Photosensitive composition, method for manufacturing laminate, method for forming cured pattern, and laminate

Abstract

To provide a photosensitive composition that can form a cured pattern of a good shape.SOLUTION: A photosensitive composition comprises a polyfunctional aromatic epoxy compound and a photoacid generator, the photoacid generator comprising a compound represented by the general formula (I-0), where R01-R03 independently represent an optionally substituted cyclic group or the like. L01-L03 independently represent -SO2- or the like. Ar1-Ar3 independently represent an optionally substituted aromatic hydrocarbon group, where, all of Ar1-Ar3 may not be -Ar001-S-Ar002. Ar001 and Ar002 independently represent an optionally substituted aromatic hydrocarbon group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition, a method for producing a laminate, a method for forming a cured pattern, and a laminate. [Background technology]

[0002] 2. Description of the Related Art Wire-wound inductors, which are one type of passive element in electric and electronic circuits, are used, each having an insulating portion made of a cured resin film and a coil pattern made of a plated layer of copper or the like. Fig. 10 is a partial cross-sectional view showing an example of a wire-wound inductor. Wire-wound inductor 200 shown in Fig. 10 is made up of coil-shaped cured pattern 120 formed on support 20 and plating layer 30 filling the space between cured pattern 120. A wire-wound inductor is manufactured by forming a resist layer on a support, selectively exposing this resist layer through a photomask, developing it, and then curing it to form a coil-shaped cured pattern (cured resin film) that will become the insulating part, and then plating is applied between these insulating parts.

[0003] As a technology for manufacturing a wire-wound inductor, materials have been disclosed for use in a method for manufacturing a coil component that includes a first insulating layer, a spirally wound coil pattern formed on the first insulating layer, an intralayer insulating pattern formed on the first insulating layer and arranged along the coil pattern, and a second insulating layer that covers the coil pattern and the intralayer insulating pattern (see Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-136466 [Patent Document 2] Japanese Patent Application Publication No. 2020-136467 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, the increasing multi-functionality of electrical and electronic components has led to demands for inductors to be smaller while maintaining current capacity. To meet these demands, it is necessary to miniaturize cured patterns. However, conventional manufacturing methods sometimes fail to form cured patterns with a good shape. For example, when forming a cured pattern in the shape of a spirally wound coil, pattern distortion can occur in the cured pattern, preventing the formation of a uniform shape or causing the cured pattern to peel off from the support. Pattern distortion refers to a state in which a pattern leans against an adjacent pattern.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive composition capable of forming a cured pattern with a good shape, a method for producing a laminate using the photosensitive composition, a laminate, and a cured pattern formed by the laminate. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a photosensitive composition containing a polyfunctional aromatic epoxy compound and a photoacid generator, wherein the photoacid generator contains a compound represented by the following general formula (I-0):

[0008] [ka] [In the formula, R 01 ~R 03 L each independently represents 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. 01 ~L 03 are each independently a single bond, -CO- or -SO2-. 1 ~Ar 3 are each independently an aromatic hydrocarbon group which may have a substituent. 1~Ar 3 But all -Ar 001 -S-Ar 002 It will never happen. 001 and Ar 002 are each independently an aromatic hydrocarbon group which may have a substituent.

[0009] A second aspect of the present invention is a method for producing a laminate, comprising the steps of forming a first resist layer on a support using a first photosensitive composition, and forming a second resist layer on the first resist layer using a second photosensitive composition, wherein the second photosensitive composition is the photosensitive composition according to the first aspect.

[0010] A third aspect of the present invention is a method for forming a cured pattern, comprising the steps of: exposing a laminate produced by the laminate production method according to the second aspect; developing the exposed laminate to form a resist pattern; and curing the resist pattern to obtain a cured pattern.

[0011] A fourth aspect of the present invention is a laminate of a first resist layer and a second resist layer, wherein the second resist layer is a resist layer formed from the photosensitive composition according to the first aspect. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive composition capable of forming a cured pattern with a good shape, a method for producing a laminate using the photosensitive composition, a laminate, and a cured pattern formed by the laminate. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a cross-sectional view showing one embodiment of a laminate 10 formed on a support 20. FIG. [Figure 2] FIG. 10 is a schematic diagram illustrating the step (iv) of exposing the laminate 10 formed on the support 20 to light. [Figure 3] FIG. 10 is a schematic diagram illustrating the step (v) of developing the exposed laminate 10 to form a resist pattern 110. [Figure 4] FIG. 10 is a schematic diagram illustrating step (vi) of curing the resist pattern 110 to obtain a cured pattern 120 made of a cured resin film 10c. [Figure 5] 1 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Example 1. [Figure 6] 1 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 1. [Figure 7] 1 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 2. [Figure 8] 10 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 3. [Figure 9] 10 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 4. [Figure 10] FIG. 1 is a partial cross-sectional view showing an example of a wire-wound inductor. DETAILED DESCRIPTION OF THE INVENTION

[0014] In this specification and claims, the term "aliphatic" is a relative concept to aromatic, and is defined to mean 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 alkyl groups in alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of such 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 phrase "may have a substituent" includes both the case where a hydrogen atom (-H) is replaced with a monovalent group and the case where a methylene group (-CH2-) is replaced with a divalent group. The term "exposure" is a general concept that includes irradiation with radiation.

[0015] (Photosensitive composition) The photosensitive composition of this embodiment contains a polyfunctional aromatic epoxy compound (hereinafter also referred to as "component (A)") and a photoacid generator (hereinafter also referred to as "component (I)"). When a photosensitive resin film (resist layer) is formed using such a photosensitive composition and selectively exposed to light, an acid is generated from component (I) in the exposed areas of the photosensitive resin film, and the epoxy groups in component (A) undergo ring-opening polymerization due to the action of the acid, reducing the solubility of the photosensitive resin film in a developer containing an organic solvent. Meanwhile, the solubility of the photosensitive resin film in a developer containing an organic solvent remains unchanged in the unexposed areas of the photosensitive resin film, resulting in a difference in solubility in a developer containing an organic solvent between the exposed and unexposed areas of the photosensitive resin film. Therefore, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed areas are dissolved and removed, forming a negative pattern.

[0016] <Polyfunctional aromatic epoxy compound (component (A))> The component (A) may be a compound having enough epoxy groups in one molecule to form a negative pattern upon exposure. Examples of the component (A) used in the photosensitive composition of this embodiment include novolac-type epoxy resins and bisphenol-type epoxy resins.

[0017] <Novolac epoxy resin> Suitable examples of novolac epoxy resins (hereinafter also referred to as "component (A1)") include epoxy resins represented by the following general formula (anv0).

[0018] [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. n1 is an integer of 1 to 5. R EP is an epoxy group-containing group. EP may be the same or different from each other.

[0019] In the formula (anv0), 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. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among them, R p1 , R p2 As the alkyl group, a hydrogen atom or a linear or branched alkyl group is preferred, a hydrogen atom or a linear alkyl group is more preferred, and a hydrogen atom or a methyl group is particularly preferred. In the formula (anv0), multiple R p1 may be the same or different. p2 may be the same as or different from each other.

[0020] In the formula (anv0), n1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0021] In the formula (anv0), 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 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, a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups. The hydrogen atoms of these alicyclic groups may be substituted with alkyl, alkoxy, or hydroxyl groups. 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.

[0022] 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.

[0023] 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 its structure.

[0024] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0025] Examples of the aliphatic hydrocarbon group containing a ring in its 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 straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been 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, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0026] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system 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 some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings. Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene groups or heteroarylene groups); groups in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups 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., groups in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0027] 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, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or a carbonyl group.

[0028] The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in its structure as a 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 groups in which some or all of the hydrogen atoms of the alkyl group have been 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 heteroatom, and the heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0029] In the aromatic hydrocarbon group as a divalent hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an 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 the hydrogen atom of the alicyclic hydrocarbon group.

[0030] 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.

[0031] 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-, and groups represented by the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 , -[Y 21 -C(=O)-O] m” -Y 22 -or- Y 21 -OC(=O)-Y 22 -, wherein Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 0 to 3. 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, an acyl group, 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 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same 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 preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred. 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, in the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 The group represented by - is a group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even 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, even more preferably 1 or 2, and most preferably 1.

[0032] Among them, R EP The epoxy group-containing group in is preferably a glycidyl group.

[0033] Additionally, suitable examples of the component (A1) include resins having a structural unit represented by the following general formula (anv1):

[0034] [ka] [In the formula, R EP is an epoxy group-containing group. a22 and R a23 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0035] In the formula (anv1), R a22 , R a23 The alkyl group having 1 to 5 carbon atoms is R p1 , R p2 The alkyl group has 1 to 5 carbon atoms. R a22 , R a23 The halogen atom is preferably a chlorine atom or a bromine atom. In the formula (anv1), R EP is R in the above formula (anv0). EP and a glycidyl group is preferred.

[0036] Specific examples of the constitutional unit represented by the formula (anv1) are shown below.

[0037] [ka]

[0038] The component (A1) may be a resin consisting solely of the structural unit (anv1), or it may be a resin containing the structural unit (anv1) in addition to other structural units. Examples of other structural units include structural units represented by the following general formulas (anv2) to (anv3).

[0039] [ka] [In the formula, R a24 R is a hydrocarbon group which may have a substituent. a25 ~R a26 , R a28 ~R a30 R are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.a27 represents an epoxy group-containing group or a hydrocarbon group which may have a substituent.

[0040] In the 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, and even more preferably 1 or 2. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc. Among these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0041] The branched alkyl group preferably has 3 to 10 carbon atoms, 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, with an isopropyl group being preferred.

[0042] 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 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 is preferably one having 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0043] R a24When 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 number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings. R a24 Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (an aryl group or a 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., 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 alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0044] In the formulas (anv2) and (anv3), R a25 ~R a26 , R a28 ~R a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. The alkyl group having 1 to 5 carbon atoms and the halogen atom are each defined as R a22 , R a23 is the same as:

[0045] In the formula (anv3), Ra27 R is an epoxy group-containing group or a hydrocarbon group which may have a substituent. a27 The epoxy group-containing group is R EP Similar to R a27 The hydrocarbon group which may have a substituent is R a24 is the same as:

[0046] Specific examples of the structural units represented by the formulae (anv2) to (anv3) are shown below.

[0047] [ka]

[0048] When the component (A1) contains other structural units in addition to the structural unit (anv1), there are no particular limitations on the proportion of each structural unit within the component (A1), but the total amount of structural units having an epoxy group relative to the total amount of all structural units constituting the component (A1) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %.

[0049] Commercially available products of the component (A1) include, for example, novolac epoxy resins 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.).

[0050] As the component (A1), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition of this embodiment, the content of the component (A1) relative to the total mass (mass%) of the component (A) may be 50 mass% or more, 70 mass% or more, 90 mass% or more, or even 100 mass%.

[0051] <Bisphenol-type epoxy resin> The bisphenol-type epoxy resin (hereinafter also referred to as "component (A2)") may be any resin having a structural unit containing a bisphenol skeleton, and among these, solid bisphenol-type epoxy resins are preferred. The solid bisphenol epoxy resin refers to a resin that is solid at 25°C and has a structural unit containing a bisphenol skeleton. The epoxy equivalent of the component (A2) is, for example, preferably 800 g / eq. or more, more preferably 800 to 1200 g / eq., and even more preferably 900 to 1100 g / eq.

[0052] Suitable examples of the component (A2) include epoxy resins represented by the following general formula (abp1):

[0053] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different. a31 and R a32 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. 31 is an integer between 1 and 50.

[0054] In the formula (abp1), R EP is R in the above formula (anv0). EP and a glycidyl group is preferred. In the formula (abp1), R a31 , R a32 The alkyl group having 1 to 5 carbon atoms in the formula (anv0) is R p1 , Rp2 The alkyl groups having 1 to 5 carbon atoms are the same as those in the above. a31 , R a32 are each preferably a hydrogen atom or a methyl group. R a31 , R a32 The fluorinated alkyl group having 1 to 5 carbon atoms in the formula (I) is the same as the above-mentioned R a31 , R a32 Examples of such groups include groups in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with fluorine atoms. In the formula (abp1), na 31 is an integer of 1 to 50, preferably an integer of 4 to 15, and more preferably an integer of 5 to 8.

[0055] As the component (A2), one type may be used alone, or two or more types may be used in combination. Examples of commercially available products that can be used as component (A2) include jER-4005, jER-4007, and jER-4010 (all manufactured by Mitsubishi Chemical Corporation); jER-827, jER-828, jER-834, jER-1001, jER-1002, jER-1003, jER-1055, jER-1007, jER-1009, and jER-1010 (all manufactured by Mitsubishi Chemical Corporation); and EPICLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (all manufactured by DIC Corporation).

[0056] In addition to the above-mentioned compounds, the polyfunctional aromatic epoxy compounds other than the above-mentioned components (A1) and (A2) may also include compounds represented by the following chemical formula (A3-1) and compounds represented by the following chemical formula (A3-2), respectively. An example of a commercially available product that can be used as the compound represented by the following chemical formula (A3-1) is TECHMORE VG-3101L (manufactured by Printec Co., Ltd.). Examples of commercially available products that can be used as the compound represented by the following chemical formula (A3-2) include Showfree (registered trademark) BATG (manufactured by Showa Denko KK).

[0057] [ka]

[0058] In the photosensitive composition of this embodiment, the component (A) preferably contains the component (A1). The polystyrene-equivalent weight average molecular weight of the component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and even more preferably 300 to 200,000.

[0059] The content of the component (A) in the photosensitive composition of the embodiment may be adjusted depending on the thickness of the resist layer to be formed, etc.

[0060] <Photoacid generator (component (I))> The component (I) in the photosensitive composition of the embodiment includes a compound represented by the following general formula (I-0) (hereinafter also referred to as "component (I0)").

[0061] [ka] [In the formula, R 01 ~R 03 L each independently represents 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. 01 ~L 03 are each independently a single bond, -CO- or -SO2-. 1 ~Ar 3 are each independently an aromatic hydrocarbon group which may have a substituent. 1 ~Ar 3 But all -Ar 001 -S-Ar 002 It will never happen. 001 and Ar 002 are each independently an aromatic hydrocarbon group which may have a substituent.

[0062] <Anion section> In the formula (I-0), R 01 ~R03 are each independently 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.

[0063] 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 an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0064] Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxy group, a carbonyl group, and a nitro group. The alkyl group as a 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 a 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 a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Examples of halogenated alkyl groups as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms. The carbonyl group as a substituent is a group that substitutes a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0065] The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic hydrocarbon group include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and 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.). 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.

[0066] Examples of the cyclic aliphatic hydrocarbon group include aliphatic hydrocarbon groups containing a ring in the structure. The cyclic aliphatic hydrocarbon group preferably has 3 to 50 carbon atoms, more preferably 4 to 45 carbon atoms, and more preferably 5 to 40 carbon atoms. 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 interposed 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 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 one or more hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane is more preferably a polycycloalkane having a bridged ring polycyclic skeleton, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a fused ring polycyclic skeleton, such as a cyclic group having a steroid skeleton.

[0067] The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0068] The cyclic hydrocarbon group may contain a heteroatom, such as a heterocyclic ring. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the heterocyclic ring include aromatic heterocyclic rings such as a pyridine ring and a thiophene ring; and aliphatic heterocyclic rings such as tetrahydrofuran, tetrahydropyran, and tetrahydrothiophene.

[0069] The cyclic hydrocarbon group may be a fused ring group containing a fused ring formed by condensing an aliphatic hydrocarbon ring with an aromatic ring. Examples of the fused ring include a polycycloalkane having a bridged ring polycyclic skeleton to which one or more aromatic rings are condensed. Specific examples of the bridged ring polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane.

[0070] The cyclic hydrocarbon group may be a group in which two or more aliphatic rings and / or aromatic rings are linked by a linear or branched aliphatic hydrocarbon group, which may have a substituent. In the linear or branched aliphatic hydrocarbon group linking the alicyclic hydrocarbon groups, a methylene group (-CH-) constituting the aliphatic hydrocarbon chain may be substituted with a divalent group containing a heteroatom. Examples of the divalent group containing a heteroatom include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)-, and -S(=O)-O-.

[0071] A chain alkyl group which may have a substituent: The chain alkyl group may be either a straight chain or a branched chain. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10. 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.

[0072] Examples of the substituent on the chain alkyl group include the same as the substituent on the cyclic group described above. Among these, the substituent in the chain alkyl group is preferably a halogenated alkyl group, more preferably a halogenated alkyl group in which some or all of the hydrogen atoms in an alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms, and even more preferably a fluorinated alkyl group in which some or all of the hydrogen atoms in an alkyl group having 1 to 5 carbon atoms have been substituted with fluorine atoms.

[0073] An optionally substituted chain alkenyl group: 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, even more 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 branched alkenyl groups include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group.

[0074] Examples of the substituent in the chain 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, and the above-mentioned cyclic groups.

[0075] Among the above, R 01 ~R 03 are each independently preferably a chain-like alkyl group which may have a substituent, more preferably a chain-like alkyl group which has a substituent, still more preferably a halogenated alkyl group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms, and particularly preferably a fluorinated alkyl group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms have been substituted with fluorine atoms.

[0076] In the above formula (I-0), L 01 ~L 03 are each independently a single bond, -CO- or -SO2-, among which L 01 ~L 03 is preferably -SO2-.

[0077] The anion moiety of the component (I0) is preferably an anion represented by the following general formula (an-I0).

[0078] [ka] [In the formula, R 001 ~R003 are each independently a chain alkyl group having a fluorine atom.

[0079] In the formula (an-I0), R 001 ~R 003 are each independently a chain alkyl group having a fluorine atom. R 001 ~R 003 Among the above, each of the above is preferably a fluorinated alkyl group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms have been substituted with fluorine atoms, more preferably a fluorinated alkyl group in which some or all of the hydrogen atoms of an alkyl group having 1 to 3 carbon atoms have been substituted with fluorine atoms, and even more preferably a trifluoromethyl group.

[0080] Specific examples of the anion moiety of the component (I0) include anions represented by the following formula (an-1-1).

[0081] [ka]

[0082] <Cation section> In the formula (I-0), Ar 1 ~Ar 3 are each independently an aromatic hydrocarbon group which may have a substituent.

[0083] Ar 1 ~Ar 3 The aromatic hydrocarbon group in the formula (I) 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 some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings. Specific examples of the aromatic hydrocarbon group include groups in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl groups or heteroaryl groups); groups in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups 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, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0084] Ar 1 ~Ar 3 Examples of the substituent that the aromatic hydrocarbon group in the formula (I) may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulas (ca-r-1) to (ca-r-10):

[0085] [ka] [In the formula, R' 201 are each independently 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.

[0086] In the above general formulae (ca-r-1) to (ca-r-10), R' 201The optionally substituted cyclic group, the optionally substituted chain alkyl group, and the optionally substituted chain alkenyl group in the general formula (I-0) are R 01 ~R 03 Examples of the alkyl group include the cyclic group which may have a substituent, the chain alkyl group which may have a substituent, and the chain alkenyl group which may have a substituent in the above formula (1).

[0087] In the formula (I-0), Ar 1 ~Ar 3 All -Ar 001 -S-Ar 002 It will never happen. 001 and Ar 002 are each independently an aromatic hydrocarbon group which may have a substituent. 001 and Ar 002 The aromatic hydrocarbons which may have a substituent in the above formula include Ar 1 ~Ar 3 The aromatic hydrocarbons may be the same as those optionally having a substituent in the above.

[0088] Specific examples of the cation moiety of the component (I0) include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0089] [ka]

[0090] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent. The substituent includes 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

[0091] Additionally, as the cationic moiety of the component (I0), cations represented by the following formulas (ca-1-25) to (ca-1-34) are also preferred.

[0092] [ka]

[0093] [ka] [In the formula, R' 211 is an alkyl group. hal is a hydrogen atom or a halogen atom.

[0094] Furthermore, as the cationic moiety of the component (I0), cations represented by the following chemical formulas (ca-1-35) to (ca-1-47) are also preferred.

[0095] [ka]

[0096] As the cation moiety of the component (I0), among the above, Ar in the above general formula (I-0) 1 and Ar 2 A cation in which at least one of the above is an aromatic hydrocarbon group having a substituent represented by the above formula (ca-r-8) is preferred, and a cation represented by the above chemical formula (ca-1-28) is more preferred.

[0097] Of the above, the component (I0) preferably contains a compound represented by the following general formula (I-0-1) (hereinafter also referred to as "component (I01)").

[0098] [ka] [In the formula, R 001 ~R 003 are each independently a chain alkyl group having a fluorine atom. 1 ~Ar 3are each independently an aromatic hydrocarbon group which may have a substituent. 1 ~Ar 3 But all -Ar 001 -S-Ar 002 It will never happen. 001 and Ar 002 are each independently an aromatic hydrocarbon group which may have a substituent.

[0099] The anion portion of the component (I01) is the same as the anion represented by the above-mentioned general formula (an-I0). The cationic moiety of the component (I01) is the same as the cationic moiety of the component (I0) described above.

[0100] Specific preferred examples of the component (I0) are shown below.

[0101] [ka]

[0102] <Other cationic photopolymerization initiators> Examples of photocationic polymerization initiators other than the above component (I0) include onium borate salts (hereinafter also referred to as "component (I1)"), compounds represented by the following general formula (I2-1) or (I2-2) (hereinafter referred to as "component (I2)"), and compounds represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "component (I3)").

[0103] (I1) Ingredients: The component (I1) is a compound represented by the following general formula (I1). The component (I1) generates a relatively strong acid upon exposure to light.

[0104] [ka] [In the formula, R b01 ~R b04 are each independently an aryl group which may have a substituent, or a fluorine atom; q is an integer of 1 or more;q+ is a q-valent organic cation.

[0105] Anion section In the formula (I1), R b01 ~R b04 The aryl group in the formula (I) preferably has 5 to 30 carbon atoms, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include a naphthyl group, a phenyl group, and an anthracenyl group, with a phenyl group being 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 enhanced, which is preferable. Among them, R in formula (I1) b01 ~R b04 As each of the groups, a fluorinated phenyl group is preferred, and a perfluorophenyl group is particularly preferred.

[0106] A preferred example of the anion moiety of the compound represented by formula (I1) is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - );Tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - );Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ); Trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - );Tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - ) etc. Among them, tetrakis(pentafluorophenyl)borate ([B(C6F5)4]- ) is particularly preferred.

[0107] Cation part In formula (I1), q is an integer of 1 or more, and Q q+ is a q-valent organic cation. This Q q+ Examples of the cation moiety include those similar to those of the cation moiety of the component (I0) described above. In addition, Q q+ In this case, Ar 1 ~Ar 3 But all -Ar 001 -S-Ar 002 Also included are cations where:

[0108] Specific examples of suitable components (I1) are listed below.

[0109] [ka]

[0110] (I2) Ingredients: The component (I2) is a compound represented by the following general formula (I2-1) or (I2-2). The component (I2) generates a relatively strong acid upon exposure to light.

[0111] [ka] [In the formula, R b05 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b05 may be the same or different from each other. q is an integer of 1 or more, and Q q+ is a q-valent organic cation.

[0112] [ka] [In the formula, R b06 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b06may be the same or different from each other. q is an integer of 1 or more, and Q q+ is a q-valent organic cation.

[0113] Anion section In the above formula (I2-1), R b05 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b05 may be the same as or different from each other. R b05 The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. 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.

[0114] The anion moiety of the compound represented by formula (I2-1) is preferably represented by the following general formula (b0-2a).

[0115] [ka] [In the formula, R bf05 is a fluorinated alkyl group which may have a substituent. 1 is an integer between 1 and 5.

[0116] In formula (b0-2a), R bf05 The optionally substituted fluorinated alkyl group in R b05 The same applies to the fluorinated alkyl group which may have a substituent as mentioned above. 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.

[0117] In the above formula (I2-2), R b06 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b06 may be the same as or different from each other. R b06 The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. 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 b06 As the alkyl group, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferred, and a fluorine atom is even more preferred.

[0118] Cation part In formula (I2-1) and formula (I2-2), q is an integer of 1 or more, and Q q+ is a q-valent organic cation. This Q q+ Examples of the cation moiety include those similar to those of the cation moiety of the component (I0) described above. In addition, Q q+ In this case, Ar 1 ~Ar 3 But all -Ar 001 -S-Ar 002 Also included are cations where:

[0119] Specific examples of suitable components (I2) are listed below.

[0120] [ka]

[0121] (I3) Ingredients: The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2). Component (I3) is a compound that generates a weaker acid than component (I0) upon exposure, and acts as a quencher (acid diffusion controller) that traps the acid generated from component (I0) upon exposure. The component (I3) does not function as a quencher in the exposed areas of the resist film because it decomposes and loses its acid diffusion control properties (basicity), but it does function as a quencher in the unexposed areas of the resist film.

[0122] [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 m-valent organic cation.

[0123] {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 is 201 Among the cyclic groups, chain alkyl groups and chain alkenyl groups in the explanation of (1), those which have no substituent or those which have a substituent other than a halogen atom are exemplified. R b12 The alkyl group 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 3 to 10. The aliphatic cyclic group is preferably a group (which may have a substituent other than a halogen atom) in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor. R b12 The hydrocarbon group may have a substituent other than a halogen atom, and the substituent may be 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. Here, "may have a substituent other than a halogen atom" not only excludes cases where a substituent consists of only halogen atoms, but also excludes cases where a substituent contains at least one halogen atom (for example, when the substituent is a fluorinated alkyl group).

[0124] Preferred examples of the anion moiety of the component (I3-1) are shown below.

[0125] [ka]

[0126] Cation part In formula (I3-1), M m+ is an m-valent organic cation. M m+ Examples of the organic cation include the same as the cation moiety of the component (I0) described above. In addition, M m+ In this case, Ar 1 ~Ar 3 But all -Ar 001 -S-Ar 002 Also included are cations where: It takes M m+Suitable organic cations include, for example, the cations represented by the above formulas (ca-1-25), (ca-1-27) to (ca-1-35), (ca-1-37), (ca-1-45), and (ca-1-46), and among these, the cation represented by the above formula (ca-1-28) is preferred.

[0127] {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 is 201 Among the cyclic groups, chain alkyl groups and chain alkenyl groups in the explanation of (1), those which have no substituent or those which have a substituent other than a halogen atom are exemplified.

[0128] 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 is preferred. Examples of the substituent that these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is 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). In the following general formulas (y-al-1) to (y-al-7), R in the above formula (I3-2) b11 The bond to V' in the following general formulas (y-al-1) to (y-al-7) is 101 is.

[0129] [ka] [In the formula, V' 101V' is a single bond or an alkylene group having 1 to 5 carbon atoms. 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.]

[0130] 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.

[0131] 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 (I) include a methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; an ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3)CH2 -, etc.; a trimethylene group (n-propylene group) [-CH2CH2CH2-]; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; a tetramethylene group [-CH2CH2CH2CH2-]; alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and a pentamethylene group [-CH2CH2CH2CH2CH2-]. Also, V' 101 or V' 102 In the above, some methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is represented by R' 201A divalent group obtained by removing one hydrogen atom from a cyclic aliphatic hydrocarbon group (a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group) is preferred, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferred.

[0132] 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, and specific examples thereof include straight-chain 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-chain 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.

[0133] R b11 As the group, a cyclic group which may have a substituent other than a halogen atom is preferred. Preferred examples of the anion moiety of the component (I3-2) are shown below.

[0134] [ka]

[0135] 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:

[0136] Specific examples of suitable components (I3) are listed below.

[0137] [ka]

[0138] As the component (I), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition of this embodiment, the component (I) preferably contains the component (I0) and the component (I3), and more preferably consists of only the component (I0) and the component (I3).

[0139] In the component (I) of the photosensitive composition of this embodiment, the total content of the components (I0) and (I3) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, relative to 100% by mass of the total amount of the component (I).

[0140] The content of component (I) in the photosensitive composition of this embodiment is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.3 to 1 part by mass, per 100 parts by mass of component (A). When the content of component (I) is at least the lower limit of the above-mentioned preferred range, sufficient sensitivity is obtained, and the lithography properties of the resist pattern are further improved. In addition, the strength of the cured resin film is further increased. On the other hand, when the content is at most the upper limit of the above-mentioned preferred range, sensitivity is appropriately controlled, and a resist pattern with a good shape is more easily obtained.

[0141] The content of the component (I0) in the photosensitive composition of this embodiment is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.3 to 1 part by mass, per 100 parts by mass of the component (A). When the amount of component (I0) is at least as large as the lower limit of the above-mentioned preferred range, a resist pattern with a good shape is more likely to be obtained, while when the amount is no greater than the upper limit of the above-mentioned preferred range, both sensitivity and resist pattern shape can be achieved.

[0142] The content of component (I3) in the photosensitive composition of this embodiment is preferably 0.005 to 1 part by mass, more preferably 0.005 to 0.1 part by mass, and even more preferably 0.01 to 0.05 part by mass, per 100 parts by mass of component (A). When the content of component (I3) is at least the lower limit of the above-mentioned preferred range, the acid generated from component (I0) upon exposure diffuses appropriately, making it easier to obtain a resist pattern with a good shape. On the other hand, when the content is at most the upper limit of the above-mentioned preferred range, sufficient sensitivity is obtained, and the lithography properties of the resist pattern are further improved.

[0143] <<Optional ingredients>> The photosensitive composition of the present embodiment may contain other components (optional components) as needed, in addition to the above-described component (A) and component (I). If desired, the photosensitive composition may contain, as appropriate, miscible additives such as aliphatic epoxy compounds, metal oxides, silane coupling agents, sensitizer components, solvents, additional resins for improving the performance of the film, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and antihalation agents.

[0144] Aliphatic epoxy compounds Suitable examples of the aliphatic epoxy compound include compounds represented by the following general formula (ta1) (hereinafter also referred to as "component (ta1)"). When the photosensitive composition of the present embodiment further contains an aliphatic epoxy compound, the pattern shape at the interface with the support becomes better.

[0145] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different from each other.

[0146] In the formula (ta1), R EPis an epoxy group-containing group, and R in the formula (anv0) EP is the same as:

[0147] Commercially available products that can be used as component (ta1) include, for example, the TEPIC series (manufactured by Nissan Chemical Industries, Ltd.), such as TEPIC-VL, TEPIC, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, and TEPIC-UC; MA-DGIC, DA-MGIC, and TOIC (manufactured by Shikoku Chemical Industries, Ltd.);

[0148] As the component (ta1), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition of this embodiment, the content of the component (ta1) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total parts by mass of the component (A).

[0149] Further, examples of the aliphatic epoxy compound include compounds containing a partial structure represented by the following general formula (m1) (hereinafter also referred to as "component (m1)").

[0150] [ka] [In the formula, n2 is an integer of 1 to 4. * indicates a bond.]

[0151] In the formula (m1), n2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0152] Examples of the component (m1) include compounds in which a plurality of partial structures represented by the general formula (m1) are bonded via a divalent linking group or a single bond. Among these, compounds in which a plurality of partial structures represented by the general formula (m1) are bonded via a divalent linking group are preferred. The divalent linking group here 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. Here, the divalent hydrocarbon group which may have a substituent and the divalent linking group which contains a hetero atom are represented by R in the above formula (anv0). 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 preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred.

[0153] Examples of commercially available products that can be used as the (m1) component include ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (all manufactured by ADEKA Corporation); CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (all manufactured by Daicel Corporation); and DENACOL EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase ChemteX Corporation).

[0154] The aliphatic epoxy compound may also be a polyfunctional aliphatic epoxy compound, and examples of the polyfunctional aliphatic epoxy compound include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, and inositol hexaglycidyl ether.

[0155] Silane coupling agents Examples of the silane coupling agent include silane coupling agents having a reactive substituent 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, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0156] The silane coupling agent may be used alone or in combination of two or more kinds. In the photosensitive composition of this embodiment, the content of the silane coupling agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total parts by mass of component (A).

[0157] Metal oxides Examples of metal oxides (hereinafter also referred to as "component (M)") include oxides of metals such as silicon (metallic silicon), titanium, zirconium, and hafnium. Of these, silicon oxides are preferred, and among these, silica is particularly preferred. The inclusion of component (M) makes it easier to obtain a cured resin film with improved film strength and heat resistance, and also enables the formation of a resist pattern with a good shape and high resolution. The component (M) is preferably in the form of particles.

[0158] Sensitizer ingredients The sensitizer component is not particularly limited as long as it can absorb energy due to exposure and transfer that 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, acetophenone-based photosensitizers, naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone.

[0159] The photosensitive composition of this embodiment may further contain a solvent (hereinafter also referred to as "component (S)"). Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; monoalkyl ethers or monoalkyl ethers of the above polyhydric alcohols or the above compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether; Examples of suitable organic solvents include derivatives of polyhydric alcohols such as compounds having an ether bond, such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane; and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethyl sulfoxide (DMSO).

[0160] The component (S) may be used alone or as a mixed solvent of two or more types.

[0161] When component (S) is contained, the amount used is not particularly limited, and is set appropriately depending on the thickness of the coating film at a concentration that allows the photosensitive composition to be applied to a substrate or the like without dripping. For example, the (S) component can be used so that the solid content concentration is 50% by mass or more, and the (S) component can be used so that the solid content concentration is 60% by mass or more. It is also possible to employ an embodiment in which the component (S) is substantially not contained (that is, an embodiment in which the solid content concentration is 100% by mass).

[0162] The photosensitive composition of the present embodiment described above contains the compound represented by the general formula (I-0) as a photoacid generator. The compound has specific anion and cation moieties that provide appropriate dispersibility in the photosensitive composition of the present embodiment, ease of acid generation upon exposure, strength of the acid generated upon exposure, and acid diffusibility. This allows the reaction of the acid generated upon exposure in the resist layer formed from the photosensitive composition of the present embodiment to proceed uniformly in the height direction of the resist layer. Therefore, a photosensitive composition containing this compound can form a cured pattern with a good shape.

[0163] (Method of manufacturing laminate) The method for producing a laminate of this embodiment includes the steps of forming a first resist layer on a support using a first photosensitive composition, and forming a second resist layer on the first resist layer using a second photosensitive composition. This laminate production method is characterized in that the second photosensitive composition is the photosensitive composition of the above-described embodiment.

[0164] Specific examples of the first photosensitive composition include photosensitive compositions containing a polyfunctional aromatic epoxy compound and a photoacid generator, wherein the photoacid generator does not contain the compound represented by the general formula (I-0) described above. Examples of the polyfunctional aromatic epoxy compound include the same compounds as those used as the component (A) in the photosensitive composition of the above-described embodiment. Examples of the photoacid generator include those similar to the component (I2) in the photosensitive composition of the above-described embodiment. Among them, a compound represented by any one of the above chemical formulas (I2-1-1), (I2-1-2), or (I2-2-1) is preferred, and a compound represented by the above chemical formula (I2-2-1) is more preferred.

[0165] When the first photosensitive composition contains the component (I2) as a photoacid generator, the content of the component (I2) is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the component (A).

[0166] As one embodiment of a method for manufacturing such a laminate, a method for manufacturing a laminate 10 shown in FIG. 1 will be described. FIG. 1 is a cross-sectional view showing one embodiment of a laminate 10 formed on a support 20. As shown in FIG. The laminate 10 is formed by laminating a first resist layer 11 in contact with a support 20, a second resist layer 12, a third resist layer 13, and a fourth resist layer 14 in this order.

[0167] The laminate 10 can be produced by a production method including the steps of: (i) forming a first resist layer 11 on a support 20 using a first photosensitive composition; (ii) forming a second resist layer 12 on the first resist layer 11 using a second photosensitive composition; and (iii) forming a third resist layer 13 and a fourth resist layer 14 on the second resist layer 12 in this order. Each of the steps (i) to (iii) will be explained below.

[0168] <Process (i)> In step (i), a first resist layer 11 is formed on a support 20 using a first photosensitive composition. The method for forming the first resist layer 11 on the support 20 may be, for example, a method in which the first photosensitive composition in a solution state is applied to the support and a pre-baking (PAB) treatment is performed, or a method in which the first photosensitive composition in a film form is laminated to the support.

[0169] When using the first photosensitive composition in a solution state, the first photosensitive composition in a solution state is first applied onto the support 20 by a known method such as spin coating, roll coating, or screen printing, and then baked (post-apply bake (PAB)) for 2 to 60 minutes at a temperature of 50 to 150°C, for example, to form a first resist layer 11 (photosensitive resin film) on the support 20.

[0170] When a first photosensitive composition in the form of a film is used, a laminated film (1) in which a photosensitive resin film has been formed on a base film in advance in the same manner as described above is laminated so that the photosensitive resin film and the support 20 are adjacent to each other, thereby forming a first resist layer 11 (photosensitive resin film) on the support 20. The conditions for laminating the photosensitive resin film using the first photosensitive composition onto the support 20 are preferably, for example, a temperature of 30 to 100° C., a pressure of 0.1 to 0.5 MPa, and a processing speed of 0.2 to 1.0 m / min.

[0171] The thickness of the first resist layer 11 (photosensitive resin film) is preferably 60 μm or less, more preferably 5 to 60 μm, and even more preferably 20 to 50 μm.

[0172] The substrate film constituting the laminated film (1) can be a known film, such as a thermoplastic resin film. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 to 150 μm.

[0173] The support 20 may be a conventionally known one, for example, a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. More specifically, examples of substrates for electronic components include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. Examples of materials for the wiring pattern include copper, aluminum, nickel, and gold. The support 20 may also be a substrate such as the above-described one on which an organic material film is provided. Examples of organic material films include organic anti-reflective coatings (organic BARCs) and organic films such as lower organic films in multilayer resist methods. The support 20 may also be a substrate such as the above impregnated with a thermosetting resin (a substrate containing a thermosetting resin). Examples of the thermosetting resin include bismaleimide triazine resin. In the present embodiment, the support 20 is preferably one having a substrate containing a thermosetting resin, and more preferably one having a substrate containing a bismaleimide triazine resin, from the standpoints of heat resistance, electrical properties, ease of processing, cost, etc.

[0174] <Process (ii)> In step (ii), a second photosensitive composition is used to form a second resist layer 12 on the first resist layer 11. In this embodiment, the second photosensitive composition is the photosensitive composition of the above-described embodiment. As a method for forming the second resist layer 12 on the first resist layer 11, a method of laminating the first resist layer 11 with a second photosensitive composition in the form of a film can be mentioned. A laminated film (2) in which a photosensitive resin film has been previously formed on a base film in the same manner as described above using a second photosensitive composition in the form of a film is then laminated so that the photosensitive resin film using the second photosensitive composition and the first resist layer 11 are adjacent to each other, thereby forming a second resist layer 12 on the first resist layer 11. The conditions for laminating the photosensitive resin film using the second photosensitive composition and the first resist layer 11 are preferably, for example, a temperature of 30 to 100°C, a pressure of 0.1 to 0.5 MPa, and a processing speed of 0.2 to 1.0 m / min.

[0175] The thickness of the second resist layer 12 (photosensitive resin film) is preferably 60 μm or less, more preferably 5 to 60 μm, and even more preferably 20 to 50 μm.

[0176] The base film constituting the laminated film (2) can be a known material, such as 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.

[0177] <Step (iii)> In step (iii), a third resist layer 13 and a fourth resist layer 14 are formed in this order on the second resist layer 12. The third photosensitive composition and the fourth photosensitive composition may each be the same as the second photosensitive composition used in the step (ii). In the operation of step (iii), first, the second resist layer 12 and a film-shaped third photosensitive composition are laminated together to form a third resist layer 13 on the second resist layer 12. Next, the third resist layer 13 and a film-shaped fourth photosensitive composition are laminated together to form a fourth resist layer 14 on the third resist layer 13.

[0178] The lamination conditions for forming the third resist layer 13 and the lamination conditions for forming the fourth resist layer 14 are the same as the conditions for forming the second resist layer 12, respectively. The thickness of the third resist layer 13 (photosensitive resin film) is preferably 60 μm or less, more preferably 5 to 60 μm, and even more preferably 20 to 50 μm. The thickness of the fourth resist layer 14 (photosensitive resin film) is preferably 60 μm or less, more preferably 5 to 60 μm, and even more preferably 20 to 50 μm.

[0179] Next, the first to fourth resist layers laminated on the support 20 are subjected to baking (post-apply bake (PAB)) treatment as required, for example, at a temperature of 30 to 50° C. for 20 to 80 minutes. As a result of the above, a laminate 10 can be produced on the support 20, in which a first resist layer 11, a second resist layer 12, a third resist layer 13, and a fourth resist layer 14 are stacked in this order.

[0180] Regarding the laminate 10: The laminate 10 manufactured by the manufacturing method including the above-mentioned steps (i), (ii), and (iii) is a laminate of four resist layers. In FIG. 1, the height of the laminate 10 from the surface of the support 20, ie, the total thickness of the four resist layers, is, for example, 60 to 260 μm.

[0181] In the laminate manufacturing method of the embodiment described above, the photosensitive composition of the above-described embodiment is used as the second photosensitive composition for forming the second resist layer 12. Therefore, this laminate manufacturing method makes it possible to manufacture a laminate 10 that can form a uniformly shaped cured pattern. Specifically, in the laminate 10 having four resist layers stacked together, the photosensitive composition of the above-described embodiment is used as the second photosensitive composition for forming the second resist layer 12, the third resist layer 13, and the fourth resist layer 14, so that when the cured pattern is formed, the cured pattern is less likely to become distorted.

[0182] In one embodiment of the laminate manufacturing method described above, the third photosensitive composition for forming the third resist layer 13 and the fourth photosensitive composition for forming the fourth resist layer 14 can be the same as the second photosensitive composition for forming the second resist layer 12, but the present invention is not limited to this. The third photosensitive composition and the fourth photosensitive composition can each be appropriately selected within the scope of the effects of the present invention.

[0183] In one embodiment of the laminate manufacturing method described above, the second resist layer 12, the third resist layer 13, and the fourth resist layer 14 are laminated in steps (ii) and (iii) by laminating a film-shaped photosensitive composition, but the present invention is not limited to this. For example, the second resist layer 12, the third resist layer 13, and the fourth resist layer 14 can also be laminated by selecting a solvent that does not easily dissolve the lower layer, applying a photosensitive composition in solution onto the lower layer, and performing a pre-baking (PAB) process.

[0184] In one embodiment of the method for manufacturing the laminate described above, the laminate has a four-layer structure, but this is not limited to this and may have a structure of two or more layers, and the number of layers may be set according to the desired height and aspect ratio. In one embodiment of the method for producing the laminate described above, a method including steps (i) to (iii) has been described, but the method is not limited to this and may include other steps as necessary.

[0185] (Cured pattern forming method) The method for forming a cured pattern of this embodiment includes the steps of exposing a laminate manufactured by the method for manufacturing a laminate of the above-described embodiment, developing the exposed laminate to form a resist pattern, and curing the resist pattern to obtain a cured pattern.

[0186] The cured pattern can be produced by a production method including a step (iv) of exposing the laminate 10 formed on the support 20 shown in FIG. 1 to light, a step (v) of developing the exposed laminate 10 to form a resist pattern 110, and a step (vi) of curing the resist pattern 110 to obtain a cured pattern 120 made of a cured resin film 10c. Each of steps (iv) to (vi) will be explained below.

[0187] <Process (iv)> In step (iv), the laminate 10 formed on the support 20 is exposed to light. For example, using a known exposure device, the laminate 10 is selectively exposed to light through a photomask 90 on which a pattern in the shape of a spirally wound coil is formed, as shown in FIG. By the exposure treatment in step (iv), the exposed laminate 10 becomes an exposed portion 10b whose solubility in a developer has changed due to the exposure, and an unexposed portion 10d that remains unchanged.

[0188] After the selective exposure, the exposed laminate 10 is subjected to a baking (post-exposure bake (PEB)) treatment, for example, at a temperature of 50 to 80° C. for 30 to 60 minutes, if necessary.

[0189] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet light having a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm), or visible light is selectively irradiated (exposed). As the radiation source for these radiations, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc. can be used. Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc. For example, when an ultra-high pressure mercury lamp is used, it is 100 to 2000 mJ / cm. 2 is.

[0190] The method of exposing the laminate 10 may be normal exposure (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion lithography.

[0191] <Process (v)> In the step (v), the exposed laminate 10 is developed to form a resist pattern 110 in the shape of a spirally wound coil. For example, by developing the exposed laminate 10 with a developer containing an organic solvent (organic developer), the unexposed portions 10d of the laminate 10 are dissolved and removed, and the exposed portions 10b remain as residual images, forming a negative resist pattern 110, as shown in FIG. 3. The content of the organic solvent in the developer containing the organic solvent is, for example, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more, relative to the total amount of the developer, and may be 100% by mass. After development, a rinse treatment is preferably carried out, and a bake treatment (post-bake) may be carried out as necessary.

[0192] The organic solvent contained in the organic developer may be any solvent capable of dissolving the components of the photosensitive composition, and may be appropriately selected from known organic solvents. Specific examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0193] 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.

[0194] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, 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 alkyl esters 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, butyl acetate or PGMEA is preferred as the ester solvent.

[0195] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0196] The organic developer may contain known additives as needed. 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 nonionic surfactant, and more preferably a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant. When a surfactant is added, the amount added is usually 0.001 to 5 mass %, preferably 0.005 to 2 mass %, and more preferably 0.01 to 0.5 mass %, based on the total amount of the organic developer.

[0197] The development process can be carried out by a known development method, such as a method of immersing a laminate on a support in a developer for a certain period of time (dip method), a method of piling up developer on the surface of the laminate by surface tension and leaving it to stand for a certain period of time (puddle method), a method of spraying developer onto the surface of the laminate (spray method), or a method of continuously applying developer while scanning a developer application nozzle at a constant speed onto a laminate rotating at a constant speed (dynamic dispense method).

[0198] 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 laminate rotating at a constant speed (spin coating method), a method of immersing the laminate in the rinse liquid for a certain period of time (dipping method), or a method of spraying the rinse liquid onto the surface of the laminate (spray method). The rinsing treatment is preferably carried out using a rinsing liquid containing an organic solvent.

[0199] <Process (vi)> In step (vi), the resist pattern 110 formed in step (v) is cured to obtain a cured pattern 120. For example, the resist pattern 110 formed in step (v) is subjected to a heat treatment (curing operation) to harden it, thereby obtaining a hardened pattern 120 made of a hardened resin film 10c as shown in FIG. In the cured resin film 10c, the first to fourth resist layers are cured and integrated. The heat treatment (curing operation) in step (vi) can be carried out under conditions such as a temperature of 100 to 250° C. and a time of 0.5 to 2 hours.

[0200] Regarding cure pattern 120: 4, the cured pattern 120 is a spirally wound coil-shaped pattern and can constitute an insulating part of the inductor as a permanent film. The spaces between the cured resin films 10c are plated with copper or the like. The height (h) of the cured pattern 120 is, for example, 60 to 260 μm. The width (w) of the cured pattern 120 is, for example, 1 to 100 μm. The distance (space) between the cured patterns 120 is, for example, 1 to 100 μm. The aspect ratio (h / w) of the cured pattern 120 is, for example, 1 to 80.

[0201] The method for forming a cured pattern according to the present embodiment described above uses the laminate 10 manufactured by the method for manufacturing a laminate according to the above embodiment. Therefore, this method for forming a cured pattern makes it possible to manufacture a cured resin film 10c with a good shape without any twists at the nodes between layers.

[0202] Furthermore, this hardened pattern forming method makes it possible to stably achieve miniaturization of the insulating portion that constitutes an inductor, and is therefore useful for manufacturing the insulating portion of an inductor.

[0203] In one embodiment of the above-described method for forming a cured pattern, in step (v), the exposed laminate 10 is developed with a developer containing an organic solvent (organic developer), but the present invention is not limited to this, and depending on the properties of the photosensitive composition, development may be performed with an alkaline developer. Examples of alkaline developers include a 0.1 to 10 mass % aqueous solution of tetramethylammonium hydroxide (TMAH).

[0204] (Laminate) The laminate of this embodiment is a laminate of a first resist layer and a second resist layer, wherein the second resist layer is a resist layer formed from the photosensitive composition of the above-described embodiment.

[0205] One embodiment of such a laminate is a laminate of a first resist layer 11 and a second resist layer 12 produced by steps (i) and (ii) in the above-mentioned (method for producing a laminate).

[0206] The laminate of the present embodiment described above has a resist layer formed from the photosensitive composition of the above-described embodiment, and therefore can stably produce a cured pattern with a good shape. [Example]

[0207] 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.

[0208] <Preparation of Photosensitive Composition> Each component shown in Table 1 was mixed and dissolved in MEK, and the mixture was filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Corporation) to prepare a photosensitive composition (solution with a solid content of 50 to 80% by mass) for each example.

[0209] [Table 1]

[0210] In Table 1, the abbreviations have the following meanings: The values ​​in brackets [ ] are the amounts of each component blended (parts by mass; solid content equivalent). (A)-1: Novolac epoxy resin represented by the following chemical formula (A1-1), product name "jER-157S70", manufactured by Mitsubishi Chemical Corporation.

[0211] [ka]

[0212] (ta1)-1: an aliphatic epoxy compound represented by the following chemical formula (ta1-1), trade name "TEPIC-VL", manufactured by Nissan Chemical Industries, Ltd.

[0213] [ka]

[0214] (I0)-1: A photoacid generator represented by the following chemical formula (I0-1). (I3)-1: A photoacid generator represented by the following chemical formula (I3-1-1).

[0215] [ka]

[0216] (I)-1: A photoacid generator represented by the following chemical formula (I2-2-1). (I)-2: A photoacid generator represented by the following chemical formula (I1-4). (I)-3: A photoacid generator represented by the following chemical formula (I1-5). (I)-4: A photoacid generator represented by the following chemical formula (I1-1).

[0217] [ka]

[0218] (X)-1: Glycidoxypropyltrimethoxysilane, trade name "XIAMETER OFS-6040 Silane", manufactured by Dow Toray Industries, Inc.

[0219] <Formation of hardened pattern> Using the photosensitive compositions of Example 1 and Comparative Examples 1 to 4, and Photosensitive Composition A, attempts were made to form a cured pattern in the shape of a spirally wound coil.

[0220] Preparation of laminated film: Photosensitive composition A was applied to a substrate film using an applicator and dried in an oven at 70°C for 10 minutes to form a photosensitive resin film A with a thickness of 45 μm, thereby obtaining a photosensitive laminate film A.

[0221] Except for changing the photosensitive composition A to the photosensitive composition of Example 1, the coating and drying were carried out as described above to form a photosensitive resin film (1a) with a thickness of 45 μm on the substrate film, thereby obtaining a photosensitive laminate film (F1a).

[0222] Except for changing the photosensitive composition A to the photosensitive composition of Comparative Example 1, the coating and drying were carried out as described above to form a photosensitive resin film (1b) with a thickness of 45 μm on the substrate film, thereby obtaining a photosensitive laminate film (F1b).

[0223] Except for changing the photosensitive composition A to the photosensitive composition of Comparative Example 2, the coating and drying were carried out as described above to form a photosensitive resin film (2b) with a thickness of 45 μm on the substrate film, thereby obtaining a photosensitive laminate film (F2b).

[0224] Except for changing the photosensitive composition A to the photosensitive composition of Comparative Example 3, the coating and drying were carried out as described above to form a photosensitive resin film (3b) with a thickness of 45 μm on the substrate film, thereby obtaining a photosensitive laminate film (F3b).

[0225] Except for changing the photosensitive composition A to the photosensitive composition of Comparative Example 4, the coating and drying were carried out as described above to form a photosensitive resin film (4b) with a thickness of 45 μm on the substrate film, thereby obtaining a photosensitive laminate film (F4b).

[0226] Example 1 forming a first resist layer; The photosensitive resin film A formed on the base film of laminated film A and a 5-inch silicon substrate (support) containing bismaleimide triazine resin were laminated under conditions of 45°C, 0.3 MPa, and 0.5 m / min so that the photosensitive resin film A and the support were adjacent to each other, thereby forming a first resist layer on the support.

[0227] forming a second resist layer; Next, the substrate film in contact with the photosensitive resin film A constituting the first resist layer was peeled off, and the exposed photosensitive resin film A and the photosensitive resin film (1a) formed on the substrate film of the laminated film (F1a) were laminated under conditions of 45°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (1a-1) of the support, the first resist layer, and the second resist layer.

[0228] forming a third resist layer; Next, the base film in contact with the photosensitive resin film (1a) constituting the second resist layer was peeled off, and the exposed photosensitive resin film (1a) and the photosensitive resin film (1a) formed on the base film of the laminated film (F1a) were laminated under conditions of 45°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (1a-2) of the laminate (1a-1) and the third resist layer.

[0229] forming a fourth resist layer; Next, the substrate film in contact with the photosensitive resin film (1a) constituting the third resist layer was peeled off, and the exposed photosensitive resin film (1a) and the photosensitive resin film (1a) formed on the substrate film of the laminated film (F1a) were laminated under conditions of 45°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (1a-3) in which the first to fourth resist layers were laminated in this order on the support. The resulting laminate (1a-3) was then subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

[0230] Regarding the laminate (1a-3) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive resin film A Second resist layer: 45 μm thick photosensitive resin film (1a) Third resist layer: 45 μm thick photosensitive resin film (1a) Fourth resist layer: 45 μm thick photosensitive resin film (1a)

[0231] exposing the laminate to light: Next, the laminate (1a-3) after the baking treatment (PAB) was irradiated with 1600 mJ / cm 2 using an aligner (Canon, PLA-501F) through a mask having a spirally wound coil-shaped pattern. 2 (i-line integrated value) was exposed. Thereafter, post-exposure baking was carried out in an oven at 62°C for 45 minutes.

[0232] Developing process: Next, the laminate (1a-3) after post-exposure baking was subjected to solvent development (dip, vertical) using PGMEA as a developer at 23°C for 40 minutes, thereby obtaining a resist pattern in the shape of a spirally wound coil. Thereafter, a rinsing treatment was carried out with PGMEA for 5 minutes.

[0233] Steps for obtaining a hardened pattern: Next, the resist pattern after the rinsing treatment was subjected to a heat treatment in an oven at a temperature of 200°C for 60 minutes, thereby obtaining a spirally wound coil-shaped cured pattern (pattern width: 3 μm, space width: 40 μm) using the photosensitive composition of Example 1.

[0234] (Comparative Example 1) forming a first resist layer; In the same manner as in Example 1, a first resist layer was formed on a support.

[0235] Steps of forming second to fourth resist layers: Next, the steps of forming second to fourth resist layers (respectively the photosensitive resin films (1b)) using a laminate film (F1b) on the photosensitive resin film A, which is the first resist layer, were carried out in the same manner as in Example 1, thereby obtaining a laminate (1b-3) in which the second to fourth resist layers were laminated in this order on the support. The resulting laminate (1b-3) was then subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

[0236] Regarding the laminate (1b-3) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive resin film A Second resist layer: 45 μm thick photosensitive resin film (1b) Third resist layer: 45 μm thick photosensitive resin film (1b) Fourth resist layer: 45 μm thick photosensitive resin film (1b)

[0237] A step of exposing a laminate to light, a step of developing the laminate, and a step of obtaining a hardened pattern: Next, the laminate (1b-3) after baking (PAB) was subjected to the same operations as in Example 1, including the step of exposing the laminate, the step of developing, and the step of obtaining a cured pattern, to obtain a spirally wound coil-shaped cured pattern using the photosensitive composition of Comparative Example 1.

[0238] (Comparative Example 2) forming a first resist layer; In the same manner as in Example 1, a first resist layer was formed on a support.

[0239] Steps of forming second to fourth resist layers: Next, the steps of forming second to fourth resist layers (respectively the photosensitive resin films (2b)) using a laminate film (F2b) on the photosensitive resin film A, which is the first resist layer, were carried out in the same manner as in Example 1, thereby obtaining a laminate (2b-3) in which the second to fourth resist layers were laminated in this order on the support. The resulting laminate (2b-3) was then subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

[0240] Regarding the laminate (2b-3) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive resin film A Second resist layer: 45 μm thick photosensitive resin film (2b) Third resist layer: 45 μm thick photosensitive resin film (2b) Fourth resist layer: 45 μm thick photosensitive resin film (2b)

[0241] A step of exposing a laminate to light, a step of developing the laminate, and a step of obtaining a hardened pattern: Next, the laminate (2b-3) after baking (PAB) was subjected to the same operations as in Example 1, including the step of exposing the laminate, the step of developing, and the step of obtaining a cured pattern, to obtain a spirally wound coil-shaped cured pattern using the photosensitive composition of Comparative Example 2.

[0242] (Comparative Example 3) forming a first resist layer; In the same manner as in Example 1, a first resist layer was formed on a support.

[0243] Steps of forming second to fourth resist layers: Next, the steps of forming second to fourth resist layers (respectively the photosensitive resin films (3b)) using a laminate film (F3b) on the photosensitive resin film A, which is the first resist layer, were carried out in the same manner as in Example 1, thereby obtaining a laminate (3b-3) in which the second to fourth resist layers were laminated in this order on the support. The resulting laminate (3b-3) was then subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

[0244] Regarding the laminate (3b-3) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive resin film A Second resist layer: 45 μm thick photosensitive resin film (3b) Third resist layer: 45 μm thick photosensitive resin film (3b) Fourth resist layer: 45 μm thick photosensitive resin film (3b)

[0245] A step of exposing a laminate to light, a step of developing the laminate, and a step of obtaining a hardened pattern: Next, the laminate (3b-3) after baking (PAB) was subjected to the same operations as in Example 1, including the step of exposing the laminate, the step of developing, and the step of obtaining a cured pattern, to obtain a spirally wound coil-shaped cured pattern using the photosensitive composition of Comparative Example 3.

[0246] Comparative Example 4 forming a first resist layer; In the same manner as in Example 1, a first resist layer was formed on a support.

[0247] Steps of forming second to fourth resist layers: Next, the steps of forming second to fourth resist layers (respectively the photosensitive resin films (4b)) using a laminate film (F4b) on the photosensitive resin film A, which is the first resist layer, were carried out in the same manner as in Example 1, thereby obtaining a laminate (4b-3) in which the second to fourth resist layers were laminated in this order on the support. The resulting laminate (4b-3) was then subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

[0248] Regarding the laminate (4b-3) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive resin film A Second resist layer: 45 μm thick photosensitive resin film (4b) Third resist layer: 45 μm thick photosensitive resin film (4b) Fourth resist layer: 45 μm thick photosensitive resin film (4b)

[0249] A step of exposing a laminate to light, a step of developing the laminate, and a step of obtaining a hardened pattern: Next, the laminate (4b-3) after baking (PAB) was subjected to the same operations as in Example 1, including the step of exposing the laminate, the step of developing, and the step of obtaining a cured pattern, to obtain a spirally wound coil-shaped cured pattern using the photosensitive composition of Comparative Example 4.

[0250] [Evaluation of cured pattern shape] The spirally wound coil-shaped cured patterns formed in each example by the above <Formation of Cured Patterns> were observed from above, and OM (optical microscope) images (magnification 100x) were obtained. The OM images are shown in Figures 5 to 9.

[0251] FIG. 5 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Example 1. As shown in FIG. 5, the spirally wound coil-shaped cured pattern using the photosensitive composition of Example 1 had uniform widths between patterns and was a well-shaped cured pattern.

[0252] FIG. 6 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 1. As shown in FIG. 6, the spirally wound coil-shaped cured pattern using the photosensitive composition of Comparative Example 1 collapsed entirely during development or spin drying after development, peeled off from the substrate, and could not be observed.

[0253] FIG. 7 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 2. As shown in FIG. 7, the spirally wound coil-shaped cured pattern using the photosensitive composition of Comparative Example 2 did not collapse or peel off in the center, but from about the third turn from the inside, the cured pattern collapsed and leaned inward, or peeled off from the substrate and wound inward.

[0254] FIG. 8 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 3. As shown in FIG. 8, the spirally wound coil-shaped cured pattern using the photosensitive composition of Comparative Example 3 had peeled off from the substrate and shifted to one side from about the third turn from the center.

[0255] FIG. 9 is an OM image of a cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 4. As shown in FIG. 9, the cured pattern in the shape of a spirally wound coil using the photosensitive composition of Comparative Example 4 had the effect pattern peeled off from the third outermost turn and wrapped around the adjacent pattern. As shown in FIGS. 7 to 9, the cured patterns in the shape of a spirally wound coil using the photosensitive compositions of Comparative Examples 2 to 4 had non-uniform widths between the patterns.

[0256] From the above, it was confirmed that the photosensitive compositions of the Examples were able to form cured patterns with better shapes than the photosensitive compositions of the Comparative Examples.

[0257] While the preferred embodiment of the present invention has been described above with reference to the accompanying drawings, it goes without saying that the present invention is not limited to such an embodiment. The shapes and combinations of the components shown in the above example are merely examples, and various modifications can be made based on design requirements, etc., without departing from the spirit of the present invention. [Explanation of symbols]

[0258] 10 laminate, 10b exposed portion, 10c resin cured film, 10d unexposed portion, 11 first resist layer, 12 second resist layer, 13 third resist layer, 14 fourth resist layer, 20 support, 90 photomask, 110 resist pattern, 120 cured pattern

Claims

1. A composition comprising a polyfunctional aromatic epoxy compound, a photoacid generator, and a compound represented by general formula (ta1), The photosensitive composition includes a compound represented by the following general formula (I-0-1) and a compound represented by the following general formula (I3-1-1): 【Chemistry 1】 [In the formula, R EP represents an epoxy group-containing group. Multiple R EP s may be the same or different.] 【Chemistry 2】 [In the formula, R 001 to R 003 each independently represent a chain alkyl group having a fluorine atom. Ar 1 to Ar 3 each independently represent an aromatic hydrocarbon group which may have a substituent, and at least one is -Ar 001 -S-Ar 002 . However, Ar 1 to Ar 3 are not all -Ar 001 -S-Ar 002 . Ar 001 and Ar 002 each independently represent an aromatic hydrocarbon group which may have a substituent.] 【Transformation 3】 [In the formula, Rb １２ 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. Ar 11 to Ar 31 are each independently an aromatic hydrocarbon group which may have a substituent, and at least one is -Ar 001 -S-Ar 002 . Ar 001 and Ar 002 are each independently an aromatic hydrocarbon group which may have a substituent.]

2. 2. The photosensitive composition according to claim 1, wherein the content of the photoacid generator is 0.1 to 5 parts by mass based on 100 parts by mass of the polyfunctional aromatic epoxy compound.

3. forming a first resist layer on a support using a first photosensitive composition; forming a second resist layer on the first resist layer using a second photosensitive composition; A method for producing a laminate, comprising: A method for producing a laminate, comprising using the photosensitive composition according to claim 1 or 2 as the second photosensitive composition.

4. a step of exposing a laminate manufactured by the method for manufacturing a laminate according to claim 3 to light; developing the exposed laminate to form a resist pattern; a step of hardening the resist pattern to obtain a hardened pattern; A method for forming a hardened pattern, comprising:

5. The method for forming a cured pattern according to claim 4 , wherein the cured pattern is a spirally wound coil-shaped pattern.

6. The method for forming a hardened pattern according to claim 5 , wherein the hardened pattern constitutes an insulating portion of an inductor.

7. A laminate of a first resist layer and a second resist layer, A laminate, wherein the second resist layer is a resist layer formed from the photosensitive composition according to claim 1 or 2.

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