollow structure 100 in which the exposure area 30A (top plate area) is made of a cured photosensitive resin film 30 40. The heat treatment is carried out, for example, at a temperature of 150 to 300°C for 10 minutes to 5 hours, preferably 1 to 3 hours. A nitrogen atmosphere is preferred for the heat treatment. In Figure 1, the cured body 40 is formed by the curing and integration of the photosensitive resin material that forms the side wall 20 and the photosensitive resin film 30.

[0185] In the manufacturing method of the hollow structure of the embodiment described above, since the negative-type photosensitive resin composition described above is used, deformation and bulging (doming) of the top plate portion due to the curing operation are suppressed. This makes it possible to stably reduce the height of electronic components.

[0186] (polymer compound) A polymer compound according to a third aspect of the present invention has a constituent unit (a01) represented by the following general formula (a0-1), a constituent unit (a00) represented by the following general formula (a0-0), and a constituent unit (a02) represented by the following general formula (a0-2).

[0187] [ka] [In the formula, R 11 , R 12 , R 21 , R 22 , R 01 and R 02 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R x1a and R x1b R is a group containing a cationic polymerizable group. x2a and R x2b R is a group containing a radical polymerizable group. x0a and R x0b One of these groups contains a cationic polymerizable group, and the other contains a radical polymerizable group. R x1a and Rx1b They may be identical or different from each other. x2a and R x2b They may be identical or different from one another. l, m, and n represent the proportions of each constituent unit in the polymer compound. l+m+n≦1. <l+mである。0<m+nである。]

[0188] In the general formulas (a0-0) to (a0-2) above, l, m, and n represent the proportion of each constituent unit in the polymer compound. Here, the proportion refers to the ratio of the number of repeating units of each constituent unit to the total number of repeating units of all constituent units that make up the polymer compound (which is set to 1). l+m+n≦1. <l+mである。0<m+nである。 It is preferable that 0.3 ≤ l + m + n, more preferably that 0.5 ≤ l + m + n, even more preferably that 0.7 ≤ l + m + n, particularly preferably that 0.8 ≤ l + m + n, and most preferably that 0.9 ≤ l + m + n.

[0189] In the polymer compound, l+m+n=1. In this case, the polymer compound consists of constituent units (a01), (a00), and (a02).

[0190] Alternatively, in the polymer compound, l + m ≤ 1 and n = 0. In this case, the polymer compound has constituent units (a01) and (a00).

[0191] Alternatively, in the polymer compound, m+n≦1 and l=0. In this case, the polymer compound has constituent units (a00) and (a02).

[0192] Alternatively, in the polymer compound, m ≤ 1 and l = n = 0. In this case, the polymer compound has a constituent unit (a00).

[0193] Among these, the polymer compound is preferably composed of constituent unit (a01), constituent unit (a00), and constituent unit (a02).

[0194] In the polymer compound, it is preferable that the ratio of constituent unit (a01), constituent unit (a02), and constituent unit (a00) satisfies the relationship 1 ≤ (2l + m) / (m + 2n). The ratio of constituent units (a01), (a02), and (a00) preferably satisfies (2l+m) / (m+2n)≦9, more preferably (2l+m) / (m+2n)≦6, and even more preferably (2l+m) / (m+2n)≦4. Among these, it is preferable that (2l+m) / (m+2n)≦3, more preferably (2l+m) / (m+2n)≦2, and even more preferably (2l+m) / (m+2n)≦1.5. The polymer compound in which l, m, and n satisfy the above relationship is suitable as a component of a negative-type photosensitive resin composition used to form the top plate portion of a hollow structure. A negative-type photosensitive resin composition containing the polymer compound in which l, m, and n satisfy the above relationship. The top plate portion of the hollow structure formed from this material is more susceptible to doming caused by heating during hardening.

[0195] [Method for producing polymer compounds] The polymer compound according to this embodiment can be produced, for example, by a manufacturing method that includes the following partial esterification step (see, for example, Japanese Patent Application Publication No. 2019-052273).

[0196] In the partial esterification step, a compound having a cationic polymerizable group is reacted with a compound having a radical polymerizable group. The cationic polymerizable group is not particularly limited, and examples include epoxy groups. The compound having a cationic polymerizable group is not particularly limited, and examples include phenol novolac type epoxy resins. The radical polymerizable group is not particularly limited and examples include acrylic acid and methacrylic acid.

[0197] The reaction temperature conditions for the esterification step are not particularly limited, but are, for example, around 0 to 120°C. The reaction time for the esterification step is not particularly limited, but can range from approximately 1 to 72 hours.

[0198] Examples of reaction solvents used in the esterification process include ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methoxybutyl acetate, diethylene glycol dimethyl ether, and methyl isobutyl ketone.

[0199] Furthermore, a catalyst and an acid may be used in the esterification reaction. Examples of catalysts include quaternary onium salts, tertiary phosphine derivatives, and tertiary amine derivatives. Examples of acids include alkyl sulfonic acid, hydroxyalkyl sulfonic acid, carboxyalkyl sulfonic acid, phenyl sulfonic acid, phenol sulfonic acid, and carboxyphenyl sulfonic acid. The raw materials used in each process may be commercially available or synthesized. [Examples]

[0200] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0201] <Examples of polymer compound synthesis> Polymer compounds (A-1) to (A-4) were each produced using the method described in Japanese Patent Publication No. 2019-52273.

[0202] The raw material for polymer compounds (A-1) to (A-4) was compound (A-5), represented by the following chemical formula (A-5), namely bisphenol A novolac epoxy resin (product name "jER-157S70", manufactured by Mitsubishi Chemical Corporation).

[0203] [ka]

[0204] [Synthesis of polymer compound (A-1)] From the measured epoxy equivalent of compound (A-5), the molar amount of epoxy groups per unit of use was calculated, and 50% of that molar amount of acrylic acid was reacted with compound (A-5) using the method described in Japanese Patent Publication No. 2019-52273. This yielded polymer compound (A-1), in which acryloyl groups were introduced into the glycidyl groups. From the 1H-NMR spectrum measurement results of polymer compound (A-1), it was confirmed that the molar ratio of epoxy groups to acryloyl groups in polymer compound (A-1) is epoxy groups:acryloyl groups = 56.5:43.5. That is, l+m+n=1 and (2l+m) / (m+2n)=1.30.

[0205] [Synthesis of polymer compounds (A-2)] From the measured epoxy equivalent of compound (A-5), the molar amount of epoxy groups per unit of use was calculated, and 20% of that molar amount of acrylic acid was reacted with compound (A-5) using the method described in Japanese Patent Application Publication No. 2019-52273. This yielded polymer compound (A-2), in which acryloyl groups were introduced into the glycidyl groups. From the 1H-NMR spectrum measurement results of polymer compound (A-2), it was confirmed that the molar ratio of epoxy groups to acryloyl groups in polymer compound (A-2) is epoxy groups:acryloyl groups = 76.4:23.6. That is, l+m+n=1 and (2l+m) / (m+2n)=3.24.

[0206] [Synthesis of polymer compounds (A-3)] From the measured epoxy equivalent of compound (A-5), the molar amount of epoxy groups per unit of use was calculated, and 50% of that molar amount of methacrylic acid was reacted with compound (A-5) using the method described in Japanese Patent Publication No. 2019-52273. This yielded polymer compound (A-3), in which methacryloyl groups were introduced into the glycidyl groups. From the 1H-NMR spectrum measurement results of polymer compound (A-3), it was confirmed that the molar ratio of epoxy groups to methacryloyl groups in polymer compound (A-3) is epoxy groups:methacryloyl groups = 56.1:43.9. That is, l+m+n=1 and (2l+m) / (m+2n)=1.28.

[0207] [Synthesis of polymer compounds (A-4)] From the measured epoxy equivalent of compound (A-5), the molar amount of epoxy groups per unit of use was calculated, and 20% of that molar amount of methacrylic acid was reacted with compound (A-5) using the method described in Japanese Patent Application Publication No. 2019-52273. This yielded polymer compound (A-4), in which methacryloyl groups were introduced into the glycidyl groups. From the 1H-NMR spectrum measurement results of polymer compound (A-4), it was confirmed that the molar ratio of epoxy groups to methacryloyl groups in polymer compound (A-4) is epoxy groups:methacryloyl groups = 75.9:24.1. That is, l+m+n=1 and (2l+m) / (m+2n)=3.15.

[0208] The epoxy equivalent and acid value of the above polymer compounds (A-1) to (A-4) were measured according to the measurement methods described in JIS K-7236 and JIS K2501. The results of these measurements are shown in Table 1. The epoxy equivalent of compound (A-5) was 210 g / eq. From the epoxy equivalent measurement results, it was confirmed that in polymer compounds (A-1) to (A-2), an acryloyl group was introduced to the glycidyl group, and in polymer compounds (A-3) to (A-4), a methacryloyl group was introduced to the glycidyl group.

[0209] [Table 1]

[0210] <Preparation of Negative-Type Photosensitive Resin Composition> (Examples 1-5, Comparative Example 1) Each component shown in Table 2 was mixed and dissolved in methyl ethyl ketone (MEK), and the mixture was filtered using a PTFE filter (pore size 1 μm, manufactured by PALL) to prepare negative-type photosensitive resin compositions (solutions with a solid content concentration of 70-75% by mass) for each example.

[0211] [Table 2]

[0212] In Table 2, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount of each component (parts by mass; on a solid content basis). (A)-1~(A)-4: The above polymer compounds (A-1)~(A-4) (A)-5: The above compound (A-5)

[0213] (I)-1: A cationic polymerization initiator represented by the following chemical formula (I2-1-2).

[0214] [ka]

[0215] (C)-1: A photoradical polymerization initiator represented by the following chemical formula (C-1). Trade name "Omnirad 651", manufactured by IGM Resins BV.

[0216] [ka]

[0217] <Manufacturing of hollow structures> Using the negative-type photosensitive resin compositions of Examples 1-5 and Comparative Example 1, hollow structures were obtained for each example. The hollow structures were obtained by the following first step (S1) and second step (S2).

[0218] [First step (S1)] A substrate having recesses on its surface was obtained by forming side walls on a silicon substrate through the following film formation, exposure, and development processes.

[0219] Film formation process: TMMFS2000 (a dry film resist manufactured by Tokyo Ohka Kogyo Co., Ltd., with a film thickness of 20 μm) was laminated onto a silicon wafer under the conditions of 80°C, 0.3 MPa, and 0.5 m / min to achieve a film thickness of 20 μm.

[0220] Exposure process: The base film in contact with the photosensitive resin film having a thickness of 20 μm is peeled off, and 200 mJ / cm³ is applied to the photosensitive resin film using a Züss Microtec MA / BA 8 Gen4 Pro. 2 The GHI rays were irradiated with the specified dose through a mask having an aperture pattern of 500 μm × 500 μm. Subsequently, the photosensitive resin film after exposure was heat-treated on a hot plate at 90°C for 5 minutes.

[0221] Development process: The photosensitive resin film, after heat treatment, was paddle-developed at 23°C using propylene glycol monomethyl ether acetate as the developer to form a negative-type pattern that would form the sidewall. The aforementioned negative pattern was further cured by heating in an oven (nitrogen atmosphere, 200°C, 1 hour) to form a substrate with recesses on its surface, which is made of a cured photosensitive resin film.

[0222] [Second process (S2)] A hollow structure was fabricated by forming a top plate portion that closes the opening surface of the recess in the substrate obtained in the first step, using the following steps (i) to (v).

[0223] Step (i): A step of positioning the photosensitive resist film such that the photosensitive resist film covers the opening surface of a recess in the substrate. Step (ii): A step of exposing the photosensitive resin film after step (i). Step (iii): A step of performing a heat treatment on the photosensitive resin film after step (ii). Step (iv): After step (iii), develop the photosensitive resin film to form a negative pattern (exposed area) that closes the opening surface of the recess. Step (v): A step in which the negative pattern (exposure area) after step (iv) is further hardened by heat treatment to obtain a hollow structure in which the exposure area that will become the top plate is made of the hardened photosensitive resin film.

[0224] [[Process (i)]] First, a substrate having recesses on its surface, obtained in the first step described above, was prepared. Each example of the negative-type photosensitive resin composition was applied to a substrate film using an applicator, and a photosensitive resist film was obtained by baking (PAB) in an oven at 70°C for 10 minutes to form a photosensitive resin film with a thickness of 20-30 μm. The photosensitive resist film was positioned such that the surface of the photosensitive resin film of the photosensitive resist film covers the opening of the side wall in a substrate having a side wall. Subsequently, the substrate film was peeled from the photosensitive resin film of the photosensitive resist film. This operation formed a hollow, sealed space (cavity) surrounded by the substrate, the side wall, and the photosensitive resin film.

[0225] [[Step (ii)]] Next, the photosensitive resin film was irradiated with ghi rays using a Züß Microtec MA / BA 8 Gen4 Pro. The irradiation dose in Example 1 was 400 mJ / cm². 2 In Example 2, the concentration was 400 mJ / cm². 2 In Example 3, the concentration was 600 mJ / cm². 2 In Example 4, the concentration was 400 mJ / cm². 2In Example 5, the concentration was 600 mJ / cm². 2 In Comparative Example 1, the concentration was 200 mJ / cm². 2 That was the case.

[0226] [[Step (iii)]] The photosensitive resin film after exposure in step (ii) above was subjected to a heat treatment on a hot plate at 90°C for 5 minutes (PEB treatment). As a result of the PEB treatment in step (iii), the photosensitive resin film after exposure consisted of an exposed area (top plate area) where the epoxy groups and (meth)acryloyl groups in component (A) were polymerized, and an unexposed area that remained unchanged.

[0227] [[Step (iv)]] The photosensitive resin film after the heat treatment in step (iii) above was paddle-developed at 23°C using propylene glycol monomethyl ether acetate as the developer to form a negative-type pattern that would form the top plate. During development in step (iv), the unexposed areas were dissolved and removed, leaving the exposed areas (top plate) as a negative pattern.

[0228] [[Process (v)]] The negative pattern after step (iv) above was further cured by heat treatment (curing operation) in an oven (nitrogen atmosphere, 200°C, 1 hour) to obtain a hollow structure in which the top plate portion is made of a cured photosensitive resin film made of the negative photosensitive resin composition of each example.

[0229] <Evaluation of doming> For each example of hollow structure obtained, the doming of the top plate after high-temperature heat treatment during the curing process was measured using a stylus-type profiling system (Bruker, Dektak XT). For the evaluation of doming, the height (H0) from the substrate to the top surface of the top plate of the PEB was measured in advance (after step (ii) and before step (iii)). In Table 3, "After Cure" refers to the value obtained by subtracting the height from the substrate to the top surface of the top plate before PEB treatment (H0) from the height from the substrate to the top surface of the cured body (H1) after the high-temperature heat treatment of the curing operation (after step (v)) (H1). This value (H1-H0) is shown as the measurement result in Table 3.

[0230] [Table 3]

[0231] As shown in Table 3, the top plate portion of the hollow structure formed using the negative-type photosensitive resin compositions of Examples 1 to 5 to which the present invention was applied showed suppressed doming due to high-temperature heat treatment during the heat treatment and curing operation of the PEB compared to the top plate portion of the hollow structure formed using the negative-type photosensitive resin composition of Comparative Example 1. [Explanation of symbols]

[0232] 10 Substrate, 15 Recess, 20 Sidewall, 30 Photosensitive resin film, 30A Exposed area (top plate), 30B Unexposed area, 30F Photosensitive resist film, 40 Cured body, 60 Photomask

Claims

1. It contains a resin component (A), a cationic polymerization initiator, and a photoradical polymerization initiator. The resin component (A) is a negative-type photosensitive resin composition comprising only a polymer compound consisting of a constituent unit (a01) represented by the following general formula (a0-1), a constituent unit (a00) represented by the following general formula (a0-0), and a constituent unit (a02) represented by the following general formula (a0-2). 【Chemistry 1】 [In the formula, R １１ , R １２ , R ２１ , R ２２ , R ０１ and R ０２ Each of these is independently either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ｘ１ａ and R ｘ１ｂ are groups containing a cationically polymerizable group. R ｘ２ａ and R ｘ２ｂ are groups containing a radically polymerizable group. R ｘ０ａ and R ｘ０ｂ are such that one is a group containing a cationically polymerizable group and the other is a group containing a radically polymerizable group. R ｘ１ａ and R ｘ１ｂ They may be identical or different from one another. ｘ２ａ and R ｘ２ｂ They may be identical or different from one another. l, m, and n represent the proportions of each constituent unit in the resin component (A). l + m + n = 1. 0 < l + m. 0 < m + n.

2. The negative-type photosensitive resin composition according to claim 1, wherein the ratio of the constituent unit (a01), the constituent unit (a02), and the constituent unit (a00) in the resin component (A) satisfies the relationship 1 ≤ (2l + m) / (m + 2n).

3. The negative-type photosensitive resin composition according to Claim 2, wherein the ratio of the constituent unit (a01), the constituent unit (a02), and the constituent unit (a00) in the resin component (A) satisfies the relationship 1 ≤ (2l + m) / (m + 2n) ≤ 2.

4. The negative-type photosensitive resin composition according to claim 1, wherein the cationic polymerizable group is an epoxy group.

5. The negative-type photosensitive resin composition according to claim 4, wherein the epoxy equivalent of the resin component (A) is 300 to 750 g / eq.

6. The negative-type photosensitive resin composition according to claim 5, wherein the epoxy equivalent of the resin component (A) is 500 to 750 g / eq.

7. The negative-type photosensitive resin composition according to claim 1, wherein the radical polymerizable group is one or more groups selected from the group consisting of acryloyl groups and methacryloyl groups.

8. A negative-type photosensitive resin composition according to any one of claims 1 to 7, used to form the top plate portion of a hollow structure comprising a recess and a top plate portion that closes the opening surface of the recess.

9. A method for manufacturing a hollow structure comprising a recess and a top plate portion that closes the opening surface of the recess, A method for manufacturing a hollow structure, wherein the top plate portion is formed using the negative-type photosensitive resin composition described in any one of claims 1 to 7.

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