Negative photosensitive resin composition, photosensitive resist film, pattern forming method, cured film, production method and roller

Abstract

The present invention uses a negative photosensitive resin composition or a photosensitive resist film containing an epoxy resin, a metal oxide and a cationic polymerization initiator, which is used to form a negative pattern by developing with a developer containing an organic solvent as a photosensitive material for forming a hollow structure. The Martens hardness of a photosensitive resin film with a thickness of 20 μm formed on a silicon wafer using the negative photosensitive resin composition is less than 235 [N / mm 2 ] and a cured film obtained by curing the photosensitive resin film has a tensile elastic modulus (E*) of 2.1 [GPa] or more at a temperature of 175°C when viscoelasticity is measured at a frequency of 1.0 Hz.

Description

Technical Field

[0001] The present invention relates to a negative photosensitive resin composition, a photosensitive resist film, a pattern forming method, a cured film, a method for producing a cured film, and a roller. This application claims priority based on Japanese Patent Application No. 2019-185122 filed in Japan on October 8, 2019, and the contents thereof are incorporated herein by reference. Background Art

[0002] In recent years, the development of micro electronic devices such as surface acoustic wave (SAW) filters has been advancing. The package that seals such electronic devices has a hollow structure for ensuring the propagation of surface acoustic waves and the mobility of movable parts of the electronic devices.

[0003] The hollow structure is formed by keeping the wiring substrate on which the electrodes are formed hollow and molding it with a photosensitive material. The photosensitive material used here requires a thinner cured film and stronger strength.

[0004] As a photosensitive material for forming the hollow structure, a negative photosensitive resin composition and a photosensitive resist film containing an epoxy resin, a metal oxide, and a specific cationic polymerization initiator that generates a relatively strong acid upon exposure have been disclosed in the past. According to such a negative photosensitive resin composition and a photosensitive resist film, a pattern with a good shape can be formed, and the strength of the cured film can be improved (see Patent Document 1).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2018-36533 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] The development of microelectronic devices is advancing, and there is a demand for further reduction in the height of modules. In response to this, in the package, it is necessary to achieve miniaturization of the hollow structure while ensuring a space near the electrodes formed on the wiring substrate.

[0010] However, when miniaturizing the hollow structure in this way, the cured film obtained by curing the conventional negative photosensitive resin composition or photosensitive resist film has insufficient strength and may be difficult to maintain the hollow structure against high pressure applied during molding, for example.

[0011] On the other hand, in the photosensitive resist film, if the hardness of the film is only increased in order to achieve improved strength after curing, cracks or poor pressure bonding may occur in the film, or poor adhesion between the film and a silicon wafer may occur, for example, when manufacturing a main roll.

[0012] The present invention has been completed in view of the above situation, and its purpose is to provide a photosensitive resist film that can obtain a higher strength cured film and is easy to roll and has excellent lamination properties to a substrate, etc., a negative photosensitive resin composition that can produce the photosensitive resist film, a pattern forming method, a cured film and its manufacturing method, and a roller.

[0013] Solutions for solving the above technical problems

[0014] The present invention includes the following aspects.

[0015] The first embodiment of the present invention is a negative photosensitive resin composition, which contains an epoxy resin (A), a metal oxide (M) and a cationic polymerization initiator (I), and forms a negative pattern by developing with a developer containing an organic solvent, characterized in that, in the negative photosensitive resin composition, when the negative photosensitive resin composition is coated on a silicon wafer and baked at 90° C. for 5 minutes to obtain a photosensitive resin film with a film thickness of 20 μm, the Martens hardness of the photosensitive resin film is less than 235 [N / mm 2 ], and if the photosensitive resin film is irradiated with an amount of 200 mJ / cm 2 The film was exposed to i-line, and then post-exposure baking was performed at 90°C for 5 minutes, followed by baking at 200°C for 1 hour, thereby curing to obtain a cured film. When the viscoelasticity of the cured film was measured at a frequency of 1.0 Hz, the tensile elastic modulus (E*) at a temperature of 175°C was greater than 2.1 [GPa].

[0016] A second aspect of the present invention is a photosensitive resist film obtained by laminating a negative photosensitive resin film containing an epoxy resin (A), a metal oxide (M) and a cationic polymerization initiator (I) on a base film, wherein when the photosensitive resin film is laminated on a silicon wafer with a film thickness of 20 μm, the photosensitive resin film has a Martens hardness of less than 235 [N / mm 2 ], and if the photosensitive resin film is irradiated with an amount of 200 mJ / cm 2 The film was exposed to i-line, and then post-exposure baking was performed at 90°C for 5 minutes, followed by baking at 200°C for 1 hour, thereby curing to obtain a cured film. When the viscoelasticity of the cured film was measured at a frequency of 1.0 Hz, the tensile elastic modulus (E*) at a temperature of 175°C was greater than 2.1 [GPa].

[0017] The third scheme of the present invention is a pattern forming method, characterized in that it comprises: a process of forming a photosensitive resin film on a support body using the negative photosensitive resin composition of the first scheme or the photosensitive resist film of the second scheme, a process of exposing the photosensitive resin film, and a process of developing the exposed photosensitive resin film to form a negative pattern.

[0018] A fourth aspect of the present invention is a cured film obtained by curing the negative photosensitive resin composition of the first aspect.

[0019] The fifth embodiment of the present invention is a method for producing a cured film, characterized in that it comprises: a step of forming a photosensitive resin film on a support using the negative photosensitive resin composition of the first embodiment or the photosensitive resist film of the second embodiment; and a step of curing the photosensitive resin film to obtain a cured film.

[0020] A sixth aspect of the present invention is a roll body characterized by being obtained by winding the photosensitive resist film according to the second aspect around a core.

[0021] Effects of the Invention

[0022] According to the present invention, there can be provided a photosensitive resist film which can obtain a higher strength cured film and which is easy to roll and has excellent lamination properties to a substrate, a negative photosensitive resin composition for making the photosensitive resist film, a pattern forming method, a cured film and a method for producing the same, and a roller. DETAILED DESCRIPTION

[0023] In the present specification and the present claims, "aliphatic" is a relative concept with respect to aromatic, and is defined to mean a group or a compound that does not have aromaticity.

[0024] Unless otherwise specified, "alkyl" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.

[0025] Unless otherwise specified, the term "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups.

[0026] The "haloalkyl group" is a group in which a part or all of the hydrogen atoms of an alkyl group are substituted with halogen atoms, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0027] The "fluoroalkyl group" refers to a group in which a part or all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms.

[0028] The "structural unit" refers to a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).

[0029] When "may have a substituent" is described, both cases of replacing a hydrogen atom (-H) with a monovalent group and a case of replacing a methylene group (-CH2-) with a divalent group are included.

[0030] “Exposure” is a concept that includes all exposure to radiation.

[0031] (Negative photosensitive resin composition)

[0032] The negative photosensitive resin composition of this embodiment (hereinafter sometimes referred to as "photosensitive composition") contains epoxy group-containing resin (A), metal oxide (M), and cationic polymerization initiator (I). Hereinafter, these components are also referred to as (A) component, (M) component, and (I) component, respectively.

[0033] In addition, when the photosensitive composition of the present embodiment is applied on a silicon wafer and baked at 90° C. for 5 minutes to obtain a photosensitive resin film with a film thickness of 20 μm, the Martens hardness of the photosensitive resin film is less than 235 [N / mm 2 ], and if the photosensitive resin film is irradiated with an amount of 200 mJ / cm 2 The film was exposed to i-line, and then post-exposure baking was performed at 90°C for 5 minutes, followed by baking at 200°C for 1 hour, thereby curing to obtain a cured film. When the viscoelasticity of the cured film was measured at a frequency of 1.0 Hz, the tensile elastic modulus (E*) at a temperature of 175°C was greater than 2.1 [GPa].

[0034] When a photosensitive resin film is formed using the photosensitive composition and the photosensitive resin film is selectively exposed, the cationic part of the component (I) decomposes in the exposed part of the photosensitive resin film to generate an acid. The epoxy group in the component (A) undergoes ring-opening polymerization by the action of the acid, and the solubility of the component (A) in a developer containing an organic solvent decreases. On the other hand, in the unexposed part of the photosensitive resin film, the solubility of the component (A) in a developer containing an organic solvent does not change, so that a difference in solubility in a developer containing an organic solvent occurs between the exposed part and the unexposed part of the photosensitive resin film. Therefore, when the photosensitive resin film is developed using a developer containing an organic solvent, the unexposed part is dissolved and removed to form a negative pattern.

[0035] <Epoxy-containing resin (A)>

[0036] The epoxy group-containing resin (component (A)) is not particularly limited as long as it is a resin having epoxy groups sufficient to form a pattern by exposure in one molecule.

[0037] (A) As a component, a novolac type epoxy resin (Anv), a bisphenol A type epoxy resin (Abp), a bisphenol F type epoxy resin, an aliphatic epoxy resin, and an acrylic resin (Aac) are mentioned, for example.

[0038] 《Novolac type epoxy resin (Anv)》

[0039] As the novolac epoxy resin (Anv), preferably, there may be mentioned a resin (A1) represented by the following general formula (A1) (hereinafter also referred to as “component (A1)”).

[0040]

Chemistry 1

[0041]

[0042] [Where R p1 and R p2 Each of R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 They may be the same or different from each other. p2 They may be the same or different from each other. n1 is an integer of 1 to 5. EP Is a group containing epoxy group. EP They may be the same or different from each other.]

[0043] In the formula (A1), R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl, and examples of the cyclic alkyl group include cyclobutyl and cyclopentyl.

[0044] Among them, as R p1 , R p2 , preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, particularly preferably a hydrogen atom or a methyl group.

[0045] In formula (A1), multiple R p1 They may be the same or different from each other. p2 They may be the same as or different from each other.

[0046] In formula (A1), n1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0047] In formula (A1), REP It is a group containing an epoxy group.

[0048] As R EP The epoxy-containing group is not particularly limited, and examples thereof include a group consisting only of an epoxy group; a group consisting only of an alicyclic epoxy group; and a group having an epoxy group or an alicyclic epoxy group and a divalent connecting group.

[0049] The alicyclic epoxy group refers to an alicyclic group having an oxirane structure which is a three-membered cyclic ether, and specifically refers to a group having an alicyclic group and an oxirane structure.

[0050] The alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. In addition, examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, etc. In addition, the hydrogen atoms of these alicyclic groups may be substituted by alkyl, alkoxy, hydroxyl, etc.

[0051] In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, the epoxy group or the alicyclic epoxy group is preferably bonded via a divalent linking group bonded to an oxygen atom (—O—) in the formula.

[0052] Here, the divalent linking group is not particularly limited, and preferably includes a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like.

[0053] Regarding the divalent hydrocarbon group which may have a substituent:

[0054] The above-mentioned divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0055] The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0056] More specifically, the aliphatic hydrocarbon group may, for example, be a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing a ring in its structure.

[0057] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specific examples thereof include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0058] The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably has 2 to 6 carbon atoms, further preferably has 2 to 4 carbon atoms, and most preferably has 2 or 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically, examples thereof include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2-, and -CH2CH(CH3)CH2-; alkylbutylene groups such as -CH(CH3)CH2CH2-, and -CH2CH(CH3)CH2CH2-, and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0059] Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group obtained by bonding an alicyclic hydrocarbon group to the terminal of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same aliphatic hydrocarbon groups as described above.

[0060] The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0061] The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane.

[0062] The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane, and the polycyclic alkane is preferably a polycyclic alkane having 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0063] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be a monocyclic or polycyclic ring. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. As the aromatic ring, specifically, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene can be mentioned; aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon rings are substituted by heteroatoms, etc. As heteroatoms in the aromatic heterocyclic ring, oxygen atoms, sulfur atoms, nitrogen atoms, etc. can be mentioned. As the aromatic heterocyclic ring, specifically, pyridine rings, thiophene rings, etc. can be mentioned.

[0064] As the aromatic hydrocarbon group, specifically, there can be mentioned a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) in which one hydrogen atom is replaced by an alkylene group (e.g., a group obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms of 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.

[0065] The divalent hydrocarbon group may have a substituent.

[0066] The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent, and examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

[0067] The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in the structure as the divalent hydrocarbon group may or may not have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.

[0068] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0069] The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and most preferably a methoxy group and an ethoxy group.

[0070] The halogen atom of the substituent may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferred.

[0071] Examples of the haloalkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

[0072] In the alicyclic hydrocarbon group, part of the carbon atoms constituting the ring structure may be substituted by a heteroatom-containing substituent. As the heteroatom-containing substituent, -O-, -C(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O- are preferred.

[0073] In the aromatic hydrocarbon group as a divalent hydrocarbon group, the hydrogen atom possessed by the aromatic hydrocarbon group may be substituted by a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted by a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and the like.

[0074] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0075] The alkoxy group, halogen atom and haloalkyl group as the substituent may be the groups exemplified as the substituent substituting the hydrogen atom which the alicyclic hydrocarbon group has.

[0076] Regarding the divalent linking group containing a heteroatom:

[0077] The hetero atom in the hetero atom-containing divalent linking group refers to an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom.

[0078] Among the divalent linking groups containing heteroatoms, preferred linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted by a substituent such as an alkyl group or an acyl group); -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -、-Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 、-[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -represented by a group [wherein, Y 21 and Y 22Each independently represents a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m" represents an integer of 0 to 3] and the like.

[0079] When the heteroatom-containing divalent linking group is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, its H may be substituted by a substituent such as an alkyl group or an acyl group. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0080] Formula-Y 21 -OY 22 -、-Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -、-[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -Medium,Y 21 and Y 22 Each independently represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same groups as those exemplified as the "divalent hydrocarbon group which may have a substituent" in the description of the above-mentioned divalent linking group.

[0081] As Y 21 , preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, further preferably a straight-chain alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0082] As Y 22 , preferably a straight-chain 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 straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

[0083] In the form of -[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 a group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 -, particularly preferably a group represented by the formula -Y 21 -C(=O)-OY 22 - represented by a group. Among them, preferably a group represented by the formula -(CH2) a’-C(=O)-O-(CH2) b’ -. In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further 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, further preferably 1 or 2, and most preferably 1.

[0084] Among them, as R EP The epoxy-containing group is preferably a glycidyl group.

[0085] Furthermore, as the novolac-type epoxy resin (Anv), a resin having a structural unit represented by the following general formula (anv1) may also be preferably mentioned.

[0086]

Chemistry 2

[0087]

[0088] [Where R EP is an epoxy group, R a22 , R a23 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.]

[0089] In formula (anv1), R a22 , R a23 The alkyl group having 1 to 5 carbon atoms and R in the formula (A1) p1 , R p2 The carbon number of the alkyl group is the same as that of the alkyl group having 1 to 5 carbon atoms. a22 , R a23 The halogen atom is preferably a chlorine atom or a bromine atom.

[0090] In formula (anv1), R EP and R in the formula (A1) EP Likewise, glycidyl is preferred.

[0091] Specific examples of the structural unit represented by the above formula (anv1) are shown below.

[0092]

Chemistry 3

[0093]

[0094] The novolac epoxy resin (Anv) may be a resin consisting of the structural unit (anv1) alone, or may be a resin having the structural unit (anv1) and other structural units. Examples of the other structural units include structural units represented by the following general formulae (anv2) to (anv3).

[0095]

Chemistry 4

[0096]

[0097] [Where R a24 is a hydrocarbon group which may have a substituent. a25 ~R a26 , R a28 ~R a30 R are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. a27 It is an epoxy group-containing group or a hydrocarbon group which may have a substituent.]

[0098] In the formula (anv2), R a24 The hydrocarbon group which may have a substituent is a linear or branched alkyl group or a cyclic hydrocarbon group.

[0099] The number of carbon atoms in the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc. may be mentioned. Among them, methyl, ethyl or n-butyl is preferred, and methyl or ethyl is more preferred.

[0100] The number of carbon atoms in the branched alkyl group is preferably 3 to 10, more preferably 3 to 5. Specific examples thereof include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl and 2,2-dimethylbutyl, and isopropyl is preferred.

[0101] In R a24 In the case of a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.

[0102] The aliphatic hydrocarbon group as the monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.

[0103] The aliphatic hydrocarbon group as the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0104] In R a24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0105] The aromatic ring is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons, and may be a monocyclic or polycyclic ring. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. As the aromatic ring, specifically, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene can be mentioned; aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon rings are substituted by heteroatoms, etc. As heteroatoms in the aromatic heterocyclic ring, oxygen atoms, sulfur atoms, nitrogen atoms, etc. can be mentioned. As the aromatic heterocyclic ring, specifically, pyridine rings, thiophene rings, etc. can be mentioned.

[0106] As R a24 The aromatic hydrocarbon group in the above-mentioned group may specifically include a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group obtained by replacing one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocyclic ring with an alkylene group (e.g., arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0107] In formula (anv2) and (anv3), R a25 ~R a26 , R a28 ~R a30 are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and the alkyl group having 1 to 5 carbon atoms and the halogen atom are respectively a22 , R a23 same.

[0108] In formula (anv3), R a27 is an epoxy group-containing group or a hydrocarbon group which may have a substituent. a27 The epoxy-containing group and R in the formula (A1) EP Likewise, R a27 The hydrocarbon group which may have a substituent and R a24 same.

[0109] Specific examples of the structural units represented by the formulae (anv2) to (anv3) are shown below.

[0110]

Chemistry 5

[0111]

[0112] When the novolac-type epoxy resin (Anv) has other structural units in addition to the structural unit (anv1), the ratio of each structural unit in the resin (Anv) is not particularly limited, but the total of the structural units having an epoxy group is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and further preferably 30 to 70 mol % relative to the total of all the structural units constituting the resin (Anv).

[0113] 《About Bisphenol A Epoxy Resin (Abp)》

[0114] As the bisphenol A type epoxy resin (Abp), an epoxy resin having a structure represented by the following general formula (abp1) may be mentioned.

[0115]

Chemistry 6

[0116]

[0117] [Where R EP is an epoxy group, R a31 , R a32 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 31 is an integer from 1 to 50.]

[0118] In formula (abp1), R a31 , R a32 The alkyl group having 1 to 5 carbon atoms and R in the formula (A1) p1 , R p2 The carbon number of the alkyl group is the same as that of the alkyl group having 1 to 5 carbon atoms. a31 , R a32 , preferably a hydrogen atom or a methyl group.

[0119] R EP and R in the formula (A1) EP Likewise, glycidyl is preferred.

[0120] 《Aliphatic Epoxy Resin, Acrylic Resin (Aac)》

[0121] Examples of the aliphatic epoxy resin and acrylic resin (Aac) include resins having epoxy group-containing units represented by the following general formulas (a1-1) to (a1-2), respectively.

[0122]

Chemistry 7

[0123]

[0124] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Va 41 It is a divalent hydrocarbon group which may have a substituent. 41is an integer from 0 to 2. a41 , R a42 It is a group containing epoxy group. 42 Is 0 or 1. 41 for(na 43 +1) valence aliphatic hydrocarbon group. 43 is an integer from 1 to 3.]

[0125] In the formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.

[0126] The alkyl group having 1 to 5 carbon atoms represented by R is preferably linear or branched, and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl.

[0127] The haloalkyl group having 1 to 5 carbon atoms of R is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, and a fluorine atom is particularly preferred.

[0128] R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

[0129] In the formula (a1-1), Va 41 is a divalent hydrocarbon group which may have a substituent, and examples thereof include EP The same group as the divalent hydrocarbon group which may have a substituent as described above.

[0130] Among the above, Va 41 The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, further preferably a linear aliphatic hydrocarbon group, and particularly preferably a linear alkylene group.

[0131] In formula (a1-1), na 41 It is an integer of 0 to 2, and preferably 0 or 1.

[0132] In formula (a1-1) and (a1-2), R a41 , R a42 is an epoxy group, and R EP same.

[0133] In formula (a1-2), Wa 41 (na 43The aliphatic hydrocarbon group having a valence of (+1) means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. As the aliphatic hydrocarbon group, there may be mentioned a straight-chain or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a group obtained by combining a straight-chain or branched aliphatic hydrocarbon group with an aliphatic hydrocarbon group containing a ring in the structure.

[0134] In formula (a1-2), na 43 It is an integer of 1 to 3, and preferably 1 or 2.

[0135] Specific examples of the structural unit represented by the above formula (a1-1) or (a1-2) are shown below.

[0136]

Chemistry 8

[0137]

[0138]

Chemistry 9

[0139]

[0140]

Chemistry 10

[0141]

[0142]

Chemistry 11

[0143]

[0144] In the above formula, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0145] R a51 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. a52 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. a53 Represents a hydrogen atom or a methyl group. 51 An integer from 0 to 10.

[0146] R a51 , R a52 , R a53 They may be the same or different.

[0147] Furthermore, for the purpose of appropriately controlling physical and chemical properties, the acrylic resin (Aac) may also have structural units derived from other polymerizable compounds. As such polymerizable compounds, known free radical polymerizable compounds and anionic polymerizable compounds may be cited. As such polymerizable compounds, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (Meth)acrylic acid aromatic esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; polymerizable compounds containing chlorine such as vinyl chloride and vinylidene chloride; polymerizable compounds containing amide bonds such as acrylamide and methacrylamide, etc.

[0148] When the aliphatic epoxy resin or acrylic resin (Aac) has other structural units, the content of the epoxy group-containing unit in the resin is preferably 5 to 40 mol %, more preferably 10 to 30 mol %, and most preferably 15 to 25 mol %.

[0149] Furthermore, as the aliphatic epoxy resin, a compound including a partial structure represented by the following general formula (m1) (hereinafter also referred to as “component (m1)”) may also be preferably mentioned.

[0150]

Chemistry 12

[0151]

[0152] [In the formula, n2 is an integer of 1 to 4. * represents a chemical bond.]

[0153] In formula (m1), n2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0154] The component (m1) may be a compound having a plurality of partial structures represented by the general formula (m1) bonded via a divalent linking group or a single bond. Among them, a compound having a plurality of partial structures represented by the general formula (m1) bonded via a divalent linking group is preferred.

[0155] The divalent linking group is not particularly limited, but preferably includes a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. The divalent hydrocarbon group which may have a substituent, the divalent linking group containing a heteroatom, and the like are preferably EP The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom described in (epoxy-containing group) are the same, among which the divalent linking group containing a heteroatom is preferred, and the one containing -Y is more preferred. 21 -C(=O)-O-, -C(=O)-OY 21 -represented by a group. 21 , preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, further preferably a straight-chain alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0156] Furthermore, as the aliphatic epoxy resin, a compound represented by the following general formula (m2) (hereinafter also referred to as "component (m2)") may also be preferably mentioned.

[0157]

Chemistry 13

[0158]

[0159] [Where R EP Is a group containing epoxy group. EP They may be the same or different from each other.]

[0160] In formula (m2), R EP is an epoxy group, and R EP same.

[0161] (A) As the component, one type may be used alone, or two or more types may be used in combination.

[0162] The component (A) preferably contains at least one resin selected from the group consisting of a novolac epoxy resin (Anv), a bisphenol A epoxy resin (Abp), a bisphenol F epoxy resin, an aliphatic epoxy resin, and an acrylic resin (Aac).

[0163] Among them, it is more preferred that the component (A) contains at least one resin selected from the group consisting of a novolac epoxy resin (Anv), a bisphenol A epoxy resin (Abp), an aliphatic epoxy resin, and an acrylic resin (Aac).

[0164] Among them, component (A) further preferably includes at least one resin selected from the group consisting of a novolac type epoxy resin (Anv), an aliphatic epoxy resin, and an acrylic resin (Aac), and particularly preferably includes two or more resins selected from the group consisting of a novolac type epoxy resin (Anv), an aliphatic epoxy resin, and an acrylic resin (Aac).

[0165] When two or more kinds are used as the component (A), the component (A) preferably comprises a combination of a novolac epoxy resin (Anv) and an aliphatic epoxy resin from the viewpoint of improving film properties (rolling, lamination properties) when forming a photosensitive resist film.

[0166] Specifically, such a combination may be a combination of component (A1) and at least one selected from the group consisting of component (m1) and component (m2) (hereinafter referred to as "component (m)"). Among them, a combination of component (A1), component (m1) and component (m2) is most preferred.

[0167] In the case of both component (m1) and component (m2), the ratio of component (m1) to component (m2) is preferably 2 / 8 to 8 / 2, more preferably 3 / 7 to 7 / 3, and even more preferably 4 / 6 to 6 / 4, as the mass ratio expressed as component (m1) / component (m2). If the mass ratio is within the above preferred range, the film properties (rolling, lamination) are further improved when the photosensitive resist film is prepared.

[0168] In particular, from the perspective of the balance between strength and flexibility of the cured film, component (A) contains component (A1), component (m1) and component (m2), and the mass % of the total content of component (m1) and component (m2) in the total content of component (A1), component (m1) and component (m2) is preferably 15 mass % or more, more preferably 20 mass % or more, further preferably 25 mass % or more, particularly preferably more than 25 mass %, and most preferably more than 25 mass % and 30 mass % or less.

[0169] The polystyrene-equivalent mass average molecular weight of the component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and even more preferably 300 to 200,000. By setting such a mass average molecular weight, peeling from the support is unlikely to occur, and the strength of the formed cured film is sufficiently improved.

[0170] The molecular weight distribution coefficient of the component (A) is preferably 1.05 or more. By setting the molecular weight distribution coefficient to such a value, the photolithographic characteristics in pattern formation are further improved.

[0171] The molecular weight distribution coefficient referred to herein refers to a value obtained by dividing the mass average molecular weight by the number average molecular weight.

[0172] Commercially available products of the component (A) include, for example, novolac-type epoxy resins (Anv), such as JER-152, JER-154, JER-157S70, and JER-157S65 (all manufactured by Mitsubishi Chemical Corporation); EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, and EPICLON HP5000 (all manufactured by DIC Corporation); and EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.).

[0173] Examples of bisphenol A epoxy resins (Abp) include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, and JER-1010 (all manufactured by Mitsubishi Chemical Corporation); EPICLON 860, EPICLON 1050, EPICLON 1051, and EPICLON 1055 (all manufactured by DIC Corporation); and the like.

[0174] Examples of bisphenol F-type epoxy resins include JER-806, JER-807, JER-4004, JER-4005, JER-4007, and JER-4010 (all manufactured by Mitsubishi Chemical Corporation); EPICLON 830 and EPICLON 835 (all manufactured by DIC Corporation); and LCE-21 and RE-602S (all manufactured by Nippon Kayaku Co., Ltd.).

[0175] Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, and ADEKA RESIN EP-4088S (all manufactured by ADEKA Corporation); CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (all manufactured by Daicel Corporation); DENACOL EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase Chemical Co., Ltd.); Chemtex) Co., Ltd.); TEPIC-VL (Nissan Chemical Industries, Ltd.) and the like.

[0176] The content of the component (A) in the photosensitive composition of the embodiment may be adjusted according to the film thickness of the photosensitive resin film to be formed.

[0177] <Metal Oxide (M)>

[0178] The photosensitive composition of the present embodiment contains a metal oxide (component (M)) in addition to the components (A) and (I), thereby providing a cured film having improved strength and forming a high-resolution pattern in a good shape.

[0179] As the component (M), for example, oxides of metals such as silicon (metal silicon), titanium, zirconium, and hafnium may be mentioned. Among the above, oxides of silicon are preferred, and silicon dioxide is particularly preferably used.

[0180] Furthermore, the shape of the component (M) is preferably particulate.

[0181] The above-mentioned particulate (M) component is preferably a substance consisting of a particle group having a volume average particle size of 5 to 40 nm, more preferably a substance consisting of a particle group having a volume average particle size of 5 to 30 nm, and further preferably a substance consisting of a particle group having a volume average particle size of 10 to 20 nm.

[0182] If the volume average particle size of component (M) is above the lower limit of the preferred range, the strength of the cured film is easily improved. On the other hand, if it is below the upper limit of the preferred range, it is difficult to generate residues during pattern formation, and it is easy to form a pattern with higher resolution.

[0183] The particle size of the (M) component can be appropriately selected according to the exposure light source. Generally, the influence of light scattering can be almost ignored for particles having a particle size of 1 / 10 or less relative to the wavelength of light. Therefore, for example, in the case of forming a microstructure by photolithography using i-line (365nm), as the (M) component, it is preferred to use a particle group (particularly preferably a silica particle group) having a primary particle size (volume average) of 10 to 20nm.

[0184] As the component (M), one type may be used alone, or two or more types may be used in combination.

[0185] The content of the component (M) is preferably more than 30 parts by mass and 180 parts by mass or less, more preferably 40 to 170 parts by mass, and even more preferably 50 to 150 parts by mass, based on 100 parts by mass of the component (A).

[0186] When the content of the component (M) exceeds the lower limit of the preferred range, the strength of the cured film is further improved. On the other hand, when it is at most the upper limit of the preferred range, the fluidity of the photosensitive composition is easily maintained.

[0187] <Cationic Polymerization Initiator (I)>

[0188] The cationic polymerization initiator (component (I)) is a compound that generates cations upon irradiation with active energy rays such as ultraviolet rays, extreme ultraviolet rays, excimer lasers such as KrF and ArF, X-rays, and electron beams, and the cations can serve as a polymerization initiator.

[0189] The component (I) in the photosensitive composition of the present embodiment is not particularly limited, and examples thereof include a compound represented by the following general formula (I1) (hereinafter referred to as "component (I1)"), a compound represented by the following general formula (I2) (hereinafter referred to as "component (I2)"), and a compound represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "component (I3)").

[0190] Among the above, both the component (I1) and the component (I2) generate a relatively strong acid upon exposure. Therefore, when a pattern is formed using a photosensitive composition containing the component (I), sufficient sensitivity can be obtained to form a good pattern.

[0191] 《(I1)Component》

[0192] The component (I1) is a compound represented by the following general formula (I1).

[0193]

Chemistry 14

[0194]

[0195] [Where R b01 ~Rb04 Each is independently an aryl group or a fluorine atom which may have a substituent. q is an integer greater than 1, and Q q+ are each independently a q-valent organic cation.]

[0196] Anion part

[0197] In the formula (I1), R b01 ~R b04 Each independently represents an aryl group which may have a substituent or a fluorine atom.

[0198] R b01 ~R b04 The aryl group in preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples thereof include naphthyl, phenyl, and anthracenyl, and phenyl is preferred from the viewpoint of easy availability.

[0199] R b01 ~R b04 The aryl group in may have a substituent. The substituent is not particularly limited, but preferably a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, and preferably a carbon number of 1 to 5), a haloalkyl group, more preferably a halogen atom or a haloalkyl group with a carbon number of 1 to 5, and particularly preferably a fluorine atom or a fluorinated alkyl group with a carbon number of 1 to 5. By making the aryl group have a fluorine atom, the polarity of the anion part is improved, so it is preferred.

[0200] Among them, R as formula (I1) b01 ~R b04 , preferably a fluorinated phenyl group, and particularly preferably a perfluorophenyl group.

[0201] Preferred specific examples of the anion portion of the compound represented by formula (I1) include 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] - )wait.

[0202] Among them, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ).

[0203] ·Cationic part

[0204] In formula (I1), q is an integer greater than 1, and Qq+ Each independently is a q-valent organic cation.

[0205] As the Q q+ Preferred examples include sulfonium cations and iodonium cations, and particularly preferred are organic cations represented by the following general formulae (ca-1) to (ca-5).

[0206]

Chemistry 15

[0207]

[0208] [Where R 201 ~R 207 and R 211 ~R 212 R each independently represents an aryl group, a heteroaryl group, an alkyl group or an alkenyl group which may have a substituent. 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 They may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 It is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO2-containing cyclic group which may have a substituent. 201 represents -C(=O)- or -C(=O)-O-. 201 W represents independently an arylene group, an alkylene group or an alkenylene group. x is 1 or 2. 201 represents a (x+1)-valent linking group.]

[0209] As R 201 ~R 207 and R 211 ~R 212 The aryl group in the above-mentioned may be an unsubstituted aryl group having 6 to 20 carbon atoms, and preferably a phenyl group or a naphthyl group.

[0210] As R 201 ~R 207 and R 211 ~R 212 The heteroaryl group in the above-mentioned aryl group may be a heteroaryl group in which a part of the carbon atoms constituting the aryl group is substituted with a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, etc. Examples of the heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthenyl; examples of the substituted heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthen-9-one, etc.

[0211] As R201 ~R 207 and R 211 ~R 212 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0212] As R 201 ~R 207 and R 211 ~R 212 The alkenyl group in the alkylene group preferably has 2 to 10 carbon atoms.

[0213] As R 201 ~R 207 and R 210 ~R 212 The substituent that may be possessed includes, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, and groups represented by the following formulae (ca-r-1) to (ca-r-10), respectively.

[0214]

Chemistry 16

[0215]

[0216] [Wherein, R' 201 Each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.]

[0217] In the formulas (ca-r-1) to (ca-r-10), R' 201 Each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0218] The cyclic group which may have a substituent:

[0219] The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group represents a hydrocarbon group that does not have aromaticity. In addition, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and a saturated aliphatic hydrocarbon group is usually preferred.

[0220] R' 201 The aromatic hydrocarbon group in 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, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. The number of carbon atoms in the substituent is not included in the number of carbon atoms.

[0221] As R' 201Specifically, the aromatic ring possessed by the aromatic hydrocarbon group in the ring may be benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which a part of the carbon atoms constituting these aromatic rings are replaced by a heteroatom, or a ring in which a part of the hydrogen atoms constituting these aromatic rings or aromatic heterocyclic rings are replaced by an oxo group or the like. As the heteroatom in the aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. may be mentioned.

[0222] As R' 201 Specifically, the aromatic hydrocarbon group in the above-mentioned group may be a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl, naphthyl, anthracenyl, etc.), a group obtained by replacing one hydrogen atom of the aromatic ring with an alkylene group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), a group obtained by removing one hydrogen atom from a ring in which a part of hydrogen atoms constituting the aromatic ring are replaced with an oxo group or the like (for example, anthraquinone, etc.), a group obtained by removing one hydrogen atom from an aromatic heterocyclic ring (for example, 9H-thioxanthen, 9H-thioxanthen-9-one, etc.), etc. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atoms.

[0223] R' 201 The cyclic aliphatic hydrocarbon group in the above-mentioned may include an aliphatic hydrocarbon group containing a ring in the structure.

[0224] Examples of the aliphatic hydrocarbon group containing a ring in its structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group obtained by bonding an alicyclic hydrocarbon group to the terminal of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups.

[0225] The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.

[0226] The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferred. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferred, and specifically, cyclopentane, cyclohexane, etc. can be mentioned. As a polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, a polycycloalkane having 7 to 30 carbon atoms is preferred. Among them, as the polycycloalkane, polycycloalkane having a cross-linked ring type polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. is more preferred; polycycloalkane having a condensed ring type polycycloalkane such as a cyclic group having a steroid skeleton.

[0227] Among them, as R' 201The cyclic aliphatic hydrocarbon group in the is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably a group obtained by removing one hydrogen atom from a polycycloalkane, particularly preferably adamantyl and norbornyl, and most preferably adamantyl.

[0228] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

[0229] As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples thereof include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0230] The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically, examples thereof include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2-, and -CH2CH(CH3)CH2-; alkylbutylene groups such as -CH(CH3)CH2CH2-, and -CH2CH(CH3)CH2CH2-, and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0231] The chain alkyl group may have a substituent:

[0232] As R' 201 The chain alkyl group may be straight chain or branched chain.

[0233] The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, the linear alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, and a docosyl group.

[0234] The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl and the like can be mentioned.

[0235] The chain alkenyl group which may have a substituent:

[0236] As R' 201 The chain alkenyl group may be straight-chain or branched, preferably has 2 to 10 carbon atoms, more preferably has 2 to 5 carbon atoms, further preferably has 2 to 4 carbon atoms, and particularly preferably has 3 carbon atoms. Examples of the straight-chain alkenyl group include vinyl, propenyl (allyl), butynyl, etc. Examples of the branched alkenyl group include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, 2-methylpropenyl, etc.

[0237] As the chain alkenyl group, among the above, a straight-chain alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0238] As R' 201 The substituents in the cyclic group, chain alkyl group or chain alkenyl group include, for example, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, oxo groups, the above R' 201 Cyclic groups, alkylcarbonyl groups, thienylcarbonyl groups, etc.

[0239] Among these, R' 201 Preferred are a cyclic group which may have a substituent and a chain alkyl group which may have a substituent.

[0240] In R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When they are bonded to each other to form a ring together with the sulfur atom in the formula, the ring may be mediated by a sulfur atom, an oxygen atom, a nitrogen atom or other heteroatom, a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH- or -N(R N )-(The R Nis an alkyl group having 1 to 5 carbon atoms) or the like. As the formed ring, it is preferred that the ring containing the sulfur atom in the formula in the ring skeleton is a three- to ten-membered ring including the sulfur atom, and particularly preferably a five- to seven-membered ring. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, and the like.

[0241] In the formula (ca-3), R 208 ~R 209 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 208 ~R 209 In the case of an alkyl group, they may be bonded to each other to form a ring.

[0242] In the formula (ca-3), R 210 It is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO2-containing cyclic group which may have a substituent.

[0243] As R 210 The aryl group in the above-mentioned may be an unsubstituted aryl group having 6 to 20 carbon atoms, and preferably a phenyl group or a naphthyl group.

[0244] As R 210 The alkyl group in the group is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0245] As R 210 The alkenyl group in the alkylene group preferably has 2 to 10 carbon atoms.

[0246] In the formula (ca-4) and formula (ca-5), Y 201 Each independently represents an arylene group, an alkylene group or an alkenylene group.

[0247] Y 201 The arylene group in R' can be exemplified by 201 The aromatic hydrocarbon group in is a group obtained by removing one hydrogen atom from the aryl group exemplified in the above.

[0248] Y 201 The alkylene group and alkenylene group in R' 201 A group obtained by removing one hydrogen atom from the groups exemplified as the chain alkyl group and the chain alkenyl group.

[0249] In the above formula (ca-4) and formula (ca-5), x is 1 or 2.

[0250] W 201It is a (x+1)-valent, that is, a divalent or trivalent linking group.

[0251] As W 201 The divalent linking group in the formula (A1) is preferably a divalent hydrocarbon group which may have a substituent, and is preferably connected to R EP The same group as the divalent hydrocarbon group which may have a substituent as exemplified in 201 The divalent linking group in can be any of linear, branched, and cyclic, preferably cyclic. Among them, preferably a group obtained by combining two carbonyl groups at both ends of the arylene group, or a group consisting only of an arylene group. As the arylene group, phenylene, naphthyl, etc. can be mentioned, and phenylene is particularly preferred.

[0252] As W 201 The trivalent linking group in can be exemplified by W 201 A group obtained by removing one hydrogen atom from the divalent linking group in the formula (a), a group obtained by further bonding the divalent linking group to the divalent linking group, and the like. 201 The trivalent linking group in is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0253] Specific examples of preferred cations represented by the formula (ca-1) include cations represented by the following formulae (ca-1-1) to (ca-1-24).

[0254]

Chemistry 17

[0255]

[0256]

Chemistry 18

[0257]

[0258] [Wherein, R” 201 is a hydrogen atom or a substituent. 201 ~R 207 and R 210 ~R 212 The substituents that may be possessed are the same as those exemplified above.]

[0259] Furthermore, as the cation represented by the above formula (ca-1), cations represented by the following general formulae (ca-1-25) to (ca-1-35) are also preferred.

[0260]

Chemistry 19

[0261]

[0262]

Chemistry 20

[0263]

[0264] [wherein, R' 211 is an alkyl group. R hal is a hydrogen atom or a halogen atom.]

[0265] In addition, as the cation represented by the formula (ca-1), cations represented by the following chemical formulas (ca-1-36) to (ca-1-46) are also preferred.

[0266] [Chemical formula 21]

[0267]

[0268] As the preferred cation represented by the formula (ca-2), specifically, diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc. can be exemplified.

[0269] As the preferred cation represented by the formula (ca-3), specifically, cations represented by the following formulas (ca-3-1) to (ca-3-6) can be exemplified.

[0270] [Chemical formula 22]

[0271]

[0272] As the preferred cation represented by the formula (ca-4), specifically, cations represented by the following formulas (ca-4-1) to (ca-4-2) can be exemplified.

[0273] [Chemical formula 23]

[0274]

[0275] In addition, as the cation represented by the formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferred.

[0276] [Chemical formula 24]

[0277]

[0278] [wherein, R' 212 is an alkyl group or a hydrogen atom. R' 211 is an alkyl group.]

[0279] Among the above, the cation part [(Q q+ ) 1 / q preferably uses the cation represented by the general formula (ca-1), more preferably the cations represented by the formulas (ca-1-1) to (ca-1-46), and further preferably the cation represented by the formula (ca-1-29).

[0280] 《(I2) ingredient》

[0281] The component (I2) is a compound represented by the following general formula (I2).

[0282]

Chemistry 25

[0283]

[0284] [Where R b05 is a fluorinated alkyl group which may have a substituent or a fluorine atom. b05 They may be the same or different from each other. q is an integer greater than 1, and Q q+ are each independently a q-valent organic cation.]

[0285] Anion part

[0286] In the formula (I2), R b05 is a fluorinated alkyl group which may have a substituent or a fluorine atom. b05 They may be the same as or different from each other.

[0287] R b05 The fluorinated alkyl group in the above-mentioned group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 5 carbon atoms. Specifically, the fluorinated alkyl group may be a group in which a part or all of hydrogen atoms in an alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms.

[0288] Among them, as R b05 , preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, further preferably a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group.

[0289] The anion part of the compound represented by the formula (I2) is preferably an anion part represented by the following general formula (b0-2a).

[0290]

Chemistry 26

[0291]

[0292] [Where R bf05 is a fluorinated alkyl group which may have a substituent. 1 is an integer from 1 to 5.]

[0293] In formula (b0-2a), R bf05 The fluoroalkyl group which may have a substituent is b05 The fluoroalkyl group which may have a substituent is the same as exemplified in.

[0294] In formula (b0-2a), nb 1Preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.

[0295] · Cationic part

[0296] In formula (I2), q is an integer of 1 or more, and Q q+ are each independently an organic cation of q valence.

[0297] As this Q q+ , the same cations as those in the above formula (I1) can be exemplified. Among them, cations represented by the general formula (ca-1) are preferred, cations represented by formulas (ca-1-1) to (ca-1-46) are more preferred, and cations represented by formula (ca-1-35) are further preferred.

[0298] 《Component (I3)》

[0299] Component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0300]

Chemical formula 27

[0301]

[0302] [In the formula, R b11 ~R b12 are a cyclic group which may have a substituent other than a halogen atom, a linear alkyl group which may have a substituent other than a halogen atom, or a linear alkenyl group which may have a substituent other than a halogen atom. m is an integer of 1 or more, and M m+ are each independently an organic cation of m valence.]

[0303] {(I3-1) component}

[0304] · Anionic part

[0305] In formula (I3-1), R b12 is a cyclic group which may have a substituent other than a halogen atom, a linear alkyl group which may have a substituent other than a halogen atom, or a linear alkenyl group which may have a substituent other than a halogen atom, and the cyclic group, linear alkyl group, and linear alkenyl group in the description of the above R' 201 without a substituent or having a substituent other than a halogen atom can be exemplified.

[0306] As R b12 , a linear alkyl group which may have a substituent other than a halogen atom or an aliphatic cyclic group which may have a substituent other than a halogen atom is preferred.

[0307] The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 3 to 10 carbon atoms. 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 a substituent other than a halogen atom); or a group obtained by removing one or more hydrogen atoms from camphor, etc.

[0308] R b12 The hydrocarbon group may have a substituent other than a halogen atom, and examples of the substituent include the following: b11 The substituents other than the halogen atoms that the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) may have are the same as those in the above.

[0309] The phrase “may have a substituent other than a halogen atom” herein excludes not only a case where the group has a substituent consisting only of a halogen atom but also a case where the group has a substituent containing at least one halogen atom (for example, a case where the substituent is a fluoroalkyl group, etc.).

[0310] Preferred specific examples of the anion part of the component (I3-1) are shown below.

[0311]

Chemistry 28

[0312]

[0313] ·Cationic part

[0314] In formula (I3-1), M m+ It is an m-valent organic cation.

[0315] As M m+ The organic cations may be preferably the same organic cations as those represented by the above general formulae (ca-1) to (ca-5), and the cations represented by the above general formula (ca-1) are more preferred. Among them, R in the above general formula (ca-1) is particularly preferred from the viewpoint of improving resolution and roughness characteristics. 201 , R 202 , R 203 At least one of them is an organic group having 16 or more carbon atoms which may have a substituent (aryl group, heteroaryl group, alkyl group or alkenyl group), that is, a sulfonium cation.

[0316] As substituents that the organic group may have, the same as those mentioned above, examples include alkyl groups, halogen atoms, halogenated alkyl groups, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the above formulae (ca-r-1) to (ca-r-10), respectively.

[0317] The carbon number in the organic group (aryl, heteroaryl, alkyl or alkenyl) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18. As the above M m+ of the organic cation, 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) can be preferably exemplified. Among them, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0318] {(I3-2) component}

[0319] · Anionic part

[0320] In formula (I3-2), R b11 is a cyclic group which may have substituents other than a halogen atom, a chain alkyl which may have substituents other than a halogen atom, or a chain alkenyl which may have substituents other than a halogen atom, and the cyclic group, chain alkyl, and chain alkenyl in the description of the above R’ 201 without substituents or with substituents other than a halogen atom can be exemplified.

[0321] Among these, as R b11 , an aromatic hydrocarbon group which may have substituents other than a halogen atom, an aliphatic cyclic group which may have substituents other than a halogen atom, or a chain alkyl which may have substituents other than a halogen atom is preferred. As the substituents which these groups may have, 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 can be exemplified.

[0322] When an ether bond or an ester bond is included as a substituent, it can be via an alkylene group. As the substituent in this case, a linking group represented by the following general formulas (y-al-1) to (y-al-7) is preferred.

[0323]

Chemical formula 29

[0324]

[0325] [In the formula, V’ 101 is a single bond or an alkylene group having 1 to 5 carbon atoms, and V’ 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.]

[0326] The divalent saturated hydrocarbon group in V’ 102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and further preferably an alkylene group having 1 to 5 carbon atoms.

[0327] As V’ 101 and V’102 The alkylene group in may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred.

[0328] As V' 101 and V' 102 The alkylene group in the above-mentioned group specifically includes methylene [—CH2-]; alkylmethylene groups such as —CH(CH3)-, —CH(CH2CH3)-, —C(CH3)2-, —C(CH3)(CH2CH3)-, —C(CH3)(CH2CH2CH3)-, and —C(CH2CH3)2-; ethylene [—CH2CH2-]; —CH(CH3)CH2-, —CH(CH3)CH(CH3)-, —C(CH3)2CH2-, -CH(CH2CH3)CH2- and other alkylethylene groups; propylene (n-propylene) [-CH2CH2CH2-]; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and other alkylpropylene groups; butylene [-CH2CH2CH2CH2-]; -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkylbutylene groups; pentylene [-CH2CH2CH2CH2CH2-] and the like.

[0329] In addition, V' 101 or V' 102 A part of the methylene groups in the alkylene group in the above-mentioned group may be substituted by a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably substituted by R' 201 A divalent group obtained by further removing one hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group), more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.

[0330] As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is more preferable.

[0331] The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.

[0332] The chain alkyl group preferably has 1 to 10 carbon atoms. Specifically, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; and branched-chain alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl and 4-methylpentyl.

[0333] As R b11 , it is preferably a cyclic group which may have substituents other than halogen atoms.

[0334] Hereinafter, preferred specific examples of the anionic part of the component (I3-2) are shown.

[0335]

Chemical formula 30

[0336]

[0337] · Cationic part

[0338] In formula (I3-2), M m+ is an m-valent organic cation, which is the same as M in the formula (I3-1). m+ Similarly.

[0339] Furthermore, from the viewpoints of high elasticization of the resin film and easy formation of a fine structure without residue, the component (I) is preferably a cationic polymerization initiator that generates an acid with a pKa (acid dissociation constant) of -5 or less upon exposure. By using a cationic polymerization initiator that generates an acid with a more preferably pKa of -6 or less and further preferably pKa of -8 or less, high sensitivity to exposure can be obtained. The lower limit value of the pKa of the acid generated by the component (I) is preferably -15 or more. By using a cationic polymerization initiator that generates an acid with the above-mentioned preferred pKa, it becomes easy to achieve high sensitivity.

[0340] Here, "pKa (acid dissociation constant)" refers to a value that is usually used as an index showing the acid strength of the target substance. In addition, the pKa in this specification is the value under the temperature condition of 25 °C. Furthermore, the pKa value can be measured and obtained by a known method. In addition, the calculated value obtained by using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development Inc.) can also be used.

[0341] Hereinafter, specific examples of the preferred component (I) are exemplified.

[0342]

Chemical formula 31

[0343]

[0344]

Chemical formula 32

[0345]

[0346]

Chemical formula 33

[0347]

[0348] As the component (I), one kind can be used alone, or two or more kinds can be used in combination.

[0349] The component (I) preferably contains two or more selected from the group consisting of the component (I1), the component (I2) and the component (I3), more preferably contains two or more selected from the group consisting of the component (I1) and the component (I2), and further preferably contains a combination of the component (I1) and the component (I2).

[0350] The content of the component (I) is preferably 2.0 to 6.0 parts by mass, more preferably 2.5 to 5.5 parts by mass, and even more preferably 3.0 to 5.0 parts by mass, based on 100 parts by mass of the component (A).

[0351] If the content of component (I) is above the lower limit of the preferred range, sufficient sensitivity can be obtained, and the lithographic properties of the pattern are further improved. In addition, the strength of the cured film is further improved. On the other hand, if it is below the upper limit of the preferred range, the sensitivity is appropriately controlled, and it becomes easy to obtain a pattern with a good shape.

[0352] The content of the component (I) is preferably 1.5 to 5 parts by mass, more preferably 1.6 to 4 parts by mass, and even more preferably 1.7 to 3 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (M).

[0353] When the content of the component (I) is within the above preferred range, the strength of the cured film is further improved, and it becomes easy to form a high-resolution pattern in a good shape.

[0354] In the photosensitive composition of the present embodiment, the mass % of the content of the component (A) in the total content of the components (A), (I) and (M) is preferably 35 mass % or more and less than 70 mass %, more preferably 40 to 60 mass %, and even more preferably 45 to 55 mass %.

[0355] When the content of the component (A) is within the above preferred range, the strength of the cured film is further improved, and the film properties (rolling properties, lamination properties) when formed into a photosensitive resist film are further improved.

[0356] <Other ingredients>

[0357] The photosensitive composition of the present embodiment may contain other components as necessary in addition to the above-mentioned (A) component, (M) component, and (I) component.

[0358] The photosensitive composition of the embodiment may contain miscible additives such as additional resins for improving film performance, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, antihalation agents, etc., as desired.

[0359] 《Silane coupling agent》

[0360] In order to improve the adhesiveness with a support, the photosensitive composition of this embodiment may further contain an adhesive auxiliary agent. As the adhesive auxiliary agent, a silane coupling agent is preferred.

[0361] As the silane coupling agent, for example, there can be mentioned a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, etc. As specific examples, there can be mentioned trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0362] The silane coupling agents may be used alone or in combination of two or more.

[0363] When a silane coupling agent is added to the photosensitive composition of the embodiment, the content of the silane coupling agent is preferably 2.5 to 20 parts by mass, more preferably 3 to 15 parts by mass, and even more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the component (A).

[0364] When the content of the silane coupling agent is within the preferred range, the strength of the cured film is further improved, and the adhesion between the cured film and the support is further enhanced.

[0365] 《Sensitizer ingredients》

[0366] The photosensitive composition of the embodiment may further contain a sensitizer component.

[0367] The sensitizer component is not particularly limited as long as it can absorb energy generated by light exposure and transfer the energy to other substances.

[0368] As the sensitizer component, specifically, benzophenone-type photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-type photosensitizers, acetophenone-type photosensitizers, naphthalene-type photosensitizers such as 1,5-dihydroxynaphthalene, phenol-type photosensitizers, anthracene-type photosensitizers such as 9-ethoxyanthracene, biacetyl, eosin, rose bengal, pyrene, phenothiazine, anthrone and the like known photosensitizers can be used.

[0369] The sensitizer components may be used alone or in combination of two or more.

[0370] When a sensitizer component is added to the photosensitive composition of the embodiment, the content of the sensitizer component is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the component (A).

[0371] When the content of the sensitizer component is within the above preferred range, the sensitivity and resolution are further improved.

[0372] Solvents

[0373] The photosensitive composition of the embodiment can be produced by dissolving or dispersing a photosensitive material in a solvent (hereinafter, sometimes referred to as “(S) component”).

[0374] For example, the component (S) may include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, and 2-heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; derivatives of polyols such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the polyols or compounds having an ester bond; or compounds having an ether bond such as monophenyl ether. [methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME)]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and other esters; aromatic organic solvents such as anisole, ethyl benzyl ether, methyl tolyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropyltoluene, and mesitylene; dimethyl sulfoxide (DMSO), etc.

[0375] The component (S) may be used alone or as a mixed solvent of two or more.

[0376] The amount of the component (S) used is not particularly limited, and is appropriately set in accordance with the coating film thickness at a concentration that allows coating on a substrate or the like.

[0377] The content of the component (S) in the photosensitive composition is preferably 1 to 25% by mass, more preferably 5 to 20% by mass, based on the total amount (100% by mass) of the photosensitive composition.

[0378] [Martens hardness of photosensitive resin film]

[0379] When the negative photosensitive resin composition of the present embodiment is coated on a silicon wafer and baked at 90° C. for 5 minutes to obtain a photosensitive resin film having a thickness of 20 μm, the Martens hardness of the negative photosensitive resin composition is less than 235 [N / mm 2 ], preferably 15 to 200 [N / mm 2 ], more preferably 40 to 160 [N / mm 2 ].

[0380] If the Martens hardness of this photosensitive resin film is below the upper limit value of above-mentioned scope, then when making photosensitive resist film, there is appropriate flexibility, and its film characteristic (rolling, lamination) is excellent.On the other hand, if more than the lower limit value of above-mentioned preferred range, then the intensity of cured film during solidification is further improved.

[0381] The Martens hardness of the photosensitive resin film is measured by the nanoindentation method shown below.

[0382] Evaluation method: FISCHERSCOPE HM2000 measuring device (manufactured by Fischer Instruments) micro-hardness test according to ISO14577

[0383] Measurement conditions: Maximum test load 30mN, load application time 20 seconds, creep time 5 seconds, temperature 25°C

[0384] The Martens hardness of the photosensitive resin film can be controlled to be less than 235 [N / mm by selecting the types of components blended in the negative photosensitive resin composition or by appropriately adjusting the blending ratio thereof. 2 ].

[0385] Preferably, the type of epoxy group-containing resin (A) is selected or the blending ratio thereof is appropriately adjusted. In particular, as component (A), a combination of component (A1) and component (m) may be used, and as component (m), a combination of component (m1) and component (m2) may be used.

[0386] [Tensile elastic modulus of cured film (E*)]

[0387] In this embodiment, the negative photosensitive resin composition is baked at 90° C. for 5 minutes to form a photosensitive resin film with a thickness of 20 μm, and the irradiation dose is 200 mJ / cm 2 The film is exposed to i-line, and then baked at 90°C for 5 minutes after exposure. The film is then baked at 200°C for 1 hour to obtain a cured film having a tensile elastic modulus (E*) of 2.1 [GPa] or more, preferably 2.3 to 4.0 [GPa], and more preferably 2.5 to 3.5 [GPa].

[0388] If the tensile elastic modulus (E*) of the cured film is above the lower limit of the above range, the cured film has sufficient strength and can fully maintain the space even when a high pressure is applied when forming a hollow structure. On the other hand, if it is below the upper limit of the above preferred range, it becomes easy to suppress the generation of cracks in the cured film.

[0389] The tensile elastic modulus (E*) of the cured film is a value measured at a temperature of 175° C. when viscoelasticity of the cured film is measured at a frequency of 1.0 Hz.

[0390] The tensile elastic modulus (E*) of the cured film can be controlled to be 2.1 [GPa] or more by selecting the types of components blended in the negative photosensitive resin composition or appropriately adjusting the blending ratio thereof.

[0391] It is preferred to increase the content of the metal oxide (M), select the type of epoxy group-containing resin (A), or appropriately adjust the blending ratio thereof. In particular, the content of the component (M) may exceed 30 parts by mass based on 100 parts by mass of the component (A).

[0392] (Photosensitive resist film)

[0393] The photosensitive resist film of the present embodiment is obtained by laminating a negative photosensitive resin film containing an epoxy group-containing resin (A), a metal oxide (M), and a cationic polymerization initiator (I) on a base film.

[0394] In addition, when the negative photosensitive resin film in the photosensitive resist film of the present embodiment is laminated on a silicon wafer with a film thickness of 20 μm, the Martens hardness of the photosensitive resin film is less than 235 [N / mm 2 ], and if the photosensitive resin film is irradiated with an amount of 200 mJ / cm 2 The film was exposed to i-line, and then post-exposure baking was performed at 90°C for 5 minutes, followed by baking at 200°C for 1 hour, thereby curing to obtain a cured film. When the viscoelasticity of the cured film was measured at a frequency of 1.0 Hz, the tensile elastic modulus (E*) at a temperature of 175°C was greater than 2.1 [GPa].

[0395] Here, the photosensitive resin film in the photosensitive resist film of this embodiment is typically composed of a resin material in a B-stage state (semi-cured state). The above-mentioned Martens hardness is a value measured when the photosensitive resin film is laminated on a silicon wafer with a film thickness of 20 μm. The lamination is performed under the conditions of 90° C., 0.3 MPa, and 0.5 m / min.

[0396] In addition, when the thickness of the photosensitive resin film in the photosensitive resist film of the present embodiment is less than 20 μm, the Martens hardness can be measured by laminating a plurality of photosensitive resin films on a silicon wafer (grinding after lamination as needed) and adjusting the film thickness to 20 μm. In addition, when the thickness of the photosensitive resin film in the photosensitive resist film of the present embodiment exceeds 20 μm, the Martens hardness can be measured by grinding the resin film after laminating the resin film on a silicon wafer and adjusting the film thickness to 20 μm. The measurement conditions of the Martens hardness of the test object after adjusting the film thickness can be the above-mentioned nanoindentation method.

[0397] If a photosensitive resin film is formed using the above-mentioned photosensitive resist film and the photosensitive resin film is selectively exposed, the cationic part of the (I) component decomposes in the exposed part of the photosensitive resin film to generate an acid. Through the action of the acid, the epoxy group in the (A) component undergoes ring-opening polymerization, and the solubility of the (A) component in a developer containing an organic solvent decreases. On the other hand, in the unexposed part of the photosensitive resin film, the solubility of the (A) component in a developer containing an organic solvent does not change, so a difference in solubility in a developer containing an organic solvent occurs between the exposed part and the unexposed part of the photosensitive resin film. That is, the photosensitive resin film is a negative type. Therefore, if the photosensitive resin film is developed using a developer containing an organic solvent, the unexposed part is dissolved and removed to form a negative pattern.

[0398] The photosensitive resist film of the embodiment can be produced by applying the negative photosensitive resin composition of the embodiment on a base film and drying the composition to form a photosensitive resin film.

[0399] The negative photosensitive resin composition may be applied onto the base film by an appropriate method using an applicator, a knife coater, a lip coater, a comma roll coater, a coating machine, or the like.

[0400] The thickness of the photosensitive resin film is preferably 100 μm or less, more preferably 5 to 50 μm.

[0401] <Base Film>

[0402] In the photosensitive resist film of the embodiment, a known film can be used as the base film, for example, a thermoplastic resin film can be used. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The base film preferably has a thickness of 2 to 150 μm.

[0403] <Photosensitive resin film>

[0404] The negative photosensitive resin film in the photosensitive resist film of the embodiment contains an epoxy-containing resin (A), a metal oxide (M) and a cationic polymerization initiator (I). Hereinafter, these components are also referred to as (A) component, (M) component and (I) component, respectively, as in the case of the negative photosensitive resin composition described above.

[0405] The descriptions of the components (A), (M) and (I) contained in the negative photosensitive resin film are the same as the descriptions of the components (A), (M) and (I) contained in the negative photosensitive resin composition.

[0406] The negative photosensitive resin film may contain other components as required in addition to the above-mentioned components (A), (M) and (I). Other components include, for example, silane coupling agents, sensitizer components and solvents, and miscible additives (e.g., additional resins for improving film performance, dissolution inhibitors, alkaline compounds, plasticizers, stabilizers, colorants, antihalation agents, etc.).

[0407] [Martens hardness of photosensitive resin film]

[0408] The negative photosensitive resin film in the photosensitive resist film of the present embodiment has a Martens hardness of less than 235 [N / mm 2 ], preferably 15 to 200 [N / mm 2 ], more preferably 40 to 160 [N / mm 2 ].

[0409] If the Martens hardness of this photosensitive resin film is below the upper limit value of above-mentioned scope, then when making photosensitive resist film, there is appropriate flexibility, and its film characteristic (rolling, lamination) is excellent.On the other hand, if more than the lower limit value of above-mentioned preferred range, then the intensity of cured film during solidification is further improved.

[0410] As described above, a photosensitive resin film was laminated on a silicon wafer to have a film thickness of 20 μm, and the Martens hardness of the photosensitive resin film was measured by the nanoindentation method described below.

[0411] Evaluation method: FISCHERSCOPE HM2000 measuring device (manufactured by Fischer Instruments) micro-hardness test according to ISO14577

[0412] Measurement conditions: Maximum test load 30mN, load application time 20 seconds, creep time 5 seconds, temperature 25°C

[0413] [Tensile elastic modulus of cured film (E*)]

[0414] The photosensitive resin film having a film thickness of 20 μm in the photosensitive resist film of this embodiment was irradiated with an amount of 200 mJ / cm 2 The film is exposed to i-line, and then baked at 90°C for 5 minutes after exposure. The film is then baked at 200°C for 1 hour to obtain a cured film having a tensile elastic modulus (E*) of 2.1 [GPa] or more, preferably 2.3 to 4.0 [GPa], and more preferably 2.5 to 3.5 [GPa].

[0415] If the tensile elastic modulus (E*) of the cured film is above the lower limit of the above range, the cured film has sufficient strength and can fully maintain the space even when a high pressure is applied when forming a hollow structure. On the other hand, if it is below the upper limit of the above preferred range, it becomes easy to suppress the generation of cracks in the cured film.

[0416] The tensile elastic modulus (E*) of the cured film is a value measured at a temperature of 175° C. when viscoelasticity of the cured film is measured at a frequency of 1.0 Hz.

[0417] As described above, the negative photosensitive resin composition or photosensitive resist film (photosensitive material of the present embodiment) of the present embodiment has a Martens hardness of less than 235 [N / mm 2 ], and the tensile elastic modulus (E*) of its cured film (completely cured state) is above 2.1 [GPa]. Due to such characteristics, according to the photosensitive material of the present embodiment described above, a cured film with further improved strength can be obtained. As a result, the hollow structure can be maintained even in the face of a higher pressure applied during molding. In addition, in the photosensitive material of the present embodiment, the strength of the cured film is improved, and on the other hand, the decrease in adhesion in the photosensitive resin film is suppressed, so it is easy to roll, and the lamination properties to substrates, etc. are also excellent.

[0418] Furthermore, according to the photosensitive material of this embodiment, sufficient sensitivity can be obtained, and residue can be reduced, so that a high-resolution pattern can be formed in a good shape.

[0419] The photosensitive resist film according to one aspect of the present invention is not limited to the above-described embodiment, and may be, for example, a photosensitive resist film composed of a laminate in which the photosensitive resin film and a cover film are sequentially laminated on the base film.

[0420] As the cover film, a known cover film can be used, for example, a polyethylene film, a polypropylene film, etc. can be used. As the cover film, a film having a lower adhesive force 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 further preferably 5 to 50 μm.

[0421] The base film and the cover film may be made of the same film material or different films may be used.

[0422] When used, for example, a laminate of a photosensitive resin film / base film can be laminated on a support while peeling off a cover film, and a pattern can be formed on the support by peeling off the base film, exposing and developing.

[0423] (Pattern Formation Method)

[0424] The pattern forming method of the present embodiment comprises: a process of forming a photosensitive resin film on a support body using the negative photosensitive resin composition or photosensitive resist film of the above-mentioned embodiment (hereinafter referred to as the "film forming process"), a process of exposing the photosensitive resin film (hereinafter referred to as the "exposure process"), and a process of developing the exposed photosensitive resin film using a developer containing an organic solvent to form a negative pattern (hereinafter referred to as the "development process").

[0425] The pattern forming method of the present embodiment can be performed, for example, as follows.

[0426] [Film formation step]

[0427] First, the negative photosensitive resin composition of the above-mentioned embodiment is applied to the support by a known method such as spin coating, roll coating, screen printing, etc., and then baked (post apply bake (PAB)) for 2 to 60 minutes at a temperature of 50 to 150° C. to form a photosensitive resin film.

[0428] In the film formation step, a photosensitive resin film can be formed on a support by laminating a photosensitive resist film on a support. When laminating, the support and the film can be heated, pressed (laminated), etc. as needed.

[0429] The support is not particularly limited, and conventionally known supports can be used, for example, substrates for electronic components, supports on which a predetermined wiring pattern is formed, etc. More specifically, silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, or glass substrates, resin films such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, and polyethylene, etc. can be cited. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used.

[0430] In addition, the support may be a support having an inorganic and / or organic film disposed on the substrate as described above. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) may be cited. As the organic film, an organic film such as an organic anti-reflection film (organic BARC) or a lower organic film in a multilayer resist method may be cited.

[0431] The film thickness of the photosensitive resin film formed of the negative photosensitive resin composition or the photosensitive resist film is not particularly limited, but is preferably about 10 to 100 μm. The negative photosensitive resin composition of the embodiment can obtain good properties even when formed into a thick film.

[0432] [Exposure process]

[0433] Next, the formed photosensitive resin film is selectively exposed using a known exposure apparatus, such as by exposing through a mask having a predetermined pattern (mask pattern) or by drawing based on direct irradiation of electron beams without using a mask, and then, as required, a baking (post-exposure baking (PEB)) treatment is performed at a temperature of 80 to 150° C. for 40 to 600 seconds, preferably for 60 to 300 seconds.

[0434] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays with a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm) or visible light is selectively irradiated (exposed). As the source of these radiations, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc. can be used.

[0435] Here, radiation refers to ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, etc. The radiation exposure dose varies depending on the type and amount of each component in the composition, the film thickness of the coating film, etc. For example, when using an ultra-high pressure mercury lamp, it is 100 to 2000 mJ / cm 2 .

[0436] The exposure method of the photosensitive resin film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be a liquid immersion lithography.

[0437] The photosensitive resin film after the exposure step has high transparency. For example, the haze value when irradiated with i-line (wavelength 365 nm) is preferably 3% or less, more preferably 1.0 to 2.7%.

[0438] Thus, the photosensitive resin film formed using the negative photosensitive resin composition or photosensitive resist film of the above embodiment has high transparency. Therefore, during exposure in pattern formation, light transmittance is improved, and a negative pattern with good lithography characteristics is easily obtained.

[0439] The haze value of the photosensitive resin film after the exposure step is measured by a method in accordance with JIS K 7136 (2000).

[0440] [Development process]

[0441] Next, the exposed photosensitive resin film is developed with a developer containing an organic solvent (organic developer). After development, a rinse treatment is preferably performed. A baking treatment (post-baking) may also be performed as needed.

[0442] Through the above-mentioned film forming step, exposure step, and development step, a pattern can be formed.

[0443] The organic solvent contained in the organic developer can be any organic solvent that can dissolve component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, hydrocarbon solvents, etc. can be cited.

[0444] Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0445] Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, 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, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate 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, ethyl lactate, butyl lactate Ester, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. Among these, butyl acetate or PGMEA is preferred as the ester solvent.

[0446] Examples of the nitrile solvent include acetonitrile, propionitrile, valeronitrile and butyronitrile.

[0447] The organic developer may be mixed with known additives as required. Examples of such additives include surfactants. Surfactants are not particularly limited, and for example, ionic, nonionic fluorine and / or silicon surfactants may be used.

[0448] As the surfactant, a nonionic surfactant is preferred, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferred.

[0449] When a surfactant is added, the amount thereof 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, based on the total amount of the organic developer.

[0450] Development can be carried out by a known development method, for example, a method of immersing the support in a developer for a certain period of time (immersion method), a method of carrying the developer on the surface of the support by surface tension and allowing it to remain still for a certain period of time (puddle method), a method of spraying the developer onto the surface of the support (spraying method), a method of continuously discharging the developer onto a support rotating at a certain speed while scanning a developer discharge nozzle at a certain speed (dynamic distribution method), etc.

[0451] The rinsing treatment (cleaning treatment) using the rinsing liquid can be carried out by a known rinsing method. Examples of the rinsing treatment method include a method of continuously discharging the rinsing liquid onto a support body rotating at a certain speed (spin coating method), a method of immersing the support body in the rinsing liquid for a certain period of time (immersion method), and a method of spraying the rinsing liquid onto the surface of the support body (spray coating method).

[0452] The rinsing treatment preferably uses a rinsing liquid containing an organic solvent.

[0453] In the pattern forming method of the above-mentioned embodiment, since the above-mentioned negative photosensitive resin composition is used, high sensitivity can be achieved, and residue can be reduced, and a high-resolution pattern can be formed in a good shape.

[0454] (cured film)

[0455] The cured film of the present embodiment is a cured film obtained by curing the negative photosensitive resin composition of the above-mentioned embodiment.

[0456] In the cured film of the embodiment, the tensile elastic modulus (E*) at a temperature of 175° C. when viscoelasticity is measured at a frequency of 1.0 Hz is 2.1 [GPa] or more, preferably 2.3 to 4.0 [GPa], and more preferably 2.5 to 3.5 [GPa].

[0457] According to the present embodiment described above, since the strength as a cured film is further improved, the hollow structure can be stably maintained even against a high pressure applied during molding.

[0458] (Method for producing cured film)

[0459] The method for producing a cured film of the present embodiment comprises: step (i) of forming a photosensitive resin film on a support using the negative photosensitive resin composition or photosensitive resist film of the above embodiment; and step (ii) of curing the photosensitive resin film to obtain a cured film.

[0460] The operation of step (i) can be performed in the same manner as in the above-mentioned [film forming step]. The baking treatment can be performed, for example, at a temperature of 50 to 100° C. for 0.5 to 30 minutes.

[0461] The curing treatment in step (ii) can be performed, for example, at a temperature of 100 to 250° C. for 0.5 to 2 hours.

[0462] The method for producing a cured film of the embodiment may include other steps in addition to step (i) and step (ii). For example, the above-mentioned [exposure step] may be included between step (i) and step (ii), and the photosensitive resin film formed in step (i) may be selectively exposed, and the photosensitive resin film (precured film) subjected to a baking (PEB) treatment may be cured as needed to obtain a cured film.

[0463] According to the method for producing a cured film of the above-described embodiment, a cured film having further improved strength can be produced.

[0464] (Roller body)

[0465] The roll body of this embodiment is obtained by winding the photosensitive resist film of the above-mentioned embodiment around a core.

[0466] The core can be made of paper tube, wooden tube, plastic tube, etc.

[0467] In the roll body of this embodiment, since the photosensitive resist film of the above-mentioned embodiment is used, cracks and poor pressure bonding are unlikely to occur when the laminate of the photosensitive resin film / base film is wound on the core, and the roll can be easily and stably formed.

[0468] Example

[0469] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

[0470] <Preparation of Negative Photosensitive Resin Composition>

[0471] (Examples 1 to 13, Comparative Examples 1 to 3)

[0472] The components shown in Table 1 were mixed and dissolved in methyl ethyl ketone (MEK), and filtered using a PTFE filter (pore size 1 μm, manufactured by PALL) to prepare negative photosensitive resin compositions of various examples (MEK solutions having a solid content of 80 to 85% by mass).

[0473]

Table 1

[0474]

[0475] In Table 1, each abbreviation has the following meaning. The numerical value in [ ] is the blending amount of each component (parts by mass; converted to solid content).

[0476] (A)-1: An epoxy group-containing resin represented by the following general formula (A11). Trade name "JER-157S70", manufactured by Mitsubishi Chemical Corporation.

[0477] [Chemical formula 34]

[0478]

[0479] (A)-2: A compound represented by the following chemical formula (m1-1). Trade name "CELLOXIDE8010", manufactured by Daicel Corporation.

[0480] (A)-3: A compound represented by the following chemical formula (m1-2). Trade name "CELLOXIDE2021P", manufactured by Daicel Corporation.

[0481] (A)-4: A compound represented by the following chemical formula (m2-1). Trade name "TEPIC-VL", manufactured by Nissan Chemical Industries, Ltd.

[0482] [Chemical formula 35]

[0483]

[0484] (M)-1: Silica component (a). Trade name "MEK-EC-2130Y", manufactured by Nissan Chemical Industries, Ltd. Primary particle size φ = 15 nm (volume average value). A methyl ethyl ketone dispersion with a silica component concentration of 31% by mass.

[0485] (I1)-1: A cationic polymerization initiator represented by the following chemical formula (I1-1). Trade name "CPI-310B", manufactured by San-Apro Ltd.

[0486] (I2)-1: A cationic polymerization initiator represented by the following chemical formula (I2-1). Trade name "CPI-410S", manufactured by San-Apro Ltd.

[0487] [Chemical formula 36]

[0488]

[0489] [Measurement of the Martens hardness of the photosensitive resin film]

[0490] Coat the negative photosensitive resin composition of each example on a silicon wafer and perform a baking treatment at 90 °C for 5 minutes, thereby forming a photosensitive resin film with a film thickness of 20 μm on the silicon wafer. Measure the Martens hardness [N / mm 2 of the photosensitive resin film by the nanoindentation method shown below. The results are shown in Table 2.

[0491] Nanoindentation method

[0492] Evaluation method: FISCHERSCOPE HM2000 measuring device (manufactured by Fischer Instruments) micro-hardness test according to ISO14577

[0493] Measurement conditions: Maximum test load 30mN, load application time 20 seconds, creep time 5 seconds, temperature 25°C

[0494] [Evaluation of Rolling]

[0495] The negative photosensitive resin composition of each example was applied to a substrate film with a width of 200 mm and a thickness of 20 μm using an applicator, and dried to form a photosensitive resin layer.

[0496] Next, a cover film with a width of 200 mm was pressed onto the photosensitive resin layer with a rubber roller so as not to leave any bubbles, and the laminate (cover film / photosensitive resin layer / base film) was wound around a core for 150 m to produce a main roll.

[0497] At this time, the case where cracks or poor crimping occurred was evaluated as ×, and the case where cracks or poor crimping did not occur was evaluated as ○. The results are shown in Table 2.

[0498] <Manufacturing of Photosensitive Resist Film>

[0499] The negative photosensitive resin composition of each example was applied onto a substrate film using an applicator, heated at 50° C. for 3 minutes, and then baked (PAB) at 70° C. for 3 minutes to form a photosensitive resin film having a film thickness of 20 μm.

[0500] Next, a cover film is laminated on the photosensitive resin film to obtain a photosensitive resist film.

[0501] <Manufacturing of Cured Film>

[0502] Step (i):

[0503] The cover film on the photosensitive resin film in the photosensitive resist film obtained above was peeled off, and the exposed photosensitive resin film and the silicon wafer were laminated under the conditions of 90° C., 0.3 MPa, and 0.5 m / min.

[0504] Then, the base film in contact with the photosensitive resin film was peeled off, and the photosensitive resin film was irradiated with 200 mJ / cm 2 The film was irradiated with i-ray (wavelength 365 nm) at an irradiation dose of 1000 nm. Then, post-exposure heating was performed on a hot plate at 90° C. for 5 minutes to obtain a precured film.

[0505] Step (ii):

[0506] Then, the obtained pre-cured film was heated at 200° C. for 1 hour in a nitrogen atmosphere to be cured, thereby obtaining a target cured film.

[0507] [Evaluation of lamination properties]

[0508] In the step (i), when the exposed photosensitive resin film and the silicon wafer were laminated under the above conditions, the lamination properties were evaluated according to the following evaluation criteria.

[0509] Evaluation Benchmarks

[0510] ○: Successfully bonded to silicon wafer.

[0511] △: There is partial adhesion failure (less than 5% of the total area).

[0512] ×: Adhesion failure such as peeling occurs (5% or more of the total area).

[0513] [Measurement of tensile elastic modulus (E*) of cured film]

[0514] The tensile elastic modulus (E*) of the cured film obtained in the step (ii) was measured as follows.

[0515] The obtained cured film was peeled off from the silicon wafer, and the tensile elastic modulus (E*) [GPa] of the cured film at 175° C. was measured using the following evaluation device and measurement conditions. The results are shown in Table 2.

[0516] ·Evaluation device: Reogel E-4000 (manufactured by UBM)

[0517] Measurement conditions: tensile mode, frequency 1.0 Hz, distance between chucks 10 mm

[0518] The higher the tensile elastic modulus (E*), the higher the strength of the cured film.

[0519] <Pattern Formation Method>

[0520] Film formation process:

[0521] The cover film on the photosensitive resin film in the photosensitive resist film obtained above was peeled off, and the exposed photosensitive resin film and the silicon wafer were laminated under the conditions of 90° C., 0.3 MPa, and 0.5 m / min.

[0522] Exposure process:

[0523] Next, the base film in contact with the photosensitive resin film was peeled off, and the photosensitive resin film was exposed to 300 mJ / cm 2The photosensitive resin film was irradiated with i-ray (365 nm) at an irradiation dose of 1000 nm. Thereafter, post-exposure heating was performed on a hot plate at 90° C. for 5 minutes.

[0524] Development process:

[0525] Next, the exposed silicon wafer was developed with propylene glycol monomethyl ether acetate (PGMEA) at 23° C. for 5 minutes, and then rinsed and dried to form a negative pattern.

[0526] [Evaluation of photolithography characteristics]

[0527] The formed negative pattern was observed for its fine structure using a scanning electron microscope (S-4300 manufactured by Hitachi High-Technologies Corporation). Specifically, the presence or absence of residue in the negative pattern and the cross-sectional shape of the opening pattern with a hole diameter of 20 μm were observed, and the photolithography characteristics were evaluated according to the following evaluation criteria. The results are shown in Table 2.

[0528] Evaluation Benchmarks

[0529] ○: A rectangular pattern without residue was obtained.

[0530] ×: A tapered pattern was obtained.

[0531]

Table 2

[0532]

[0533] From the results shown in Table 2, it can be confirmed that the Martens hardness of the photosensitive resin film is less than 235 [N / mm 2 ] and the tensile elastic modulus (E*) of the cured film is 2.1 [GPa] or more. Compared with the negative photosensitive resin compositions of Comparative Examples 1 to 3, a cured film with further improved strength can be obtained, and it is easy to roll and has excellent lamination properties.

[0534] Furthermore, it was also confirmed that the negative photosensitive resin compositions of Examples 1 to 13 could form patterns having good shapes.

Claims

1. A negative photosensitive resin composition comprising an epoxy resin (A), a metal oxide (M) and a cationic polymerization initiator (I), which is used to form a negative pattern by developing with a developer containing an organic solvent, characterized in that: In the negative photosensitive resin composition, when the negative photosensitive resin composition is coated on a silicon wafer and baked at 90° C. for 5 minutes to obtain a photosensitive resin film with a film thickness of 20 μm, the Martens hardness of the negative photosensitive resin film is less than 235 [N / mm 2 ],and When the photosensitive resin film is irradiated with an amount of 200 mJ / cm 2 The cured film was exposed to i-line, and then subjected to post-exposure baking at 90°C for 5 minutes, and then subjected to baking at 200°C for 1 hour to be cured. When viscoelasticity of the cured film was measured at a frequency of 1.0 Hz, the tensile elastic modulus (E*) at a temperature of 175°C was 2.1 [GPa] or more. The content of the metal oxide (M) is more than 30 parts by mass and less than 180 parts by mass relative to 100 parts by mass of the epoxy group-containing resin (A). The epoxy group-containing resin (A) contains a resin (A1) represented by the following general formula (A1): In the formula, R p1 and R p2 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 Can be the same or different, multiple R p2 may be the same or different from each other, n1 is an integer from 1 to 5, R EP It is an epoxy group, with multiple R EP Can be the same or different. The epoxy group-containing resin (A) contains a compound (m1) having a partial structure represented by the following general formula (m1), 【Chemistry 2】 In the formula, n2 is an integer from 1 to 4, * represents a chemical bond, The epoxy group-containing resin (A) contains a compound (m2) represented by the following general formula (m2): In the formula, R EP It is an epoxy group, with multiple R EP Can be the same or different. The epoxy group-containing resin (A) contains the resin (A1), the compound (m1) and the compound (m2), The total content of the compound (m1) and the compound (m2) in the total content of the resin (A1), the compound (m1) and the compound (m2) is 15% by mass or more.

2. The negative photosensitive resin composition according to claim 1, wherein The content of the epoxy group-containing resin (A) in the total content of the epoxy group-containing resin (A), the cationic polymerization initiator (I), and the metal oxide (M) is 35% by mass or more and less than 70% by mass.

3. A pattern forming method, characterized in that: The method comprises: forming a photosensitive resin film on a support using the negative photosensitive resin composition according to claim 1 or 2, exposing the photosensitive resin film to light, and developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern.

4. A cured film, characterized in that: A cured film obtained by curing the negative photosensitive resin composition according to claim 1 or 2.

5. A method for producing a cured film, characterized in that: The method comprises the steps of forming a photosensitive resin film on a support using the negative photosensitive resin composition according to claim 1 or 2, and curing the photosensitive resin film to obtain a cured film.

6. A photosensitive resist film, which is obtained by laminating a negative photosensitive resin film containing an epoxy resin (A), a metal oxide (M) and a cationic polymerization initiator (I) on a substrate film, characterized in that: When the photosensitive resin film is laminated on a silicon wafer with a film thickness of 20 μm, the Martens hardness of the photosensitive resin film is less than 235 [N / mm 2 ],and When the photosensitive resin film is irradiated with an amount of 200 mJ / cm 2 The cured film was exposed to i-line, and then subjected to post-exposure baking at 90°C for 5 minutes, and then subjected to baking at 200°C for 1 hour to obtain a cured film. When viscoelasticity of the cured film was measured at a frequency of 1.0 Hz, the tensile elastic modulus (E*) at a temperature of 175°C was 2.1 [GPa] or more. The content of the metal oxide (M) is more than 30 parts by mass and less than 180 parts by mass relative to 100 parts by mass of the epoxy group-containing resin (A). The epoxy group-containing resin (A) contains a resin (A1) represented by the following general formula (A1): [Chemical 4] In the formula, R p1 and R p2 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 Can be the same or different, multiple R p2 may be the same or different from each other, n1 is an integer from 1 to 5, R EP It is an epoxy group, with multiple R EP Can be the same or different. The epoxy group-containing resin (A) contains a compound (m1) having a partial structure represented by the following general formula (m1), 【Chemistry 5】 In the formula, n2 is an integer from 1 to 4, * represents a chemical bond, The epoxy group-containing resin (A) contains a compound (m2) represented by the following general formula (m2): In the formula, R EP It is an epoxy group, with multiple R EP Can be the same or different. The epoxy group-containing resin (A) contains the resin (A1), the compound (m1) and the compound (m2), The total content of the compound (m1) and the compound (m2) in the total content of the resin (A1), the compound (m1) and the compound (m2) is 15% by mass or more.

7. The photosensitive resist film according to claim 6, wherein The content of the epoxy group-containing resin (A) in the total content of the epoxy group-containing resin (A), the cationic polymerization initiator (I), and the metal oxide (M) is 35% by mass or more and less than 70% by mass.

8. The photosensitive resist film according to claim 6 or 7, wherein: The photosensitive resin film and the cover film are sequentially laminated on the base film.

9. A pattern forming method, characterized in that: The method comprises: forming a photosensitive resin film on a support using the photosensitive resist film according to claim 6 or 7, exposing the photosensitive resin film to light, and developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern.

10. A method for producing a cured film, characterized in that: The method comprises the steps of forming a photosensitive resin film on a support using the photosensitive resist film according to claim 6 or 7, and curing the photosensitive resin film to obtain a cured film.

11. A roller body, characterized in that: A roll body obtained by winding the photosensitive resist film according to claim 6 or 7 around a core.

Images