Negative photosensitive resin composition, photosensitive resist film, pattern forming method, cured film, method for producing cured film, and roll body

Abstract

A negative-working photosensitive resin composition which can be used as a photosensitive material for forming a hollow structure, comprises an epoxy-group-containing resin, a metal oxide and a cationic polymerization initiator, can be developed with a developing solution comprising an organic solvent to form a negative-working pattern, or a photosensitive resist film is employed. A photosensitive resin film having a film thickness of 20 μm and formed on a silicon wafer using the negative-working photosensitive resin composition has Martens hardness of less than 235 [N / mm2], and a cured film produced by curing the photosensitive resin film has a tensile modulus (E*) of 2.1 [GPa] or more at a temperature of 175℃ 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 roll body. This application claims priority based on Japanese Patent Application No. 2019-185122 filed in Japan on October 8, 2019, the contents of which are incorporated herein by reference. [Background technology]

[0002] In recent years, the development of microelectronic devices such as surface acoustic wave (SAW) filters has progressed. Packages that encapsulate such electronic devices have a hollow structure to ensure the propagation of surface acoustic waves and the mobility of the movable parts of the electronic devices. The hollow structure is formed by molding a photosensitive material while maintaining a hollow space above the wiring substrate on which the electrodes are formed. The photosensitive material used here is required to form a thin and strong cured film.

[0003] As a photosensitive material for forming the hollow structure, a negative photosensitive resin composition containing an epoxy group-containing resin, a metal oxide, and a specific cationic polymerization initiator that generates a relatively strong acid upon exposure to light, and a photosensitive resist film have been disclosed. With such a negative photosensitive resin composition and photosensitive resist film, a pattern with a good shape can be formed, and the strength of the cured film is improved (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-36533 A Summary of the Invention [Problem to be solved by the invention]

[0005] As the development of microelectronic devices progresses, there is currently a demand for modules with even lower heights, and in response to this, it is necessary to miniaturize the hollow structure of the package while still ensuring space in the vicinity of the electrodes formed on the wiring substrate. However, when attempting to miniaturize the hollow structure in this manner, the strength of a cured film obtained by curing a conventional negative photosensitive resin composition or photosensitive resist film is insufficient, and it may become difficult to maintain the hollow structure against, for example, the high pressure applied during molding.

[0006] On the other hand, in the case of a photosensitive resist film, if one attempts to simply increase the hardness of the film in order to improve its strength after curing, there is a risk that the film may crack or have poor compression bonding, or that poor bonding between the film and a silicon wafer or the like may occur, for example, when producing a master roll.

[0007] The present invention has been made in consideration of the above circumstances, and has an object to provide a photosensitive resist film which gives a cured film with enhanced strength, is easily rolled, and has excellent lamination properties with respect to substrates and the like, a negative type photosensitive resin composition capable of producing the same, a pattern forming method, a cured film and a method for producing the same, and a roll body. [Means for solving the problem]

[0008] The present invention includes the following aspects. A first aspect of the present invention is a negative-type photosensitive resin composition which contains an epoxy group-containing resin (A), a metal oxide (M), and a cationic polymerization initiator (I) and forms a negative pattern by development using a developer containing an organic solvent, the negative-type photosensitive resin composition being 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 which is 235 [N / mm 2 ] or less, and the irradiation dose for the photosensitive resin film is 200 mJ / cm 2The negative photosensitive resin composition is characterized in that the cured film obtained by exposing the film to i-line at 400°C for 5 minutes, post-exposure baking at 90°C for 5 minutes, and then baking at 200°C for 1 hour has a tensile modulus of elasticity (E*) of 2.1 [GPa] or more at 175°C when the viscoelasticity is measured at a frequency of 1.0 Hz.

[0009] A second aspect of the present invention is a photosensitive resist film in which a negative photosensitive resin film containing an epoxy group-containing resin (A), a metal oxide (M) and a cationic polymerization initiator (I) is laminated on a base film, and the photosensitive resin film has a Martens hardness of 235 [N / mm 2 ] or less, and the irradiation dose for the photosensitive resin film is 200 mJ / cm 2 This photosensitive resist film is characterized in that the cured film is exposed to i-line at 400°C, post-exposure baked at 90°C for 5 minutes, and then baked at 200°C for 1 hour, and has a tensile modulus of elasticity (E*) of 2.1 [GPa] or more at a temperature of 175°C when the viscoelasticity is measured at a frequency of 1.0 Hz.

[0010] A third aspect of the present invention is a pattern forming method, comprising the steps of forming a photosensitive resin film on a support using the negative photosensitive resin composition according to the first aspect or the photosensitive resist film according to the second aspect, exposing the photosensitive resin film, and developing the exposed photosensitive resin film to form a negative pattern.

[0011] A fourth aspect of the present invention is a cured film obtained by curing the negative type photosensitive resin composition according to the first aspect.

[0012] A fifth aspect of the present invention is a method for producing a cured film, comprising the steps of: forming a photosensitive resin film on a support using the negative photosensitive resin composition according to the first aspect or the photosensitive resist film according to the second aspect; and curing the photosensitive resin film to obtain a cured film.

[0013] A sixth aspect of the present invention is a roll body, characterized in that the photosensitive resist film according to the second aspect is wound around a core. Effect of the Invention

[0014] According to the present invention, it is possible to provide a photosensitive resist film which can obtain a cured film having enhanced strength, can be easily rolled, and has excellent lamination properties for substrates and the like, a negative type photosensitive resin composition capable of producing the same, a pattern forming method, a cured film and a method for producing the same, and a roll body. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In this specification and the claims, the term "aliphatic" is a relative concept to aromaticity and is defined as meaning a group or compound that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The term "halogenated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms. The term "fluorinated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The term "optionally substituted" refers to the case where a hydrogen atom (-H) is replaced with a monovalent group, or the case where a methylene group (-CH 2 -) is replaced with a divalent group. The term "exposure" is intended to include any concept including irradiation with radiation.

[0016] (Negative-type photosensitive resin composition) The negative photosensitive resin composition of this embodiment (hereinafter sometimes simply referred to as "photosensitive composition") contains an epoxy group-containing resin (A), a metal oxide (M), and a cationic polymerization initiator (I). Hereinafter, these components are also referred to as component (A), component (M), and component (I), respectively. In addition, when the photosensitive composition of the present embodiment is applied onto 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 film is 235 [N / mm 2 ] or less, and the irradiation dose for the photosensitive resin film is 200 mJ / cm 2 The cured film is exposed to i-line at 400°C, post-exposure baked at 90°C for 5 minutes, and then baked at 200°C for 1 hour to obtain a cured film that has a tensile modulus (E*) of 2.1 GPa or more at 175°C when viscoelasticity is measured at a frequency of 1.0 Hz.

[0017] When a photosensitive resin film is formed using such a photosensitive composition and selectively exposed to light, in the exposed portion of the photosensitive resin film, the cationic portion of the (I) component is decomposed to generate an acid, and the epoxy group in the (A) component is ring-opened and polymerized by the action of the acid, decreasing the solubility of the (A) component in a developer containing an organic solvent, while in the unexposed portion of the photosensitive resin film, the solubility of the (A) component 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 portion and the unexposed portion of the photosensitive resin film. Therefore, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed portion is dissolved and removed, forming a negative pattern.

[0018] <Epoxy group-containing resin (A)> The epoxy group-containing resin (component (A)) is not particularly limited as long as it has a sufficient number of epoxy groups in one molecule to form a pattern by exposure. Examples of the component (A) include novolac type epoxy resins (Anv), bisphenol A type epoxy resins (Abp), bisphenol F type epoxy resins, aliphatic epoxy resins, and acrylic resins (Aac).

[0019] <Novolac type epoxy resin (Anv)> Suitable examples of the novolac epoxy resin (Anv) include resin (A1) (hereinafter also referred to as "component (A1)") represented by the following general formula (A1).

[0020] [ka] [In the formula, R p1 and R p2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 may be the same or different. p2 may be the same or different. 1 is an integer from 1 to 5. EP is an epoxy group-containing group. EP may be the same or different.

[0021] 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group, and examples of the cyclic alkyl group include a cyclobutyl group, and a cyclopentyl group. Among them, R p1 , R p2As the alkyl group, a hydrogen atom or a linear or branched alkyl group is preferable, a hydrogen atom or a linear alkyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable. In formula (A1), a plurality of R p1 may be the same or different. p2 may be the same or different from each other.

[0022] In formula (A1), n 1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0023] In formula (A1), R EP is an epoxy group-containing group. R EP The epoxy group-containing group is not particularly limited, and examples thereof include a group consisting of only epoxy groups; a group consisting of only alicyclic epoxy groups; and a group having an epoxy group or an alicyclic epoxy group and a divalent linking group. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically, is a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that is the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. The hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or the alicyclic epoxy group is linked via the divalent linking group bonded to an oxygen atom (—O—) in the formula.

[0024] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0025] Regarding the optionally substituted divalent hydrocarbon group: Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

[0026] 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 preferable, and specifically, a methylene group [-CH 2 -], ethylene group [-(CH 2 ) 2 -], trimethylene group [-(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] etc. 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. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc. alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 -, etc. alkyl ethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, etc.; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0027] Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms are removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0028] 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 monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0029] The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent, which may include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.

[0030] 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, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Examples of the halogenated alkyl group as the substituent include the alkyl groups in which some or all of the hydrogen atoms of the alkyl groups are substituted with the halogen atoms. In the alicyclic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) 2 -, -S(=O) 2 -O- is preferred.

[0031] In the aromatic hydrocarbon group as a divalent hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the alicyclic hydrocarbon group.

[0032] Regarding divalent linking groups containing heteroatoms: The heteroatom in the divalent linking group containing a heteroatom is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0033] In the divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group); -S-, -S(=O) 2 -, -S(=O) 2 -O-, general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 , -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -, wherein Y 21 and Y 22 each independently represents a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 0 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -Medium, Y 21 and Y 22are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same ones as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group. Y 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable. Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula − [Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 The group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH 2 ) a’ -C(=O)-O-(CH 2 ) 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, still more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0034] Among them, R EP As the epoxy group-containing group in the formula (I), a glycidyl group is preferred.

[0035] Suitable examples of the novolac epoxy resin (Anv) include resins having a structural unit represented by the following general formula (anv1).

[0036] [ka] [In the formula, R EP is an epoxy group-containing group, R a22 , R a23 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.]

[0037] In formula (anv1), R a22 , R a23 The alkyl group having 1 to 5 carbon atoms is represented by R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is the same as that of R a22 , R a23 The halogen atom is preferably a chlorine atom or a bromine atom. In formula (anv1), R EP is R in the formula (A1). EP and a glycidyl group is preferred.

[0038] Specific examples of the constitutional unit represented by the above formula (anv1) are shown below.

[0039] [ka]

[0040] 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 the structural units represented by the following general formulas (anv2) to (anv3).

[0041] [ka] [In the formula, R a24R is a hydrocarbon group which may have a substituent. a25 ~R a26 , R a28 ~R a30 R each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. a27 represents an epoxy group-containing group or a hydrocarbon group which may have a substituent.

[0042] In formula (anv2), R a24 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include a linear or branched alkyl group, and a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

[0043] The branched alkyl group preferably has a carbon number of 3 to 10, and more preferably 3 to 5. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.

[0044] R a24 When is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0045] R a24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring 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 of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. R a24 Specific examples of the aromatic hydrocarbon group in include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0046] In formulas (anv2) and (anv3), R a25 ~R a26 , R a28 ~Ra30 are each 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 each independently selected from the above R a22 , R a23 is the same as:

[0047] In formula (anv3), R a27 R is an epoxy group-containing group or a hydrocarbon group which may have a substituent. a27 The epoxy group-containing group is represented by R EP is the same as R a27 The optionally substituted hydrocarbon group is R a24 is the same as:

[0048] Specific examples of the structural units represented by the above formulas (anv2) to (anv3) are shown below.

[0049] [ka]

[0050] When the novolac epoxy resin (Anv) has other structural units in addition to the structural unit (anv1), the proportion of each structural unit in the resin (Anv) is not particularly limited, but the total of structural units having an epoxy group relative to the total of all structural units constituting the resin (Anv) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %.

[0051] <Bisphenol A epoxy resin (Abp)> The bisphenol A type epoxy resin (Abp) includes an epoxy resin having a structure represented by the following general formula (abp1).

[0052] [ka] [In the formula, R EP is an epoxy group-containing group, R a31 , R a32are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 31 is an integer between 1 and 50.

[0053] In formula (abp1), R a31 , R a32 The alkyl group having 1 to 5 carbon atoms is represented by R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is the same as that of R a31 , R a32 is preferably a hydrogen atom or a methyl group. R EP is R in the formula (A1). EP and a glycidyl group is preferred.

[0054] <Aliphatic epoxy resin, acrylic resin (Aac)> 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) and (a1-2), respectively.

[0055] [ka] [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. 41 is a divalent hydrocarbon group which may have a substituent. 41 is an integer between 0 and 2. a41 , R a42 is an epoxy group-containing group. 42 is 0 or 1. 41 Is (na 43 +1)valent aliphatic hydrocarbon group. 43 is an integer between 1 and 3.

[0056] In the above 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. The alkyl group having 1 to 5 carbon atoms represented by R is preferably linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferable.

[0057] In the formula (a1-1), Va 41 is a divalent hydrocarbon group which may have a substituent, and R in the formula (A1) EP Examples of the divalent hydrocarbon group which may have a substituent include the same groups as those explained in the above. 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.

[0058] In formula (a1-1), na 41 is an integer of 0 to 2, and preferably 0 or 1.

[0059] In formulas (a1-1) and (a1-2), R a41 , R a42 is an epoxy group-containing group, and R EP is the same as:

[0060] In formula (a1-2), Wa 41 In (na 43The aliphatic hydrocarbon group having a valence of +1 means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group in which a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure are combined.

[0061] In formula (a1-2), na 43 is an integer of 1 to 3, preferably 1 or 2.

[0062] Specific examples of the structural unit represented by formula (a1-1) or (a1-2) are shown below.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] In the above formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R a51 R represents a divalent hydrocarbon group having 1 to 8 carbon atoms. a52 R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. a53 represents a hydrogen atom or a methyl group. 51 is an integer between 0 and 10. R a51 , R a52 , R a53may be the same or different.

[0068] Furthermore, the acrylic resin (Aac) may have a structural unit derived from another polymerizable compound for the purpose of appropriately controlling the physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; fluoroalkyl esters such as ... Examples of suitable polymerizable compounds include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[0069] When the aliphatic epoxy resin or the acrylic resin (Aac) has other structural units, the content of the epoxy group-containing units in the resin is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and most preferably 15 to 25 mol%.

[0070] Suitable examples of the aliphatic epoxy resin include compounds containing a partial structure represented by the following general formula (m1) (hereinafter also referred to as "component (m1)").

[0071] [ka] [where n 2 is an integer from 1 to 4. * indicates a bond.

[0072] In formula (m1), n 2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0073] The component (m1) may be a compound in which a plurality of partial structures represented by the above general formula (m1) are bonded via a divalent linking group or a single bond. Among these, a compound in which a plurality of partial structures represented by the above general formula (m1) are bonded via a divalent linking group is preferred. The divalent linking group here is not particularly limited, but preferred examples include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, etc. The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are represented by R EP The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are the same as those described in (epoxy group-containing group), and among these, the divalent linking group containing a hetero atom is preferred. 21 A group represented by -C(=O)-O-, -C(=O)-OY 21 A group represented by Y - is more preferred. 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable.

[0074] Further, preferred examples of the aliphatic epoxy resin include the compound represented by the following general formula (m2) (hereinafter also referred to as "component (m2)").

[0075] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different.

[0076] In formula (m2), R EP is an epoxy group-containing group, and R EP is the same as:

[0077] As the component (A), one type may be used alone, or two or more types may be used in combination. The component (A) preferably contains at least one resin selected from the group consisting of novolac epoxy resins (Anv), bisphenol A epoxy resins (Abp), bisphenol F epoxy resins, aliphatic epoxy resins, and acrylic resins (Aac). Among these, it is more preferable that the component (A) contains at least one resin selected from the group consisting of novolac type epoxy resins (Anv), bisphenol A type resins (Abp), aliphatic epoxy resins, and acrylic resins (Aac). Among these, it is more preferable that the component (A) contains at least one resin selected from the group consisting of novolac type epoxy resins (Anv), aliphatic epoxy resins, and acrylic resins (Aac), and it is particularly preferable that the component (A) contains two or more resins selected from the group consisting of novolac type epoxy resins (Anv), aliphatic epoxy resins, and acrylic resins (Aac).

[0078] When two or more types of component (A) are used in combination, it is preferable that component (A) includes a combination of a novolac epoxy resin (Anv) and an aliphatic epoxy resin, since this improves the film properties (rollability and lamination properties) when made into a photosensitive resist film. Specific examples of such combinations include a combination of the (A1) component with at least one selected from the group consisting of the (m1) component and the (m2) component (hereinafter referred to as "the (m) component"). Among these, the combination of the (A1) component, the (m1) component and the (m2) component is the most preferred.

[0079] When the (m1) component and the (m2) component are both present, the ratio of the (m1) component to the (m2) component, expressed as the mass ratio (m1) component / (m2) component, is preferably 2 / 8 to 8 / 2, more preferably 3 / 7 to 7 / 3, and even more preferably 4 / 6 to 6 / 4. If the mass ratio is within the above-mentioned preferred range, the film properties (rollability, lamination properties) are further improved when the photosensitive resist film is formed.

[0080] In particular, the component (A) contains the components (A1), (m1), and (m2), and the total content of the components (m1) and (m2) in the total content of the components (A1), (m1), and (m2) is preferably 15 mass% or more, more preferably 20 mass% or more, even more preferably 25 mass% or more, particularly preferably more than 25 mass%, and most preferably more than 25 mass% and 30 mass% or less, in terms of the balance between the strength and flexibility of the cured film.

[0081] The polystyrene-equivalent weight average molecular weight of the component (A) is preferably 100 to 300000, more preferably 200 to 200000, and even more preferably 300 to 200000. By setting the weight average molecular weight within this range, peeling from the support is less likely to occur, and the strength of the cured film that is formed is sufficiently increased.

[0082] The component (A) preferably has a dispersity of at least 1.05, which leads to improved lithography properties during pattern formation. The degree of dispersion referred to here means a value obtained by dividing the mass average molecular weight by the number average molecular weight.

[0083] Commercially available products of the component (A) include, for example, novolac 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.).

[0084] Examples of bisphenol A type epoxy resins (Abp) include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (all manufactured by DIC Corporation), and the like.

[0085] Examples of bisphenol F type epoxy resins include JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (all manufactured by DIC Corporation), LCE-21, RE-602S (all manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0086] Examples of aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (manufactured by ADEKA Corporation), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (manufactured by Daicel Corporation), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation), and TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd.).

[0087] 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, etc.

[0088] <Metal oxide (M)> The photosensitive composition of the present embodiment contains a metal oxide (component (M)) in addition to components (A) and (I), and thus a cured film with enhanced strength can be obtained. In addition, a pattern with good shape and high resolution can be formed. Examples of the component (M) include oxides of metals such as silicon (metallic silicon), titanium, zirconium, hafnium, etc. Among these, oxides of silicon are preferred, and among these, it is particularly preferred to use silica.

[0089] In addition, the component (M) is preferably in the form of particles. Such particulate (M) component is preferably a particle group having a volume average particle diameter of 5 to 40 nm, more preferably a particle group having a volume average particle diameter of 5 to 30 nm, and even more preferably a particle group having a volume average particle diameter of 10 to 20 nm. When the volume average particle size of component (M) is at least the lower limit of the preferred range, the strength of the cured film tends to be increased, whereas when it is at most the upper limit of the preferred range, residues are less likely to be generated during pattern formation, making it easier to form higher resolution patterns.

[0090] The particle size of the (M) component may be appropriately selected depending on the exposure light source. In general, it is considered that the effect of light scattering is hardly considered for particles having a particle size of 1 / 10 or less of the wavelength of light. For this reason, for example, when forming a fine structure by photolithography using i-line (365 nm), it is preferable to use a particle group (particularly preferably a silica particle group) having a primary particle size (volume average value) of 10 to 20 nm as the (M) component.

[0091] As the component (M), one type may be used alone, or two or more types may be used in combination. The content of the (M) component is preferably more than 30 parts by mass and not more than 180 parts by mass, more preferably 40 to 170 parts by mass, and even more preferably 50 to 150 parts by mass, per 100 parts by mass of the (A) component. When the content of the component (M) is more than the lower limit of the above-mentioned preferred range, the strength of the cured film is further increased, whereas when the content is equal to or less than the upper limit of the above-mentioned preferred range, the flowability of the photosensitive composition is easily maintained.

[0092] <Cationic Polymerization Initiator (I)> The cationic polymerization initiator (component (I)) is a compound that generates cations when irradiated with active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF or ArF, X-rays, electron beams, etc., and the cations can serve as polymerization initiators.

[0093] 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)"). Among the above, both the component (I1) and the component (I2) generate a relatively strong acid upon exposure to light. Therefore, when a pattern is formed using a photosensitive composition containing the component (I), sufficient sensitivity can be obtained and a good pattern can be formed.

[0094] Component (I1) The component (I1) is a compound represented by the following general formula (I1).

[0095] [ka] [In the formula, R b01 ~R b04 Each of Q is independently an aryl group which may have a substituent, or a fluorine atom. q is an integer of 1 or more, q+ are each independently an organic cation having a valence of q.

[0096] Anion section In the formula (I1), R b01 ~R b04 each independently represents an aryl group which may have a substituent, or a fluorine atom. R b01 ~R b04 The aryl group in the formula (I) 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 include a naphthyl group, a phenyl group, and an anthracenyl group, and the phenyl group is preferred because of its easy availability. R b01 ~R b04 The aryl group in may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably having 1 to 5 carbon atoms), or a halogenated alkyl group, more preferably a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms, and particularly preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. When the aryl group has a fluorine atom, the polarity of the anion moiety is increased, which is preferable. Among them, R in formula (I1) b01 ~R b04 As each of these, a fluorinated phenyl group is preferable, and a perfluorophenyl group is particularly preferable.

[0097] A preferred example of the anion portion of the compound represented by formula (I1) is tetrakis(pentafluorophenyl)borate ([B(C 6 F 5 ) 4 ] - );Tetrakis[(trifluoromethyl)phenyl]borate ([B(C 6 H 4 CF 3 ) 4 ] - );Difluorobis(pentafluorophenyl)borate ([(C 6 F 5 ) 2 BF 2 ] - ); Trifluoro(pentafluorophenyl)borate ([(C 6 F 5 )B.F. 3 ] - );Tetrakis(difluorophenyl)borate ([B(C 6 H 3 F 2 ) 4 ] - ) etc. Among them, tetrakis(pentafluorophenyl)borate ([B(C 6 F 5 ) 4 ] - ) is particularly preferred.

[0098] ·Cation part In formula (I1), q is an integer of 1 or more, q+ are each independently a q-valent organic cation. This Q q+ Suitable examples of the cation include a sulfonium cation and an iodonium cation, and the organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0099] [ka] [In the formula, R 201 ~R 207 , and R 211 ~R 212R each independently represents an aryl group, a heteroaryl group, an alkyl group or an alkenyl group which may have a substituent. 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO 2 -containing cyclic group. 201 represents -C(=O)- or -C(=O)-O-. 201 each independently represents an arylene group, an alkylene group, or an alkenylene group; x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0100] R 201 ~R 207 , and R 211 ~R 212 The aryl group in may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 , and R 211 ~R 212 The heteroaryl group in the above formula (I) may be one in which a part of the carbon atoms constituting the aryl group is replaced with a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthene; examples of the substituted heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthen-9-one. R 201 ~R 207 , and R 211 ~R 212The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212 Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, and groups represented by the following formulae (ca-r-1) to (ca-r-10).

[0101] [ka] [In the formula, 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.

[0102] In the above 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.

[0103] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0104] R' 201The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, the carbon number does not include the carbon number of the substituent. R' 201 Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in the above include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R' 201 Specific examples of the aromatic hydrocarbon group in the above include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, anthracenyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), a group in which one hydrogen atom has been removed from a ring in which some of the hydrogen atoms constituting the aromatic ring have been substituted with an oxo group or the like (for example, anthraquinone, etc.), and a group in which one hydrogen atom has been removed from an aromatic heterocycle (for example, 9H-thioxanthene, 9H-thioxanthen-9-one, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0105] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system, such as a cyclic group having a steroid skeleton.

[0106] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0107] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, specifically, a methylene group [-CH 2 -], ethylene group [-(CH 2 )2 -], trimethylene group [-(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] etc. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc. alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 -, etc. alkyl ethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, etc.; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0108] Optionally substituted chain alkyl groups: R' 201 The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, and a docosyl group. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0109] An optionally substituted chain alkenyl group: R' 201 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0110] R' 201 Examples of the substituent in the cyclic group, chain alkyl group or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, the above-mentioned R' 201 In the above formula, examples include a cyclic group, an alkylcarbonyl group, and a thienylcarbonyl group.

[0111] Among them, R' 201 is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

[0112] R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When they are bonded to each other to form a ring together with the sulfur atom in the formula, they are not included in the heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, as well as in the carbonyl groups, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )-(applicable R N is an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, in which a ring containing a sulfur atom in the ring skeleton in the formula is a 3- to 10-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0113] In the above formula (ca-3), R 208 ~R 209each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups they may be bonded to each other to form a ring.

[0114] In the above formula (ca-3), R 210 represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO 2 -containing cyclic group. R 210 The aryl group in may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

[0115] In the above formula (ca-4) and formula (ca-5), Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. Y 201 The arylene group in R' 201 Examples of the aromatic hydrocarbon group in the above formula include groups in which one hydrogen atom has been removed from the aryl groups exemplified above. Y 201 The alkylene group and alkenylene group in R' 201 Examples of the chain alkyl group and the chain alkenyl group in the above formula (I) include groups in which one hydrogen atom has been removed from the groups exemplified as the chain alkyl group and the chain alkenyl group in the above formula (I).

[0116] In the above formulas (ca-4) and (ca-5), x is 1 or 2. W 201 is a (x+1)-valent linking group, that is, a divalent or trivalent linking group. W 201 The divalent linking group in the formula (A1) is preferably a divalent hydrocarbon group which may have a substituent. EPThe divalent hydrocarbon groups which may have a substituent are preferably the same as those exemplified by W. 201 The divalent linking group in may be linear, branched, or cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting of an arylene group alone is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and the phenylene group is particularly preferred. W 201 The trivalent linking group in 201 and a group in which one hydrogen atom has been removed from the divalent linking group represented by the formula: W 201 As the trivalent linking group in the formula (I), a group in which two carbonyl groups are bonded to an arylene group is preferable.

[0117] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0118] [ka]

[0119] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent. The substituent may be any of the above-mentioned R 201 ~R 207 , and R 210 ~R 212 The substituents are the same as those exemplified as the substituents that may be possessed by the

[0120] As the cation represented by the formula (ca-1), the cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferable.

[0121] [ka]

[0122] [ka] [In the formula, R' 211 is an alkyl group. hal is a hydrogen atom or a halogen atom.

[0123] As the cation represented by the formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-46) are also preferable.

[0124] [ka]

[0125] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0126] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0127] [ka]

[0128] Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0129] [ka]

[0130] As the cation represented by the formula (ca-5), the cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferable.

[0131] [ka] [In the formula, R' 212 R' is an alkyl group or a hydrogen atom. 211 is an alkyl group.

[0132] Among the above, the cationic part [(Q q+ ) 1 / q ] is preferably a cation represented by general formula (ca-1), more preferably a cation represented by formulas (ca-1-1) to (ca-1-46), and even more preferably a cation represented by formula (ca-1-29).

[0133] ≪(I2) component≫ The component (I2) is a compound represented by the following general formula (I2).

[0134] [ka] [In the formula, R b05 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b05 may be the same or different. q is an integer of 1 or more, and Q q+ are each independently an organic cation having a valence of q.

[0135] Anion section In the above formula (I2), R b05 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b05 may be the same or different from each other. R b05The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably has 1 to 8 carbon atoms, and even more preferably has 1 to 5 carbon atoms. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Among them, R b05 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and further preferably a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group.

[0136] The anion moiety of the compound represented by formula (I2) is preferably represented by the following general formula (b0-2a).

[0137] [ka] [In the formula, R bf05 is a fluorinated alkyl group which may have a substituent. 1 is an integer from 1 to 5.

[0138] In formula (b0-2a), R bf05 The optionally substituted fluorinated alkyl group in R b05 The substituents are the same as the optionally substituted fluorinated alkyl groups listed under 1. In formula (b0-2a), nb 1 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.

[0139] ·Cation part In formula (I2), q is an integer of 1 or more, q+ are each independently a q-valent organic cation. This Q q+ Examples of the cation include those represented by formula (I1) above. Among them, the cation represented by general formula (ca-1) is preferred, the cations represented by formulas (ca-1-1) to (ca-1-46) are more preferred, and the cation represented by formula (ca-1-35) is even more preferred.

[0140] ≪Component (I3)≫ The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0141] [ka] [In the formula, R b11 ~R b12 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom. m is an integer of 1 or more, and M m+ are each independently an organic cation having a valence of m.

[0142] {Component (I3-1)} Anion section In formula (I3-1), R b12 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and R' 201 Among the cyclic groups, chain alkyl groups, and chain alkenyl groups in the explanation of the above, those having no substituent or those having a substituent other than a halogen atom are exemplified. R b12 is preferably a chain alkyl group which may have a substituent other than a halogen atom, or an aliphatic cyclic group which may have a substituent other than a halogen atom. The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 3 to 10 carbon atoms. The aliphatic cyclic group is preferably a group in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like (which may have a substituent other than a halogen atom); more preferably a group in which one or more hydrogen atoms have been removed from camphor, or the like. R b12The hydrocarbon group may have a substituent other than a halogen atom, and examples of the substituent include R b11 Examples of the substituents include those similar to the substituents other than halogen atoms that may be contained in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above formula. The phrase "may have a substituent other than a halogen atom" as used herein not only excludes the case where a substituent consists of only halogen atoms, but also excludes the case where a substituent contains at least one halogen atom (for example, the case where the substituent is a fluorinated alkyl group, etc.).

[0143] Preferred specific examples of the anion portion of the component (I3-1) are shown below.

[0144] [ka]

[0145] ·Cation part In formula (I3-1), M m+ is an m-valent organic cation. M m+ Suitable examples of the organic cation include the cations represented by the above general formulas (ca-1) to (ca-5), and among these, the cation represented by the above general formula (ca-1) is more preferred. 201 , R 202 , R 203 A sulfonium cation in which at least one of the above is an organic group having 16 or more carbon atoms (aryl group, heteroaryl group, alkyl group, or alkenyl group) which may have a substituent is particularly preferred because it improves the resolution and roughness characteristics. The substituents that the organic group may have are the same as those described above, and include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, and groups represented by the above formulas (ca-r-1) to (ca-r-10). The number of carbon atoms in the organic group (aryl group, heteroaryl group, alkyl group, or alkenyl group) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18. m+ Suitable examples of the organic cation include the cations represented by the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), and (ca-1-46), and among these, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0146] {Component (I3-2)} Anion section In formula (I3-2), R b11 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and R' 201 Among the cyclic groups, chain alkyl groups, and chain alkenyl groups in the explanation of the above, those having no substituent or those having a substituent other than a halogen atom are exemplified.

[0147] Among these, R b11 As the substituent, an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a chain alkyl group which may have a substituent other than a halogen atom are preferable. The substituent which these groups may have includes a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be connected via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the following general formulas (y-al-1) to (y-al-7).

[0148] [ka] [In the formula, V' 101is 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.

[0149] V' 102 The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0150] V' 101 and V' 102 The alkylene group in may be a straight-chain alkylene group or a branched-chain alkylene group, and is preferably a straight-chain alkylene group. V' 101 and V' 102 Specific examples of the alkylene group in the formula include a methylene group [-CH 2 -];-CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; ethylene groups [-CH 2 CH 2 -];-CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, etc.; trimethylene group (n-propylene group) [-CH 2 CH 2 CH2 -];-CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and other alkyl trimethylene groups; tetramethylene groups [-CH 2 CH 2 CH 2 CH 2 -];-CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyl tetramethylene groups; pentamethylene groups [-CH 2 CH 2 CH 2 CH 2 CH 2 -] etc. Also, V' 101 or V' 102 A part of the methylene groups in the alkylene group in the formula (I) may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is represented by R' 201 A divalent group in which one hydrogen atom has been further removed from a cyclic aliphatic hydrocarbon group (a monocyclic alicyclic hydrocarbon group, a polycyclic alicyclic hydrocarbon group) such as those mentioned above is preferred, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferred.

[0151] The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group. The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The chain alkyl group preferably has 1 to 10 carbon atoms. Specific examples of the chain alkyl group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0152] R b11 is preferably a cyclic group which may have a substituent other than a halogen atom. Preferred specific examples of the anion portion of the component (I3-2) are shown below.

[0153] [ka]

[0154] ·Cation part In formula (I3-2), M m+ is an m-valent organic cation, and M in the formula (I3-1) m+ is the same as:

[0155] In addition, the component (I) is preferably a cationic polymerization initiator that generates an acid having a pKa (acid dissociation constant) of -5 or less upon exposure, from the viewpoints of increasing the elasticity of the resin film and facilitating the formation of a fine structure without leaving any residue. By using a cationic polymerization initiator that generates an acid having a pKa of -6 or less, more preferably a pKa of -8 or less, it is possible to obtain high sensitivity to exposure. The lower limit of the pKa of the acid generated by the component (I) is preferably -15 or more. By using a cationic polymerization initiator that generates an acid having such a suitable pKa, it is easy to achieve high sensitivity. Here, "pKa (acid dissociation constant)" refers to a commonly used index indicating the acid strength of a target substance. In this specification, pKa is a value at a temperature condition of 25°C. The pKa value can be determined by measurement using a known method. Alternatively, a calculated value using known software such as "ACD / Labs" (product name, manufactured by Advanced Chemistry Development) can be used.

[0156] Preferred specific examples of the component (I) are given below.

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] As the component (I), one type may be used alone, or two or more types may be used in combination. The component (I) preferably contains two or more selected from the group consisting of the components (I1), (I2), and (I3), more preferably contains two or more selected from the group consisting of the components (I1) and (I2), and even more preferably contains a combination of the components (I1) and (I2).

[0161] 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, per 100 parts by mass of the component (A). When the content of the component (I) is equal to or greater than the lower limit of the preferred range, sufficient sensitivity is obtained, and the lithography properties of the pattern are further improved. In addition, the strength of the cured film is further increased. On the other hand, when the content is equal to or less than the upper limit of the preferred range, the sensitivity is appropriately controlled, and a pattern with a good shape is easily obtained.

[0162] Furthermore, the content of the (I) component 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, per 100 parts by mass of the total amount of the (A) and (M) components. When the content of component (I) is within the above-mentioned preferred range, the strength of the cured film is further increased, making it easier to form a high-resolution pattern with a good shape.

[0163] In the photosensitive composition of this embodiment, 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 %. When the content of the component (A) is within the above-mentioned preferred range, the strength of the cured film is further increased, and the film properties (rollability, lamination ability) when made into a photosensitive resist film are further improved.

[0164] <Other ingredients> The photosensitive composition of the present embodiment may contain other components, if necessary, in addition to the components (A), (M), and (I). If desired, the photosensitive composition of the embodiment may contain compatible additives, such as additional resins for improving the performance of the film, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and antihalation agents.

[0165] <Silane coupling agent> The photosensitive composition of the embodiment may further contain an adhesion promoter to improve adhesion to the support, and a silane coupling agent is preferred as the adhesion promoter. Examples of the silane coupling agent include silane coupling agents having reactive substituents such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, etc. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. The silane coupling agents may be used alone or in combination of two or more kinds. 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 component (A). When the content of the silane coupling agent is within the above-mentioned preferred range, the strength of the cured film is further increased, and in addition, the adhesion between the cured film and the support is further increased.

[0166] Sensitizer component The photosensitive composition of the embodiment may further contain a sensitizer component. The sensitizer component is not particularly limited as long as it can absorb energy due to exposure and transmit the energy to another substance. Specific examples of the sensitizer component that can be used include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetophene-based photosensitizers, naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, and known photosensitizers such as biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone. The sensitizer component may be used alone or in combination of two or more kinds. 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 even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of component (A). When the content of the sensitizer component is within the above preferred range, the sensitivity and resolution can be further improved.

[0167] <Solvent> The photosensitive composition of the embodiment can be produced by dissolving or dispersing a photosensitive material in a solvent (hereinafter sometimes referred to as "component (S)"). Examples of the (S) component include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; polyhydric ethers such as monoalkyl ethers, monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the polyhydric alcohols or the compounds having an ester bond, and compounds having an ether bond such as monophenyl ethers. Examples of suitable organic solvents include alcohol derivatives (among which, methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene, and dimethyl sulfoxide (DMSO). The component (S) may be used alone or as a mixed solvent of two or more kinds.

[0168] There are no particular limitations on the amount of component (S) used, and it is set appropriately according to the coating film thickness so long as it is a concentration that allows coating on a substrate or the like. The content of the component (S) in the photosensitive composition is preferably from 1 to 25 mass %, and more preferably from 5 to 20 mass %, relative to the total amount (100 mass %) of the photosensitive composition.

[0169] [Martens hardness of photosensitive resin film] 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 film is 235 [N / mm 2 ], preferably 15 to 200 [N / mm 2 ], and more preferably 40 to 160 [N / mm 2 ] If the Martens hardness of the photosensitive resin film is equal to or less than the upper limit of the above range, the photosensitive resin film has appropriate flexibility when made into a photosensitive resist film, and the film has excellent film properties (rollability and lamination properties).On the other hand, if the Martens hardness is equal to or more than the lower limit of the above preferred range, the strength of the cured film when cured is further increased.

[0170] The Martens hardness of the photosensitive resin film is measured by the nanoindentation method described below. Evaluation method: FISCHERSCOPE HM2000 measuring device (manufactured by Fisher Instruments) Microhardness test in accordance with ISO14577 Measurement conditions: Maximum test load 30mN, load application time 20 seconds, creep time 5 seconds, temperature 25℃

[0171] The Martens hardness of the above-mentioned photosensitive resin film can be increased to 235 [N / mm 2 ] can be controlled. It is preferable to select the type of epoxy group-containing resin (A) or to adjust the compounding ratio appropriately. In particular, it is preferable to adopt a combination of the (A1) component and the (m) component as the (A) component, or to use the (m1) component and the (m2) component in combination as the (m) component.

[0172] [Tensile modulus of cured film (E*)] In this embodiment, the negative photosensitive resin composition is baked at 90° C. for 5 minutes to form a photosensitive resin film having a thickness of 20 μm. The irradiation dose is 200 mJ / cm. 2 The film is exposed to i-line at 400°C, post-exposure baked at 90°C for 5 minutes, and then baked at 200°C for 1 hour. This results in a cured film with a tensile modulus (E*) of 2.1 [GPa] or more, preferably 2.3 to 4.0 [GPa], and more preferably 2.5 to 3.5 [GPa]. When the tensile modulus (E*) of the cured film is equal to or greater than the lower limit of the above range, the cured film has sufficient strength, and when a hollow structure is formed, the space is sufficiently maintained even when high pressure is applied. On the other hand, when the tensile modulus is equal to or less than the upper limit of the above preferred range, the occurrence of cracks in the cured film is easily suppressed.

[0173] The tensile modulus (E*) of the cured film is the measured value at a temperature of 175°C when the viscoelasticity of the cured film is measured at a frequency of 1.0 Hz.

[0174] The tensile modulus (E*) of the cured film described above can be controlled to 2.1 [GPa] or more by appropriately selecting the types of components to be blended in the negative photosensitive resin composition or adjusting the blending ratio thereof. Preferably, the content of the metal oxide (M) is increased, or the type of the epoxy group-containing resin (A) is selected, or the compounding ratio is appropriately adjusted. In particular, the content of the (M) component is set to more than 30 parts by mass per 100 parts by mass of the (A) component.

[0175] (Photosensitive resist film) The photosensitive resist film of the present embodiment is formed 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 substrate film. In addition, the negative photosensitive resin film in the photosensitive resist film of this embodiment has a Martens hardness of 235 [N / mm] when the photosensitive resin film is laminated on a silicon wafer to a thickness of 20 μm.2 ] or less, and the irradiation dose for the photosensitive resin film is 200 mJ / cm 2 The cured film is exposed to i-line at 400°C, post-exposure baked at 90°C for 5 minutes, and then baked at 200°C for 1 hour to obtain a cured film that has a tensile modulus (E*) of 2.1 GPa or more at 175°C when viscoelasticity is measured at a frequency of 1.0 Hz.

[0176] Here, the photosensitive resin film in the photosensitive resist film of this embodiment is typically made of a resin material in a B-stage state (semi-cured state). The above-mentioned Martens hardness is a value measured when this photosensitive resin film is laminated on a silicon wafer with a thickness of 20 μm. The lamination is performed under the conditions of 90° C., 0.3 MPa, and 0.5 m / min. In addition, when the photosensitive resin film in the photosensitive resist film of this embodiment is less than 20 μm in thickness, the thickness can be adjusted to 20 μm by laminating a plurality of photosensitive resin films on a silicon wafer (grinding after lamination as necessary), and then the Martens hardness can be measured. In addition, when the photosensitive resin film in the photosensitive resist film of this embodiment is more than 20 μm in thickness, the resin film can be laminated on a silicon wafer, and then the resin film can be ground to adjust the thickness to 20 μm, and then the Martens hardness can be measured. The measurement conditions for the Martens hardness of the specimen with the adjusted thickness can be the nanoindentation method described above.

[0177] When a photosensitive resin film is formed using such a photosensitive resist film and the photosensitive resin film is selectively exposed to light, in the exposed part of the photosensitive resin film, the cationic part of the (I) component is decomposed to generate an acid, and the epoxy group in the (A) component is ring-opened and polymerized by the action of the acid, so that the solubility of the (A) component in a developer containing an organic solvent decreases, while 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 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. That is, the photosensitive resin film is negative type. Therefore, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed part is dissolved and removed, and a negative type pattern is formed.

[0178] The photosensitive resist film of the embodiment can be produced by applying the negative photosensitive resin composition of the embodiment described above onto a substrate film, and drying the composition to form a photosensitive resin film. The negative photosensitive resin composition may be applied onto the substrate film by a suitable method using an applicator, a blade coater, a lip coater, a comma coater, a film coater or the like. The thickness of the photosensitive resin film is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0179] <Base film> In the photosensitive resist film of the embodiment, the base film may be a known one, for example, a thermoplastic resin film. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm.

[0180] <Photosensitive resin film> In the photosensitive resist film of the embodiment, the negative photosensitive resin film contains an epoxy group-containing resin (A), a metal oxide (M) and a cationic polymerization initiator (I). Hereinafter, these components are also referred to as component (A), component (M) and component (I), respectively, as in the above-mentioned negative photosensitive resin composition. The explanations for the component (A), component (M), and component (I) contained in such a negative type photosensitive resin film are the same as the explanations for the component (A), component (M), and component (I) contained in the above-mentioned negative type photosensitive resin composition, respectively.

[0181] The negative photosensitive resin film may contain other components, if necessary, in addition to the components (A), (M) and (I). Examples of the other components include silane coupling agents, sensitizer components, solvents, and miscible additives (e.g., additional resins for improving the performance of the film, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, antihalation agents, etc.).

[0182] [Martens hardness of photosensitive resin film] The negative photosensitive resin film in the photosensitive resist film of this embodiment has a Martens hardness of 235 [N / mm] when laminated to a thickness of 20 μm on a silicon wafer. 2 ], preferably 15 to 200 [N / mm 2 ], and more preferably 40 to 160 [N / mm 2 ] If the Martens hardness of the photosensitive resin film is equal to or less than the upper limit of the above range, the photosensitive resin film has appropriate flexibility when made into a photosensitive resist film, and the film has excellent film properties (rollability and lamination properties).On the other hand, if the Martens hardness is equal to or more than the lower limit of the above preferred range, the strength of the cured film when cured is further increased.

[0183] The Martens hardness of the photosensitive resin film is measured by laminating the photosensitive resin film to a thickness of 20 μm on a silicon wafer as described above, and then using the nanoindentation method described below. Evaluation method: FISCHERSCOPE HM2000 measuring device (manufactured by Fisher Instruments) Microhardness test in accordance with ISO14577 Measurement conditions: Maximum test load 30mN, load application time 20 seconds, creep time 5 seconds, temperature 25℃

[0184] [Tensile modulus of cured film (E*)] In the photosensitive resist film of this embodiment, the irradiation dose is 200 mJ / cm for a photosensitive resin film having a thickness of 20 μm. 2 The film is exposed to i-line at 400°C, post-exposure baked at 90°C for 5 minutes, and then baked at 200°C for 1 hour. This results in a cured film with a tensile modulus (E*) of 2.1 [GPa] or more, preferably 2.3 to 4.0 [GPa], and more preferably 2.5 to 3.5 [GPa]. When the tensile modulus (E*) of the cured film is equal to or greater than the lower limit of the above range, the cured film has sufficient strength, and when a hollow structure is formed, the space is sufficiently maintained even when high pressure is applied. On the other hand, when the tensile modulus is equal to or less than the upper limit of the above preferred range, the occurrence of cracks in the cured film is easily suppressed.

[0185] The tensile modulus (E*) of the cured film is the measured value at a temperature of 175°C when the viscoelasticity of the cured film is measured at a frequency of 1.0 Hz.

[0186] As described above, the negative photosensitive resin composition or photosensitive resist film (photosensitive material according to this embodiment) of this embodiment has a Martens hardness of 235 [N / mm 2 ] and the tensile modulus (E*) of the cured film (fully cured state) is 2.1 [GPa] or more. With such characteristics, the photosensitive material according to this embodiment can provide a cured film with higher strength. This allows the hollow structure to be maintained even against high pressure applied during molding. In addition, in the photosensitive material according to this embodiment, the strength of the cured film is increased while the decrease in tackiness in the photosensitive resin film is suppressed, so that the material can be easily rolled and has excellent lamination properties for substrates and the like. Furthermore, the photosensitive material according to this embodiment provides sufficient sensitivity, reduces residues, and enables the formation of high-resolution patterns with good shapes.

[0187] 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 consisting of a laminate in which the photosensitive resin film and a cover film are laminated in this order on the base film. The cover film may be a known one, such as a polyethylene film or a polypropylene film. The cover film is preferably a film having a smaller adhesive strength with the photosensitive resin film than the base film. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm. The base film and the cover film may be made of the same film material, or different films may be used. When using the device, for example, the cover film is peeled off while laminating the photosensitive resin film / substrate film laminate onto a support, and then the substrate film is peeled off, exposed to light, and developed, thereby forming a pattern on the support.

[0188] (Pattern formation method) The pattern forming method of the present embodiment includes a step of forming a photosensitive resin film on a support using the negative photosensitive resin composition or photosensitive resist film of the above-described embodiment (hereinafter referred to as a "film forming step"), a step of exposing the photosensitive resin film (hereinafter referred to as an "exposure step"), and a step of developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern (hereinafter referred to as a "development step"). The pattern forming method of this embodiment can be carried out, for example, as follows.

[0189] [Film formation process] First, the negative type photosensitive resin composition of the above-mentioned embodiment is applied onto a support by a known method such as spin coating, roll coating, or screen printing, and baked (post-applied bake (PAB)) for 2 to 60 minutes at a temperature of, for example, 50 to 150°C to form a photosensitive resin film.

[0190] In the film formation step, a photosensitive resin film may be formed on a support by attaching a photosensitive resist film onto the support. When attaching, the support or the film may be heated, pressed (laminated), or the like, if necessary.

[0191] The support is not particularly limited, and conventionally known supports can be used, such as substrates for electronic components and substrates on which a predetermined wiring pattern is formed. More specifically, metal substrates such as silicon wafers, copper, chromium, iron, and aluminum, glass substrates, and resin films such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, and polyethylene can be used. Materials for the wiring pattern include, for example, copper, aluminum, nickel, and gold. The support may be a substrate as described above on which an inorganic and / or organic film is provided. Examples of inorganic films include inorganic anti-reflective coatings (inorganic BARC). Examples of organic films include organic anti-reflective coatings (organic BARC) and organic films such as lower organic films in a multi-layer resist method.

[0192] The thickness of the photosensitive resin film formed by 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 characteristics even when the film is formed as a thick film.

[0193] [Exposure process] Next, the formed photosensitive resin film is selectively exposed using a known exposure device by exposure through a mask (mask pattern) having a predetermined pattern formed thereon, or by drawing by direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) as necessary, for example, at a temperature condition of 80 to 150° C. for 40 to 600 seconds, preferably 60 to 300 seconds.

[0194] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays having a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm), or visible light is selectively irradiated (exposed). As the radiation source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used. Here, radiation means ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc. For example, when an ultra-high pressure mercury lamp is used, it is 100 to 2000 mJ / cm. 2 It is.

[0195] The exposure method for the photosensitive resin film may be a normal exposure method (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion lithography.

[0196] The photosensitive resin film after the exposure step has high transparency, and 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%. As described above, the photosensitive resin film formed using the negative photosensitive resin composition or the photosensitive resist film of the above-mentioned embodiment has high transparency, and therefore, during exposure in pattern formation, the light transmittance is increased, and a negative pattern with good lithography properties is easily obtained. The haze value of the photosensitive resin film after such an exposure step is measured using a method in accordance with JIS K 7136 (2000).

[0197] [Development process] Next, the photosensitive resin film after the exposure is developed with a developer containing an organic solvent (organic developer). After the development, a rinse treatment is preferably performed. If necessary, a bake treatment (post-bake) may be performed. A pattern can be formed by the above-mentioned film forming step, exposure step, and development step.

[0198] The organic solvent contained in the organic developer may be any solvent capable of dissolving the component (A) (the component (A) before exposure), and may be appropriately selected from known organic solvents. Specific examples of the organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0199] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), etc. Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0200] Examples of ester-based solvents 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, Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples of the lactate include ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate.Among these, the ester solvent is preferably butyl acetate or PGMEA.

[0201] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0202] The organic developer may contain known additives as necessary. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants. The surfactant is preferably a non-ionic surfactant, and more preferably a non-ionic fluorine-based surfactant or a non-ionic silicon-based surfactant. When a surfactant is added, the amount added is usually from 0.001 to 5 mass %, preferably from 0.005 to 2 mass %, and more preferably from 0.01 to 0.5 mass %, based on the total amount of the organic developer.

[0203] Development can be carried out by known developing methods, such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it there for a certain period of time (paddle method), a method of spraying the developer on the surface of the support (spray method), and a method of continuously applying the developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).

[0204] The rinse treatment (cleaning treatment) using a rinse liquid can be carried out by a known rinse method, such as a method of continuously applying the rinse liquid onto a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse liquid for a certain period of time (dip method), or a method of spraying the rinse liquid onto the surface of the support (spray method). The rinsing treatment is preferably carried out using a rinsing liquid containing an organic solvent.

[0205] In the pattern formation method of the above-described embodiment, since the above-described negative photosensitive resin composition is used, high sensitivity can be achieved, and residues can be reduced, making it possible to form a high-resolution pattern with a good shape.

[0206] (cured film) The cured film of this embodiment is obtained by curing the negative photosensitive resin composition of the above-mentioned embodiment. In the cured film of the embodiment, the tensile modulus (E*) at a temperature of 175°C, as measured by viscoelasticity 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]. According to this embodiment, the strength of the cured film is further increased, so that the hollow structure can be stably maintained even against the high pressure applied during molding.

[0207] (Method of manufacturing the cured film) The method for producing a cured film of the present embodiment includes a step (i) of forming a photosensitive resin film on a support using the negative photosensitive resin composition or the photosensitive resist film of the above-mentioned embodiment, and a step (ii) of curing the photosensitive resin film to obtain a cured film. The operation of step (i) can be performed in the same manner as in the above-mentioned [film formation step]. The baking treatment can be performed, for example, at a temperature of 50 to 100° C. for 0.5 to 30 minutes. The curing treatment in step (ii) can be carried out under conditions of, for example, a temperature of 100 to 250° C. and a time of 0.5 to 2 hours.

[0208] The method for producing a cured film according to the embodiment may have other steps in addition to steps (i) and (ii). For example, the above-mentioned [exposure step] may be included between steps (i) and (ii), and the photosensitive resin film formed in step (i) may be selectively exposed to light, and the photosensitive resin film (pre-cured film) that has been subjected to a bake (PEB) treatment as necessary may be cured to obtain a cured film. According to the method for producing a cured film of the embodiment described above, a cured film having increased strength is produced.

[0209] (Roll body) The roll body of this embodiment is formed by winding the photosensitive resist film of the above-described embodiment around a core. The core may be a paper tube, a wooden tube, a plastic tube, or the like.

[0210] In the roll body of this embodiment, the photosensitive resist film of the above-mentioned embodiment is used, so that when the photosensitive resin film / substrate film laminate is wound around a core, cracks and pressure bonding defects are unlikely to occur, and rolling can be performed easily and stably. EXAMPLES

[0211] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0212] <Preparation of negative type photosensitive resin composition> (Examples 1 to 13, Comparative Examples 1 to 3) The components shown in Table 1 were mixed and dissolved in methyl ethyl ketone (MEK), and the mixture was filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Corporation) to prepare negative-type photosensitive resin compositions (MEK solutions with solid content of 80 to 85% by mass) for each example.

[0213] [Table 1]

[0214] In Table 1, the abbreviations have the following meanings. The numbers in brackets [ ] indicate the blending amount of each component (parts by mass; solid content equivalent). (A)-1: An epoxy group-containing resin represented by the following general formula (A11), product name "JER-157S70", manufactured by Mitsubishi Chemical Corporation.

[0215] [ka]

[0216] (A)-2: A compound represented by the following chemical formula (m1-1). Product name: "Celloxide 8010", manufactured by Daicel Corporation. (A)-3: A compound represented by the following chemical formula (m1-2). Product name: "Celloxide 2021P", manufactured by Daicel Corporation. (A)-4: A compound represented by the following chemical formula (m2-1). Trade name "TEPIC-VL", manufactured by Nissan Chemical Industries, Ltd.

[0217] [ka]

[0218] (M)-1: Silica component (a). Product name "MEK-EC-2130Y", manufactured by Nissan Chemical Industries, Ltd. Primary particle diameter φ=15 nm (volume average value). Methyl ethyl ketone dispersion with a silica component concentration of 31% by mass.

[0219] (I1)-1: A cationic polymerization initiator represented by the following chemical formula (I1-1), trade name "CPI-310B", manufactured by San-Apro Ltd. (I2)-1: A cationic polymerization initiator represented by the following chemical formula (I2-1), trade name "CPI-410S", manufactured by San-Apro Ltd.

[0220] [ka]

[0221] [Measurement of Martens hardness of photosensitive resin film] The negative photosensitive resin composition of each example was applied onto a silicon wafer and baked at 90° C. for 5 minutes to form a photosensitive resin film with a thickness of 20 μm on the silicon wafer. The Martens hardness [N / mm 2 The results are shown in Table 2.

[0222] Nanoindentation Evaluation method: FISCHERSCOPE HM2000 measuring device (manufactured by Fisher Instruments) Microhardness test in accordance with ISO14577 Measurement conditions: Maximum test load 30mN, load application time 20 seconds, creep time 5 seconds, temperature 25℃

[0223] [Rolling evaluation] The negative photosensitive resin composition of each example was applied onto a substrate film to a width of 200 mm and a thickness of 20 μm using an applicator, and then dried to form a photosensitive resin layer. Next, the photosensitive resin layer was protected with a cover film having a width of 200 mm by pressing it with a rubber roller so as to remove any air bubbles, and 150 m of the laminate (cover film / photosensitive resin layer / base film) was wound around a core to produce a master roll. At this time, the samples in which cracks or poor compression bonding occurred were rated as ×, and those in which no cracks or poor compression bonding occurred were rated as ○. The results are shown in Table 2.

[0224] <Production of photosensitive resist film> 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 with a thickness of 20 μm. Next, a cover film was laminated onto the photosensitive resin film to obtain a photosensitive resist film.

[0225] <Production of cured film> Process (i): The cover film on the photosensitive resin film of the photosensitive resist film obtained above was peeled off, and the exposed photosensitive resin film and a silicon wafer were laminated under conditions of 90° C., 0.3 MPa, and 0.5 m / min.

[0226] Next, the base film in contact with the photosensitive resin film was peeled off, and the photosensitive resin film was exposed to 200 mJ / cm 2The film was then exposed to i-rays (wavelength 365 nm) at an exposure dose of 100 rpm for 5 minutes on a hot plate at 90° C. to obtain a pre-cured film.

[0227] Step (ii): The resulting pre-cured film was then heated at 200° C. for 1 hour in a nitrogen atmosphere to be cured, thereby obtaining the desired cured film.

[0228] [Evaluation of lamination properties] In 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. The results are shown in Table 2. Evaluation criteria A: Able to bond to silicon wafer. △: Partial adhesion failure (less than 5% of the total area). ×: Poor adhesion such as peeling occurred (5% or more of the total area).

[0229] [Measurement of tensile modulus (E*) of cured film] The tensile modulus (E*) of the cured film obtained in step (ii) was measured as follows. The cured film was peeled off from the silicon wafer, and the tensile 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. Evaluation device: Reogel E-4000 (UBM) Measurement conditions: tension mode, frequency 1.0Hz, chuck distance 10mm A higher tensile modulus (E*) means a stronger cured film.

[0230] <Pattern formation method> Film formation process: The cover film on the photosensitive resin film of the photosensitive resist film obtained above was peeled off, and the exposed photosensitive resin film and a silicon wafer were laminated under conditions of 90° C., 0.3 MPa, and 0.5 m / min. Exposure process: Next, the base film in contact with the photosensitive resin film was peeled off, and the photosensitive resin film was irradiated with 300 mJ / cm 2 through a negative mask having an opening pattern with a hole diameter of 20 μm. 2 The film was then irradiated with i-rays (365 nm) at an exposure dose of 100 dW. Thereafter, the film was post-exposure baked on a hot plate at 90° C. for 5 minutes. Development process: The exposed silicon wafer was then developed with propylene glycol monomethyl ether acetate (PGMEA) at 23° C. for 5 minutes, followed by rinsing and drying to form a negative pattern.

[0231] [Evaluation of lithography characteristics] The microstructure of the formed negative pattern was observed 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 lithography characteristics were evaluated according to the following evaluation criteria. The results are shown in Table 2. Evaluation criteria A: No residue was present and a rectangular pattern was obtained. ×: A tapered pattern was obtained.

[0232] [Table 2]

[0233] From the results shown in Table 2, the Martens hardness of the photosensitive resin film was 235 [N / mm 2 In the negative type photosensitive resin compositions of Examples 1 to 13, in which the tensile modulus (E*) of the cured film is less than 2.1 [GPa] and the tensile modulus (E*) of the cured film is 2.1 [GPa] or more, it can be confirmed that, compared with the negative type photosensitive resin compositions of Comparative Examples 1 to 3, the cured film has higher strength, is easy to roll, and has excellent lamination properties. In addition, it can be confirmed that the negative photosensitive resin compositions of Examples 1 to 13 enable the formation of patterns with good shapes.

Claims

1. A negative-type photosensitive resin composition which contains an epoxy group-containing resin (A), a metal oxide (M), and a cationic polymerization initiator (I), and which forms a negative-type pattern by development using a developer containing an organic solvent, The negative photosensitive resin composition is the epoxy group-containing resin (A) comprises a combination of a resin (A1) represented by the following general formula (A1) and at least one selected from the group consisting of a compound (m1) having a partial structure represented by the following general formula (m1) and a compound (m2) represented by the following general formula (m2): the content of the metal oxide (M) is more than 30 parts by mass and not more than 180 parts by mass relative to 100 parts by mass of the epoxy group-containing resin (A); The negative photosensitive resin composition was applied onto 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 film was 235 [N / mm ２ ] and The photosensitive resin film was exposed to a dose of 200 mJ / cm ２ The negative type photosensitive resin composition is exposed to i-line at 400° C., subjected to a post-exposure bake treatment at 90° C. for 5 minutes, and then subjected to a bake treatment at 200° C. for 1 hour to cure the cured film, which has a tensile modulus (E*) of 2.1 [GPa] or more at a temperature of 175° C. when the viscoelasticity is measured at a frequency of 1.0 Hz. 【Chemistry 1】 [In the formula, R p1 and R p2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Multiple R p1 s may be the same as or different from each other. Multiple R p2 s may be the same as or different from each other. n 1 is an integer of 1 to 5. R EP is an epoxy group-containing group. Multiple R EP s may be the same as or different from each other.] 【Chemistry 2】 [In the formula, n 2 is an integer of 1 to 4. * indicates a bond.] 【Chemistry 3】 [In the formula, R EP is an epoxy group-containing group. A plurality of R EP may be the same or different.]

2. The epoxy group-containing resin (A) contains the resin (A1), the compound (m1) and the compound (m2), 2. The negative type photosensitive resin composition according to claim 1, wherein a total content of the compound (m1) and the compound (m2) is 15 mass% or more in the total content of the resin (A1), the compound (m1), and the compound (m2).

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

4. A pattern forming method comprising the steps of: forming a photosensitive resin film on a support using the negative photosensitive resin composition according to any one of claims 1 to 3; exposing the photosensitive resin film; and developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern.

5. A cured film obtained by curing the negative type photosensitive resin composition according to any one of claims 1 to 3.

6. A method for producing a cured film, comprising: a step of forming a photosensitive resin film on a support using the negative photosensitive resin composition according to any one of claims 1 to 3; and a step of curing the photosensitive resin film to obtain a cured film.

7. A photosensitive resist film comprising a negative photosensitive resin film, the negative photosensitive resin film containing an epoxy group-containing resin (A), a metal oxide (M) and a cationic polymerization initiator (I), laminated on a base film, The photosensitive resin film is the epoxy group-containing resin (A) comprises a combination of a resin (A1) represented by the following general formula (A1) and at least one selected from the group consisting of a compound (m1) having a partial structure represented by the following general formula (m1) and a compound (m2) represented by the following general formula (m2): the content of the metal oxide (M) is more than 30 parts by mass and not more than 180 parts by mass relative to 100 parts by mass of the epoxy group-containing resin (A); When the photosensitive resin film was laminated on a silicon wafer to a thickness of 20 μm, the Martens hardness was 235 [N / mm ２ ] and The photosensitive resin film was exposed to a dose of 200 mJ / cm ２ The photosensitive resist film is exposed to i-line at 400° C., post-exposure baked at 90° C. for 5 minutes, and then baked at 200° C. for 1 hour to harden the cured film, which has a tensile 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. 【Chemistry 4】 [In the formula, R p1 and R p2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Multiple R p1 s may be the same as or different from each other. Multiple R p2 s may be the same as or different from each other. n 1 is an integer of 1 to 5. R EP is an epoxy group-containing group. Multiple R EP s may be the same as or different from each other.] 【Chemistry 5】 [In the formula, n 2 is an integer of 1 to 4. * indicates a bond.] 【Chemistry 6】 [In the formula, R EP is an epoxy group-containing group. A plurality of R EP may be the same or different.]

8. The epoxy group-containing resin (A) contains the resin (A1), the compound (m1) and the compound (m2), 8. The photosensitive resist film according to claim 7, wherein a total content of the compound (m1) and the compound (m2) is 15 mass% or more in the total content of the resin (A1), the compound (m1), and the compound (m2).

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

10. The photosensitive resist film according to any one of claims 7 to 9, which is a laminate in which the photosensitive resin film and a cover film are laminated in this order on the base film.

11. A pattern forming method comprising the steps of: forming a photosensitive resin film on a support using the photosensitive resist film according to any one of claims 7 to 10; exposing the photosensitive resin film; and developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern.

12. A method for producing a cured film, comprising: forming a photosensitive resin film on a support using the photosensitive resist film according to any one of claims 7 to 10; and curing the photosensitive resin film to obtain a cured film.

13. A roll comprising the photosensitive resist film according to any one of claims 7 to 10 wound around a core.

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