Method for manufacturing laminate, method for forming cured pattern, laminate, and photosensitive composition

Abstract

To provide a method for manufacturing a laminate which can be formed into a resin cured film that enables a high aspect of a pattern and is less likely to be peeled from a support, and a photosensitive composition which is useful as a material forming the lowest layer of the laminate.SOLUTION: A method for manufacturing a laminate 10 includes the steps of forming a first resist layer 11 on a support 20 using a first photosensitive composition, and forming a second resist layer 12 on the first resist layer 11 using a second photosensitive composition, wherein a photosensitive composition having sensitivity higher than that of the second photosensitive composition is used as the first photosensitive composition. The first photosensitive composition contains a polyfunctional aromatic epoxy compound, an optical acid generator, and an alicyclic epoxy compound.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a laminate, a method for forming a cured pattern, a laminate, and a photosensitive composition. [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. 5 is a partial cross-sectional view showing an example of a wire-wound inductor. Wire-wound inductor 200 shown in Fig. 5 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, a method for manufacturing a coil component has been proposed 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 multifunctionality 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 the insulating portion that constitutes the inductor. However, as the insulating portion becomes smaller, the aspect ratio of the cured pattern (cured resin film) that forms the insulating portion increases, and the contact area between the cured resin film and the support becomes smaller. In contrast, with conventional manufacturing methods, the cured resin film is prone to peeling off from the support, which can lead to short circuits.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminate that can achieve a high aspect ratio pattern and become a cured resin film that is not easily peeled off from a support, a method for producing the same, a photosensitive composition that is useful as a material for forming the bottom layer of the laminate, and a cured pattern. [Means for solving the problem]

[0007] Through investigation, the present inventors have discovered that when forming a coil-shaped cured pattern (cured resin film) that will become the insulating part of a wire-wound inductor, a laminate of a first resist layer and a second resist layer can be utilized, and the sensitivity of the first photosensitive composition that is the material for the first resist layer that contacts the support can be made higher than the sensitivity of the second photosensitive composition that is the material for the second resist layer adjacent to the first resist layer, thereby improving adhesion between the support and the first resist layer and suppressing peeling of the cured resin film from the support and collapse of the cured pattern, thereby completing the present invention. In order to solve the above problems, the present invention employs the following configuration.

[0008] That is, a first 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 first photosensitive composition is a photosensitive composition having higher sensitivity than the second photosensitive composition.

[0009] A second 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 first aspect; developing the exposed laminate to form a resist pattern; and curing the resist pattern to obtain a cured pattern.

[0010] A third aspect of the present invention is a laminate of a first resist layer and a second resist layer, characterized in that the first resist layer is a layer containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1), and the second resist layer is a layer containing a polyfunctional aromatic epoxy compound and a photoacid generator (excluding those containing the alicyclic epoxy compound).

[0011] [ka] [In the formula, R 1 ~R 18 are each independently a hydrogen atom, a halogen atom, or an organic group. X is a divalent linking group or a single bond.

[0012] A fourth aspect of the present invention is a photosensitive composition for forming a layer of an insulating part in an inductor that comes into contact with a support, the photosensitive composition comprising a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1):

[0013] [ka] [In the formula, R 1 ~R 18 are each independently a hydrogen atom, a halogen atom, or an organic group. X is a divalent linking group or a single bond. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a laminate that can achieve a high aspect ratio pattern and become a cured resin film that is not easily peeled off from a support, a method for producing the same, a photosensitive composition that is useful as a material for forming the bottom layer of the laminate, and a cured pattern. [Brief explanation of the drawings]

[0015] [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] FIG. 1 is a partial cross-sectional view showing an example of a wire-wound inductor. DETAILED DESCRIPTION OF THE INVENTION

[0016] 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 the halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The term "fluorinated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "optionally substituted" includes both cases where a hydrogen atom (-H) is replaced with a monovalent group and where a methylene group (-CH2-) is replaced with a divalent group. The term "exposure" is a general concept that includes irradiation with radiation.

[0017] The present invention is characterized by the photosensitive material used to form the bottom layer (layer in contact with the support) of the cured pattern, which can constitute the insulating portion of the inductor, and known techniques can be applied to the structures other than the bottom layer. 1 to 4 are schematic diagrams illustrating an embodiment of a process for forming a cured pattern that constitutes an insulating portion in an inductor. The process for forming a cured pattern will be described below with reference to the accompanying drawings. In the drawings, components may be shown schematically to make them easier to see, and some components may be shown on different scales.

[0018] (Method of manufacturing laminate) A first 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. This method for producing a laminate is characterized in that the first photosensitive composition is a photosensitive composition having higher sensitivity than the second photosensitive composition.

[0019] 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.

[0020] 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, and the details of the first photosensitive composition and the second photosensitive composition will be described later.

[0021] <Process (i)> In step (i), a first resist layer 11 is formed on a support 20 using a first photosensitive composition. In this embodiment, the first photosensitive composition is a photosensitive composition having higher sensitivity than the second photosensitive composition used in step (ii) described below. 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.

[0022] 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.

[0023] 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.

[0024] The thickness of the first resist layer 11 (photosensitive resin film) is preferably 50 μm or less, more preferably 5 to 50 μm, and even more preferably 10 to 40 μm.

[0025] 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.

[0026] 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.

[0027] <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 a photosensitive composition having lower sensitivity than the first photosensitive composition. 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.

[0028] The thickness of the second resist layer 12 (photosensitive resin film) is preferably 80 μm or less, more preferably 40 to 80 μm, and even more preferably 50 to 70 μm.

[0029] 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.

[0030] <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.

[0031] 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 80 μm or less, more preferably 40 to 80 μm, and even more preferably 50 to 70 μm. The thickness of the fourth resist layer 14 (photosensitive resin film) is preferably 80 μm or less, more preferably 40 to 80 μm, and even more preferably 50 to 70 μm.

[0032] 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 60 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.

[0033] 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.

[0034] <Photosensitive composition> The method for producing a laminate of this embodiment is characterized in that a photosensitive composition having higher sensitivity than the second photosensitive composition is used as the first photosensitive composition.

[0035] The "photosensitive composition having higher sensitivity than the second photosensitive composition" refers to a photosensitive composition having an optimum exposure dose Eop (mJ / cm) at which a target resist pattern of a predetermined shape is formed when a resist pattern is formed under the same conditions using each photosensitive composition. 2 ) is smaller than the optimum exposure amount Eop when the second photosensitive composition is used.

[0036] For example, when attempting to form a line and space pattern (LS pattern) with a target size of 20 μm line width / 50 μm space width, when a 25 μm thick photosensitive resin film is irradiated with ghi rays and baked at 90° C. for 5 minutes after exposure, the difference (Eop(2)-Eop(1)) between the optimum exposure dose Eop(1) of the first photosensitive composition and the optimum exposure dose Eop(2) of the second photosensitive composition is preferably 10 (mJ / cm 2 ) or more, more preferably 30 (mJ / cm 2 ) or more, and more preferably 50 to 100 (mJ / cm 2 ) When the difference (Eop(2)-Eop(1)) is equal to or greater than the lower limit of the preferred range, the adhesion between the support and the first resist layer is strengthened, making it easier to produce a laminate that is less likely to peel off from the support.

[0037] As photosensitive compositions having different sensitivities when forming a resist pattern, it is preferable to use a combination of compositions having different radiation absorption properties during exposure, or a combination of compositions having different polymerization rates of the resin components.

[0038] Hereinafter, an example of a combination of compositions having different polymerization rates of the resin components, namely, a combination of a photosensitive composition (R1) as the first photosensitive composition and a photosensitive composition (R2) as the second photosensitive composition, will be described. The photosensitive composition (R1) and the photosensitive composition (R2) differ in that they contain an alicyclic epoxy compound represented by general formula (m1) or not.

[0039] ≪Photosensitive composition (R1)≫ One embodiment of the first photosensitive composition is a photosensitive composition (R1) containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1): Since this photosensitive composition (R1) contains an alicyclic epoxy compound represented by general formula (m1), the polymerization rate of the resin component is increased, thereby achieving high sensitivity when forming a resist pattern.

[0040] Photosensitive composition (R1), which is one embodiment of the first photosensitive composition, contains a polyfunctional aromatic epoxy compound (hereinafter also referred to as "component (A)"), a photoacid generator (hereinafter also referred to as "component (I)"), and an alicyclic epoxy compound (hereinafter also referred to as "component (m1)") represented by the following general formula (m1): When a photosensitive resin film (resist layer) is formed using such photosensitive composition (R1) and selectively exposed to light, 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.

[0041] Regarding the 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 (R1) of this embodiment include novolac-type epoxy resins and bisphenol-type epoxy resins.

[0042] <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).

[0043] [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.

[0044] 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.

[0045] In the formula (anv0), n1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0046] 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.

[0047] 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.

[0048] Regarding optionally substituted divalent hydrocarbon groups: 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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-.

[0054] 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.

[0055] 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.

[0056] 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, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or- Y 21 -OC(=O)-Y 22 -Medium, Y 21 and Y 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 22The 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.

[0057] Among them, R EP The epoxy group-containing group in is preferably a glycidyl group.

[0058] Additionally, suitable examples of the component (A1) include resins having a structural unit represented by the following general formula (anv1):

[0059] [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.

[0060] 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.

[0061] Specific examples of the constitutional unit represented by the formula (anv1) are shown below.

[0062] [ka]

[0063] 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).

[0064] [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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] R a24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The 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 a24Specific 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.

[0069] 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:

[0070] In the formula (anv3), R a27 R is an epoxy group-containing group or a hydrocarbon group which may have a substituent. a27 The epoxy group-containing group is R EP Similar to R a27 The hydrocarbon group which may have a substituent is R a24 is the same as:

[0071] Specific examples of the structural units represented by the formulae (anv2) to (anv3) are shown below.

[0072] [ka]

[0073] 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 %.

[0074] 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.).

[0075] As the component (A1), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition (R1) 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%.

[0076] <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.

[0077] Suitable examples of the component (A2) include epoxy resins represented by the following general formula (abp1):

[0078] [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.

[0079] 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 , R p2 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 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.

[0080] 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).

[0081] 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).

[0082] [ka]

[0083] Furthermore, examples of polyfunctional aromatic epoxy compounds other than those mentioned above include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, and inositol hexaglycidyl ether.

[0084] In the photosensitive composition (R1) of this embodiment, the component (A) preferably contains the component (A1). The polystyrene-equivalent weight average molecular weight of component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and even more preferably 300 to 200,000. By adjusting the weight average molecular weight within this range, peeling of the first resist layer from the support becomes less likely to occur.

[0085] The content of the component (A) in the photosensitive composition (R1) of the embodiment may be adjusted depending on the thickness of the first resist layer to be formed, etc.

[0086] Photoacid generator (component (I)): In the photosensitive composition (R1) of the embodiment, it is preferable to use, as the component (I), a cationic photopolymerization initiator that generates cations upon irradiation with active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF or ArF, X-rays, or electron beams, and the cations can serve as polymerization initiators. Examples of the component (I) used in the photosensitive composition (R1) of this embodiment include an onium borate salt (hereinafter also referred to as "component (I1)") and a cationic photopolymerization initiator other than the component (I1) (another cationic photopolymerization initiator).

[0087] Onium borate salts Onium borate salts (component (I1)) generate a relatively strong acid upon exposure. Therefore, by forming a pattern using a photosensitive composition (R1) containing component (I1), sufficient sensitivity can be obtained, resulting in the formation of a good pattern. Furthermore, the use of component (I1) reduces the risk of toxicity and metal corrosion. Suitable examples of the component (I1) include compounds represented by the following general formula (I1).

[0088] [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.

[0089] 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.

[0090] 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.

[0091] Cation part In the formula (I1), Q q+ Suitable examples of the cation include sulfonium cations and iodonium cations, and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0092] [ka] [In the formula, R 201 ~R 207 , and R 211 ~R 212 R each independently represents an aryl group, a heteroaryl group, an alkyl group, or an alkenyl group, which may have a substituent. 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 represents -C(=O)- or -C(=O)-O-. Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0093] R 201 ~R 207 , and R 211 ~R 212 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 , and R 211 ~R 212 Examples of the heteroaryl group in the above formula (I) include those in which some of the carbon atoms constituting the aryl group have been substituted with heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of this heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthene; examples of the substituted heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthen-9-one. R 201 ~R 207 , and R 211 ~R 212 The alkyl group in the formula (I) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (═O), an aryl group, and groups represented by the following formulas (ca-r-1) to (ca-r-10):

[0094] [ka] [In the formula, R' 201 are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group.

[0095] In the above formulas (ca-r-1) to (ca-r-10), R' 201 are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group.

[0096] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. 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.

[0097] R' 201 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, 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. R' 201Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in the above formula 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, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R' 201 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 ring (an aryl group: for example, a phenyl group, a naphthyl group, or an anthracenyl group); a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, 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); a group in which one hydrogen atom has been removed from a ring in which some of the hydrogen atoms constituting the aromatic ring have been substituted with an oxo group or the like (for example, anthraquinone); and a group in which one hydrogen atom has been removed from an aromatic heterocycle (for example, 9H-thioxanthene or 9H-thioxanthen-9-one). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0098] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is 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.

[0099] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0100] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples 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 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.

[0101] An optionally substituted chain alkyl group: R' 201 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. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heneicosyl group, and a docosyl group. 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.

[0102] An optionally substituted chain alkenyl group: R' 201 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the chain alkenyl groups mentioned above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0103] R' 201 Examples of the substituent in the cyclic group, chain alkyl group or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, the above-mentioned R' 201 Examples of the groups include a cyclic group, an alkylcarbonyl group, and a thienylcarbonyl group.

[0104] Among them, R' 201 is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

[0105] R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When they are bonded to each other to form a ring together with the sulfur atom in the formula, they may not contain a heteroatom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(applicable R Nis an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0106] In the formula (ca-3), R 208 ~R 209 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups, they may be bonded to each other to form a ring.

[0107] In the formula (ca-3), R 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in the formula (I) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

[0108] In the formula (ca-4) and formula (ca-5), Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. Y 201 The arylene group in R' 201Examples of the aromatic hydrocarbon group in the above formula include groups in which one hydrogen atom has been removed from the aryl groups exemplified above. Y 201 The alkylene group and alkenylene group in R' 201 Examples of the chain alkyl group and chain alkenyl group include groups in which one hydrogen atom has been removed from the groups exemplified above as the chain alkyl group and chain alkenyl group.

[0109] In the above formulas (ca-4) and (ca-5), x is 1 or 2. W 201 is an (x+1)-valent, i.e., a divalent or trivalent linking group. W 201 The divalent linking group in the formula (A1) is preferably a divalent hydrocarbon group which may have a substituent. EP The same groups as the optionally substituted divalent hydrocarbon groups exemplified by W are preferred. 201 The divalent linking group in may be linear, branched, or cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting of an arylene group alone is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred. W 201 The trivalent linking group in 201 Examples of the divalent linking group include a group in which one hydrogen atom has been removed from the divalent linking group shown in the formula (1), and a group in which the divalent linking group is further bonded to the divalent linking group shown in the formula (1). 201 The trivalent linking group in the formula (I) is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0110] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0111] [ka]

[0112] [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 the group

[0113] As the cation represented by the formula (ca-1), cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferred.

[0114] [ka]

[0115] [ka] [In the formula, R' 211 is an alkyl group. hal is a hydrogen atom or a halogen atom.

[0116] As the cation represented by the formula (ca-1), cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are also preferred.

[0117] [ka]

[0118] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0119] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0120] [ka]

[0121] Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0122] [ka]

[0123] As the cation represented by the formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferred.

[0124] [ka] [In the formula, R' 212 R' is an alkyl group or a hydrogen atom. 211 is an alkyl group.

[0125] Among the above, the cation part [(Q q+ ) 1 / q ] is preferably a cation represented by general formula (ca-1), more preferably a cation represented by each of formulas (ca-1-1) to (ca-1-48), and even more preferably a cation represented by formula (ca-1-25), (ca-1-29), (ca-1-35), (ca-1-47), or (ca-1-48).

[0126] Specific examples of suitable components (I1) are listed below.

[0127] [ka]

[0128] <Other cationic photopolymerization initiators> Examples of photocationic polymerization initiators other than the component (I1) include 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)").

[0129] (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, and therefore, when a pattern is formed using a photosensitive composition containing the component (I), sufficient sensitivity is obtained and a good pattern is formed.

[0130] [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.

[0131] [ka] [In the formula, R b06 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b06 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.

[0132] 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 b05The 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.

[0133] The anion moiety of the compound represented by formula (I2-1) is preferably represented by the following general formula (b0-2a).

[0134] [ka] [In the formula, R bf05 nb is a fluorinated alkyl group which may have a substituent. 1 is an integer between 1 and 5.

[0135] In formula (b0-2a), R bf05 The optionally substituted fluorinated alkyl group in R b05 The same applies to the optionally substituted fluorinated alkyl groups listed in the 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.

[0136] 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.

[0137] 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+ As the Q in the above formula (I1), q+ Among these, cations represented by general formula (ca-1) are preferred, with cations represented by formulas (ca-1-1) to (ca-1-48) being more preferred, and cations represented by formula (ca-1-25), (ca-1-29), (ca-1-35), and (ca-1-47) being even more preferred.

[0138] Specific examples of suitable components (I2) are listed below.

[0139] [ka]

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

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

[0142] {Component (I3-1)} Anion section In formula (I3-1), R b12 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and R' 201 Among the cyclic groups, chain alkyl groups and chain alkenyl groups in the explanation of (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 in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like (which may have a substituent other than a halogen atom); or a group in which one or more hydrogen atoms have been removed from camphor, or the like. R b12 The hydrocarbon group may have a substituent other than a halogen atom, and examples of the substituent include R b11 Examples of the substituents include those similar to the substituents other than halogen atoms that may be contained in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above formula. The phrase "may have a substituent other than a halogen atom" as used herein not only excludes 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).

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

[0144] [ka]

[0145] Cation part In formula (I3-1), M m+ is an m-valent organic cation. M m+ Suitable examples of the organic cation include the same cations as those represented by the general formulas (ca-1) to (ca-5) above, and among these, the cation represented by the general formula (ca-1) above is more preferred. 201 , R 202 , R 203 A sulfonium cation in which at least one of the above is an organic group having 16 or more carbon atoms (aryl group, heteroaryl group, alkyl group, or alkenyl group) which may have a substituent is particularly preferred because it improves resolution and roughness characteristics. The substituents that the organic group may have are the same as those described above, and include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (═O), an aryl group, and groups represented by the above formulas (ca-r-1) to (ca-r-10). The number of carbon atoms in the organic group (aryl group, heteroaryl group, alkyl group, or alkenyl group) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18. m+ Suitable organic cations include those represented by the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), (ca-1-46), and (ca-1-47), and among these, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0146] {Component (I3-2)} Anion section In formula (I3-2), R b11is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and R' 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.

[0147] Among these, R b11 As the substituent, an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a chain alkyl group which may have a substituent other than a halogen atom is preferred. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is 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.

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

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

[0150] V' 101 and V' 102 The alkylene group in may be a straight-chain alkylene group or a branched-chain alkylene group, and is preferably a straight-chain alkylene group. V' 101 and V' 102 Specific examples of the alkylene group in the formula (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' 201 A 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.

[0151] The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group. The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The chain alkyl group preferably has 1 to 10 carbon atoms, 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.

[0152] R b11 As the aryl 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.

[0153] [ka]

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

[0155] Furthermore, from the viewpoints of increasing the elasticity of the resin film and facilitating the formation of a fine structure without residue, component (I) is preferably a cationic photopolymerization initiator that generates an acid with a pKa (acid dissociation constant) of -5 or less upon exposure. By using a cationic photopolymerization initiator that generates an acid with a pKa of more preferably -6 or less, and even more preferably -8 or less, high sensitivity to exposure can be achieved. The lower limit of the pKa of the acid generated by component (I) is preferably -15 or more. By using a cationic photopolymerization initiator that generates an acid with such a suitable pKa, high sensitivity can be easily achieved. Here, "pKa (acid dissociation constant)" refers to a commonly used index indicating the acid strength of a substance of interest. In this specification, pKa is a value at a temperature of 25°C. The pKa value can be determined by measurement using known methods. Alternatively, a calculated value using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development) can also be used.

[0156] Specific examples of suitable components (I3) are listed below.

[0157] [ka]

[0158] As the component (I), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition (R1) of this embodiment, the component (I) is preferably at least one selected from the group consisting of the component (I1), the component (I2), and the component (I3); more preferably a composition containing the component (I1) and the component (I3); or a composition containing the component (I2) and the component (I3); even more preferably a composition containing the component (I1) and the component (I3); or a composition containing a compound represented by general formula (I2-1) and the component (I3); and particularly preferably a composition containing the component (I1) and a compound represented by general formula (I3-1); or a composition containing a compound represented by general formula (I2-1) and a compound represented by general formula (I3-1).

[0159] In the photosensitive composition (R1) of this embodiment, the content of the component (I) is preferably 0.1 to 5 parts by mass, more preferably 0.15 to 3 parts by mass, and even more preferably 0.2 to 1 part by mass, relative to 100 parts by mass of the total parts by mass of the component (A). When the content of component (I1) 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, making it easier to obtain a resist pattern with a good shape.

[0160] Alicyclic epoxy compounds (component (m1)) represented by general formula (m1):

[0161] [ka] [In the formula, R 1 ~R 18 are each independently a hydrogen atom, a halogen atom, or an organic group. X is a divalent linking group or a single bond.

[0162] In the formula (m1), R 1 ~R 18 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0163] In the formula (m1), R 1 ~R 18 Examples of the organic group in the formula include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group containing a group in which two or more of these groups are bonded together.

[0164] R 1 ~R 18 With regard to the organic group in the above, examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. Among alkyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are particularly preferred. Among alkenyl groups having 2 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms are preferred, and alkenyl groups having 2 to 4 carbon atoms are particularly preferred. Among alkynyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 10 carbon atoms are preferred, and alkynyl groups having 2 to 4 carbon atoms are particularly preferred.

[0165] R 1 ~R 18 With regard to the organic group in the above, examples of the alicyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, and a bridged cyclic hydrocarbon group having 4 to 15 carbon atoms. Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group. Examples of the cycloalkenyl group having 3 to 12 carbon atoms include a cyclohexenyl group. Examples of the bridged cyclic hydrocarbon group having 4 to 15 carbon atoms include a bicycloheptanyl group and a bicycloheptenyl group.

[0166] R 1 ~R 18 With respect to the organic group in the above, examples of the aromatic hydrocarbon group include aryl groups having 6 to 14 carbon atoms. Among aryl groups having 6 to 14 carbon atoms, aryl groups having 6 to 10 carbon atoms are preferred, and examples thereof include a phenyl group and a naphthyl group.

[0167] R 1 ~R 18 With regard to the organic group in the formula (I), examples of the "group having two or more of these bonded together" include cycloalkyl-substituted alkyl groups having 1 to 20 carbon atoms and having 3 to 12 carbon atoms, such as a cyclohexylmethyl group; alkyl-substituted cycloalkyl groups having 1 to 20 carbon atoms and having 3 to 12 carbon atoms, such as a methylcyclohexyl group; aralkyl groups having 7 to 18 carbon atoms, such as a benzyl group or a phenethyl group (particularly preferably, an aralkyl group having 7 to 10 carbon atoms); aryl-substituted alkenyl groups having 6 to 14 carbon atoms, such as a cinnamyl group; alkyl-substituted aryl groups having 1 to 20 carbon atoms, having 6 to 14 carbon atoms, such as a tolyl group; and alkenyl-substituted aryl groups having 2 to 20 carbon atoms, having 6 to 14 carbon atoms, such as a styryl group.

[0168] R 1 ~R 18 The organic group in may contain a heteroatom, and examples thereof include a hydrocarbon group containing an oxygen atom or a halogen atom, and an alkoxy group which may have a substituent. Examples of hydrocarbon groups containing an oxygen atom or a halogen atom include the above hydrocarbon groups in which at least one hydrogen atom has been substituted with a group containing an oxygen atom or a halogen atom.

[0169] Examples of the group having an oxygen atom include a hydroxy group; a hydroperoxy group; an alkoxy group having 1 to 10 carbon atoms (such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, or an isobutyloxy group); an alkenyloxy group having 2 to 10 carbon atoms (such as an allyloxy group); an aryloxy group having 6 to 14 carbon atoms (such as a tolyloxy group or a naphthyloxy group) which may have a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a halogen atom, and an alkoxy group having 1 to 10 carbon atoms; an aralkyloxy group having 7 to 18 carbon atoms (such as a benzyloxy group or a phenethyloxy group); an acyloxy group having 1 to 10 carbon atoms (such as an acetyloxy group, a propionyloxy group, a (meth)acryloyloxy group, or a benzoyloxy group); an alkoxycarbonyl group having 1 to 10 carbon atoms (such as a methoxycarbonyl group or an ethoxy group); aryloxycarbonyl groups having 6 to 14 carbon atoms (for example, phenoxycarbonyl, tolyloxycarbonyl, naphthyloxycarbonyl, etc.) which may have a substituent selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, halogen atoms, and alkoxy groups having 1 to 10 carbon atoms; aralkyloxycarbonyl groups having 7 to 18 carbon atoms (for example, benzyloxycarbonyl group); epoxy group-containing groups such as glycidyloxy groups; oxetanyl group-containing groups such as ethyloxetanyloxy groups; acyl groups having 1 to 10 carbon atoms (for example, acetyl, propionyl, benzoyl, etc.); an isocyanate group; a sulfo group; a carbamoyl group; an oxo group; or a group in which two or more of these are bonded via a single bond or an alkylene group having 1 to 10 carbon atoms.

[0170] Examples of the halogen atom in the halogen-containing hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0171] R 1 ~R 18Regarding the organic group, the alkoxy group includes an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group.

[0172] R 1 ~R 18 With regard to the organic group in the above, examples of the substituent that the alkoxy group may have include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an alkenylthio group having 2 to 10 carbon atoms, an arylthio group having 6 to 14 carbon atoms, an acyloxy group having 7 to 18 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkenylthio group having 2 to 10 carbon atoms, an arylthio group having 6 to 14 carbon atoms, an arylthio group having 7 to 18 carbon atoms, an arylthio group having 7 to 18 carbon atoms, an aryloxy group having 7 to 18 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aryloxy ... Examples include an aralkylthio group, a carboxy group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 6 to 14 carbon atoms, an aralkyloxycarbonyl group having 7 to 18 carbon atoms, an amino group, a mono- or di-alkylamino group having 1 to 10 carbon atoms, an acylamino group having 1 to 10 carbon atoms, an epoxy group-containing group, an oxetanyl group-containing group, an acyl group having 1 to 10 carbon atoms, an oxo group, or a group in which two or more of these are bonded via a single bond or an alkylene group having 1 to 10 carbon atoms.

[0173] R in the formula (m1) 1 ~R 18 Among the above, R is preferably a hydrogen atom, 1 ~R 18 It is particularly preferred that all of these are hydrogen atoms.

[0174] In the formula (m1), examples of the divalent linking group for X include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, an amide group, or a group in which a plurality of these groups are linked together. Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms (preferably linear or branched alkylene groups having 1 to 3 carbon atoms); cycloalkylene groups having 3 to 12 carbon atoms; and cycloalkylidene groups having 3 to 12 carbon atoms (preferably cycloalkylene groups having 3 to 6 carbon atoms or cycloalkylidene groups having 3 to 6 carbon atoms). Examples of the linear or branched alkylene group having 1 to 3 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the cycloalkylene group having 3 to 12 carbon atoms include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

[0175] Among the above, X in the formula (m1) is preferably a single bond.

[0176] Suitable examples of the (m1) component include 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, (3,4,3',4'-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, and 1,2-bis(3,4-epoxycyclohexan-1-yl)ethane.

[0177] As the component (m1), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition (R1) of this embodiment, the content of the component (m1) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the total parts by mass of the component (A). When the content of component (m1) is equal to or greater than the lower limit of the preferred range, high sensitivity is achieved during resist pattern formation, and adhesion between the support and the photosensitive resin film (first resist layer) is likely to be improved. On the other hand, when the content is equal to or less than the upper limit of the preferred range, film formation is facilitated.

[0178] Regarding optional ingredients: The photosensitive composition (R1) of this embodiment may contain other components (optional components) as needed, in addition to the above-described components (A), (I), and (m1). If desired, the photosensitive composition (R1) may contain, as appropriate, miscible additives such as 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.

[0179] Examples of metal oxides (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.

[0180] 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.

[0181] 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.

[0182] The photosensitive composition (R1) of this embodiment may further contain a solvent (hereinafter sometimes 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).

[0183] The component (S) may be used alone or as a mixed solvent of two or more types.

[0184] 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).

[0185] ≪Photosensitive composition (R2)≫ An embodiment of the second photosensitive composition is a photosensitive composition (R2) containing a polyfunctional aromatic epoxy compound and a photoacid generator (excluding those containing an alicyclic epoxy compound represented by the above general formula (m1)). As described above, the photosensitive composition (R1) and the photosensitive composition (R2) differ in that they contain an alicyclic epoxy compound represented by general formula (m1). This difference allows the photosensitive composition (R1) to be adjusted to have a higher sensitivity than the photosensitive composition (R2).

[0186] The photosensitive composition (R2), which is one embodiment of the second photosensitive composition, contains a polyfunctional aromatic epoxy compound and a photoacid generator. When a photosensitive resin film (resist layer) is formed using such a photosensitive composition (R2) and selectively exposed to light, an acid is generated from the photoacid generator in the exposed areas of the photosensitive resin film, and the epoxy groups in the polyfunctional aromatic epoxy compound 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.

[0187] Polyfunctional aromatic epoxy compounds: Examples of the polyfunctional aromatic epoxy compound contained in the photosensitive composition (R2) include the same polyfunctional aromatic epoxy compound (component (A)) contained in the above-mentioned photosensitive composition (R1). In the photosensitive composition (R2) of this embodiment, the polyfunctional aromatic epoxy compound that is preferably used is one that contains the above-mentioned component (A1). The content of the polyfunctional aromatic epoxy compound in the photosensitive composition (R2) of the embodiment may be adjusted depending on the thickness of the second resist layer to be formed, etc.

[0188] About Photoacid Generators: Examples of the photoacid generator contained in the photosensitive composition (R2) include the same photoacid generators (component (I)) contained in the above-mentioned photosensitive composition (R1). In the photosensitive composition (R2) of the present embodiment, the photoacid generator is preferably at least one selected from the group consisting of the above-described components (I1), (I2), and (I3), more preferably one containing the component (I1) or one containing a compound represented by general formula (I2-2), and even more preferably one containing the component (I1). In the photosensitive composition (R2) of this embodiment, the content of the photoacid generator is preferably 0.1 to 5 parts by mass, more preferably 0.15 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass, relative to 100 parts by mass of the total parts by mass of the polyfunctional aromatic epoxy compound.

[0189] Regarding optional ingredients: The photosensitive composition (R2) of this embodiment may contain other components (optional components) as needed, in addition to the polyfunctional aromatic epoxy compound and photoacid generator described above. If desired, the photosensitive composition (R2) may contain, as appropriate, miscible additives such as 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.

[0190] In the method for producing a laminate according to the first embodiment described above, a photosensitive composition having higher sensitivity than the second photosensitive composition for forming the second resist layer 12 is used as the first photosensitive composition for forming the first resist layer 11 in contact with the support 20. Therefore, this method for producing a laminate makes it possible to produce a laminate 10 that can become a cured resin film that is difficult to peel off from the support 20.

[0191] In one embodiment of the method for producing the laminate described above, a combination of compositions having different polymerization rates of the resin components is used as the first photosensitive composition and the second photosensitive composition. However, the present invention is not limited to this combination as long as the two compositions have different sensitivities.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] (Method for forming a cured pattern) A second 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 first aspect; developing the exposed laminate to form a resist pattern; and curing the resist pattern to obtain a cured pattern.

[0196] 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 described below.

[0197] <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 coil-shaped pattern 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 exposure, and an unexposed portion 10d that remains unchanged.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] <Process (v)> In the step (v), the exposed laminate 10 is developed to form a coil-shaped resist pattern 110. For example, in the case of a combination of a photosensitive composition (R1) as the first photosensitive composition and a photosensitive composition (R2) as the second photosensitive composition, the exposed laminate 10 is developed with a developer containing an organic solvent (organic developer), whereby the unexposed portions 10d of the laminate 10 are dissolved and removed, and the exposed portions 10b remain as residual images, thereby forming a negative resist pattern 110, as shown in FIG. 3. After development, a rinse treatment is preferably carried out, and a bake treatment (post-bake) may be carried out as necessary.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0206] 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.

[0207] 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).

[0208] 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.

[0209] <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.

[0210] Regarding cure pattern 120: 4, the cured pattern 120 is a coil-shaped pattern and can constitute an insulating portion of the inductor as a permanent film. Then, 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 aspect ratio (h / w) of the cured pattern 120 is, for example, 1 to 80.

[0211] The method for forming a cured pattern according to the second aspect described above uses the laminate 10 manufactured by the method for manufacturing a laminate according to the first aspect. Therefore, this method for forming a cured pattern makes it possible to manufacture a cured resin film 10c that is difficult to peel off from the support 20.

[0212] In the above-described embodiment, a photosensitive composition (R1) is used as the first photosensitive composition, and a photosensitive composition (R2) is used as the second photosensitive composition. The photosensitive compositions (R1) and (R2) differ in that they contain an alicyclic epoxy compound (component (m1)) represented by general formula (m1). In the laminate 10, a first resist layer 11 and a second resist layer 12 are laminated in this order on a support 20. The first resist layer 11 is formed from a photosensitive composition (R1), and the second resist layer 12 is formed from a photosensitive composition (R2). The component (m1) contained in the photosensitive composition (R1) has a higher rate of ring-opening polymerization of the epoxy group than aromatic epoxy compounds, and therefore the photosensitive composition (R1) containing the component (m1) has an increased polymerization rate of the resin component, resulting in higher sensitivity. Furthermore, when forming the resist pattern 110, the first resist layer 11 in contact with the support 20 is made more sensitive than the photosensitive composition (R2) for forming the second resist layer 12 adjacent to the first resist layer 11, thereby strengthening the adhesion between the support 20 and the first resist layer 11. This allows for a high aspect ratio pattern, forms a cured resin film 10c that is not easily peeled off from the support 20, and suppresses pattern collapse, thereby enabling the stable production of a coil-shaped cured pattern 120.

[0213] 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.

[0214] 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).

[0215] (Laminate) A third aspect of the present invention is a laminate of a first resist layer and a second resist layer, characterized in that the first resist layer is a layer containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1), and the second resist layer is a layer containing a polyfunctional aromatic epoxy compound and a photoacid generator (excluding those containing the alicyclic epoxy compound).

[0216] [ka] [In the formula, R 1 ~R 18 are each independently a hydrogen atom, a halogen atom, or an organic group. X is a divalent linking group or a single bond.

[0217] 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). The explanation about the first resist layer is the same as the explanation about the first resist layer 11 described above, and the explanation about the polyfunctional aromatic epoxy compound, the photoacid generator, the alicyclic epoxy compound represented by general formula (m1), and the optional components contained in the photosensitive composition (R1) for forming the first resist layer. The explanation about the second resist layer is the same as the explanation about the second resist layer 12 described above, and the explanation about the polyfunctional aromatic epoxy compound, the photoacid generator, and the optional components contained in the photosensitive composition (R2) for forming the second resist layer.

[0218] In the laminate according to the third aspect described above, the first resist layer and the second resist layer differ in whether they contain an alicyclic epoxy compound (component (m1)) represented by general formula (m1). This component (m1) exhibits a higher rate of ring-opening polymerization of the epoxy group than aromatic epoxy compounds, and therefore, the first resist layer containing component (m1) exhibits a higher polymerization rate of the resin component during resist pattern formation, thereby achieving higher sensitivity. When forming a resist pattern, the first resist layer in contact with the support is made more sensitive than the second resist layer adjacent to the first resist layer, thereby strengthening the adhesion between the support and the first resist layer. Therefore, with this laminate, it is possible to achieve a high aspect ratio pattern, form a cured resin film that is not easily peeled off from the support, and suppress pattern collapse, making it possible to stably produce a coil-shaped cured pattern.

[0219] (Photosensitive composition) A fourth aspect of the present invention is a photosensitive composition containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1): Such a photosensitive composition is suitable as a photosensitive composition for forming a layer in contact with a support of an insulating part in an inductor.

[0220] [ka] [In the formula, R 1 ~R 18 are each independently a hydrogen atom, a halogen atom, or an organic group. X is a divalent linking group or a single bond.

[0221] The explanation of this photosensitive composition is the same as the explanation of the photosensitive composition (R1) in the above (Method for producing a laminate). Such a photosensitive composition is useful as a material for forming the first resist layer in the above-mentioned (laminate), the first resist layer 11 in the laminate 10 shown in FIG. 1, i.e., the bottom layer of the laminate (the layer in contact with the support). [Example]

[0222] 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.

[0223] <Preparation of Photosensitive Composition> Each component shown in Table 1 was mixed and dissolved in propylene glycol monomethyl ether acetate (PGMEA), 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.

[0224] [Table 1]

[0225] 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. (A)-2: Novolac epoxy resin represented by the following chemical formula (A1-2), product name "EPICLON N-770", manufactured by DIC Corporation.

[0226] [ka]

[0227] (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 (I2-1-1). (I)-4: A photoacid generator represented by the following chemical formula (I1-5). (I)-5: A photoacid generator represented by the following chemical formula (I3-1-1).

[0228] [ka]

[0229] [ka]

[0230] (m1)-1: An alicyclic epoxy compound represented by the following chemical formula (m1-1), trade name "Celloxide 8000", manufactured by Daicel Corporation.

[0231] [ka]

[0232] <Measurement of sensitivity Eop of photosensitive composition> The sensitivity of the above photosensitive compositions (1) to (7) was measured as follows. Using the photosensitive compositions (1) to (7), a photosensitive resin film of each composition was formed to a thickness of 25 μm on a 5-inch silicon wafer. Thereafter, a mask having a pattern was brought into close contact with the photosensitive resin film using an aligner (PLA-501F, manufactured by Canon Inc.), and the photosensitive resin film was irradiated with ghi rays. Thereafter, post-exposure heating was carried out on a hot plate at 90°C for 5 minutes. Thereafter, puddle development was performed with PGMEA at 23°C for 120 seconds, followed by spin-drying to obtain a line and space pattern (hereinafter simply referred to as "LS pattern"). For evaluation of the optimum exposure dose (Eop), an LS pattern with a target size of 20 μm line width / 50 μm space width was obtained. In forming the LS pattern, the optimum exposure dose Eop (mJ / cm) at which the target LS pattern is formed is 2 The result was called "sensitivity Eop (mJ / cm 2 )" in Table 2.

[0233] <Formation of hardened pattern> Using the photosensitive compositions (1) to (7), attempts were made to form a coil-shaped cured pattern.

[0234] Preparation of laminated film: The photosensitive composition (4) was applied onto the substrate film using an applicator and dried in an oven at 70°C for 10 minutes to form a photosensitive resin film (4) with a thickness of 20 μm, thereby obtaining a photosensitive laminate film (F4).

[0235] Except for changing the photosensitive composition (4) to the photosensitive composition (5), the coating and drying were carried out as described above to form a photosensitive resin film (5) with a thickness of 20 μm on the substrate film, thereby obtaining a photosensitive laminate film (F5).

[0236] Except for changing the photosensitive composition (4) to the photosensitive composition (1), the coating and drying were carried out as described above to form a photosensitive resin film (1) with a thickness of 55 μm on the substrate film, thereby obtaining a photosensitive laminate film (F1).

[0237] Except for changing the photosensitive composition (4) to the photosensitive composition (2), the coating and drying were carried out as described above to form a photosensitive resin film (2a) with a thickness of 65 μm on the substrate film, thereby obtaining a photosensitive laminate film (F2a).

[0238] Except for changing the photosensitive composition (4) to the photosensitive composition (2), the coating and drying were carried out as described above to form a photosensitive resin film (2b) with a thickness of 55 μm on the substrate film, thereby obtaining a photosensitive laminate film (F2b).

[0239] Example 1 forming a first resist layer; The photosensitive resin film (4) formed on the base film of the laminated film (F4) 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 (4) and the support were adjacent to each other, thereby forming a first resist layer on the support.

[0240] forming a second resist layer; Next, the substrate film in contact with the photosensitive resin film (4) constituting the first resist layer was peeled off, and the exposed photosensitive resin film (4) and the photosensitive resin film (2a) formed on the substrate film of the laminated film (F2a) were laminated under conditions of 50°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (4a) of the support, the first resist layer, and the second resist layer.

[0241] forming a third resist layer; Next, the base film in contact with the photosensitive resin film (2a) constituting the second resist layer was peeled off, and the exposed photosensitive resin film (2a) and the photosensitive resin film (2a) formed on the base film of the laminated film (F2a) were laminated under conditions of 50°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (4b) of the laminate (4a) and the third resist layer.

[0242] forming a fourth resist layer; Next, the substrate film in contact with the photosensitive resin film (2a) constituting the third resist layer was peeled off, and the exposed photosensitive resin film (2a) and the photosensitive resin film (2a) formed on the substrate film of the laminated film (F2a) were laminated under conditions of 50°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (4) in which the first to fourth resist layers were laminated in this order on the support. The resulting laminate (4) was then subjected to baking (PAB) at a temperature of 40° C. for 30 minutes.

[0243] Regarding laminate (4) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 20 μm thick photosensitive resin film (4) Second resist layer: 65 μm thick photosensitive resin film (2a) Third resist layer: 65 μm thick photosensitive resin film (2a) Fourth resist layer: 65 μm thick photosensitive resin film (2a)

[0244] exposing the laminate to light: Next, the laminate (4) after the baking treatment (PAB) was irradiated with 1000 mJ / cm 2 using an aligner (PLA-501F, manufactured by Canon Inc.) through a mask having a coil-shaped pattern. 2 (i-line integrated value) was exposed. Thereafter, post-exposure baking was carried out on a hot plate at 60°C for 45 minutes.

[0245] Developing process: Next, the laminate (4) after the post-exposure baking was subjected to solvent development (dip, vertical) using PGMEA as a developer at 23° C. for 45 minutes to obtain a coil-shaped resist pattern. Thereafter, a rinse treatment was carried out with PGMEA for 1 minute.

[0246] 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 1 hour, to obtain a hardened pattern in the shape of a coil.

[0247] Example 2 Steps of forming first to fourth resist layers: A laminate (5) was obtained in the same manner as in Example 1, except that the laminate film (F4) was changed to the laminate film (F5), in which the first to fourth resist layers were laminated in this order on a 5-inch silicon substrate (support) containing bismaleimide triazine resin. The resulting laminate (5) was then subjected to baking (PAB) at a temperature of 40° C. for 30 minutes.

[0248] Regarding laminate (5) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 20 μm thick photosensitive resin film (5) Second resist layer: 65 μm thick photosensitive resin film (2a) Third resist layer: 65 μm thick photosensitive resin film (2a) Fourth resist layer: 65 μm thick photosensitive resin film (2a)

[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 (5) 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 coil-shaped cured pattern.

[0250] (Comparative Example 1) Steps of forming first to fourth resist layers: A laminate (1) was obtained in the same manner as in Example 1, except that the laminate film (F4) was changed to the laminate film (F1) and the laminate film (F2a) was changed to the laminate film (F2b), and the first to fourth resist layers were laminated in this order on a 5-inch silicon substrate (support) containing bismaleimide triazine resin. The resulting laminate (1) was then subjected to baking (PAB) at a temperature of 40° C. for 30 minutes.

[0251] Regarding laminate (1) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 55 μm thick photosensitive resin film (1) Second resist layer: 55 μm thick photosensitive resin film (2b) Third resist layer: 55 μm thick photosensitive resin film (2b) Fourth resist layer: 55 μm thick photosensitive resin film (2b)

[0252] Step of exposing and developing the laminate: Next, the laminate (1) after the baking treatment (PAB) was subjected to the steps of exposing the laminate and developing it in the same manner as in Example 1. As a result, the laminate (1) was peeled off and removed from the support, and it was not possible to form a coil-shaped resist pattern.

[0253] (Comparative Example 2) Steps of forming first to fourth resist layers: A laminate (2) was obtained in the same manner as in Example 1, except that the laminate film (F4) was changed to the laminate film (F2b) and, in addition, the laminate film (F2a) was changed to the laminate film (F2b). The laminate (2) had first to fourth resist layers laminated in this order on a 5-inch silicon substrate (support) containing bismaleimide triazine resin. The resulting laminate (2) was then subjected to baking (PAB) at a temperature of 40° C. for 30 minutes.

[0254] Regarding laminate (2) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 55 μm thick photosensitive resin film (2b) Second resist layer: 55 μm thick photosensitive resin film (2b) Third resist layer: 55 μm thick photosensitive resin film (2b) Fourth resist layer: 55 μm thick photosensitive resin film (2b)

[0255] Step of exposing and developing the laminate: Next, the laminate (2) after baking (PAB) was subjected to the steps of exposing the laminate and developing it in the same manner as in Example 1. As a result, the laminate (2) was peeled off and removed from the support, and it was not possible to form a coil-shaped resist pattern.

[0256] Example 3 forming a first resist layer; The photosensitive composition (6) was applied onto the support using a spinner, prebaked (PAB) on a hot plate at 90°C for 5 minutes, and dried to form a photosensitive resin film (6) with a thickness of 25 μm as a first resist layer.

[0257] forming a second resist layer; Next, the photosensitive resin film (6) constituting the first resist layer and the photosensitive resin film (2b) formed on the base film of the laminated film (F2b) were laminated under conditions of 40°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (6a) of the support, the first resist layer, and the second resist layer.

[0258] forming a third resist layer; Next, the base film in contact with the photosensitive resin film (2b) constituting the second resist layer was peeled off, and the exposed photosensitive resin film (2b) and the photosensitive resin film (2b) formed on the base film of the laminated film (F2b) were laminated under conditions of 40°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (6b) of the laminate (6a) and the third resist layer.

[0259] forming a fourth resist layer; Next, the substrate film in contact with the photosensitive resin film (2b) constituting the third resist layer was peeled off, and the exposed photosensitive resin film (2b) and the photosensitive resin film (2b) formed on the substrate film of the laminated film (F2b) were laminated under conditions of 40°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (6) in which the first to fourth resist layers were laminated in this order on the support. The resulting laminate (6) was then subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

[0260] Regarding laminate (6) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 25 μm thick photosensitive resin film (6) Second resist layer: 55 μm thick photosensitive resin film (2b) Third resist layer: 55 μm thick photosensitive resin film (2b) Fourth resist layer: 55 μm thick photosensitive resin film (2b)

[0261] exposing the laminate to light: Next, the laminate (6) after the baking treatment (PAB) was irradiated with 1000 mJ / cm 2 using an aligner (PLA-501F, manufactured by Canon Inc.) through a mask having a coil-shaped pattern. 2 (i-line integrated value) was exposed. Thereafter, post-exposure baking was carried out on a hot plate at 60°C for 45 minutes.

[0262] Developing process: Next, the laminate (6) after the post-exposure baking was subjected to solvent development (dip, vertical) using PGMEA as a developer at 23° C. for 40 minutes to obtain a coil-shaped resist pattern. Thereafter, a rinsing treatment was carried out with PGMEA for 5 minutes.

[0263] 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 1 hour, to obtain a hardened pattern in the shape of a coil.

[0264] Example 4 forming a first resist layer; The photosensitive composition (7) was applied onto the support using a spinner, prebaked (PAB) on a hot plate at 90°C for 5 minutes, and dried to form a photosensitive resin film (7) with a thickness of 25 μm as a first resist layer.

[0265] 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 (7), which is the first resist layer, were carried out in the same manner as in Example 3, thereby obtaining a laminate (7) in which the first to fourth resist layers were laminated in this order on the support. The resulting laminate (7) was then subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

[0266] Regarding laminate (7) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 25 μm thick photosensitive resin film (7) Second resist layer: 55 μm thick photosensitive resin film (2b) Third resist layer: 55 μm thick photosensitive resin film (2b) Fourth resist layer: 55 μm thick photosensitive resin film (2b)

[0267] 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 (7) after baking (PAB) was subjected to the same operations as in Example 3, including the step of exposing the laminate, the step of developing, and the step of obtaining a cured pattern, to obtain a coil-shaped cured pattern.

[0268] (Comparative Example 3) forming a first resist layer; The photosensitive composition (3) was applied onto the support using a spinner, prebaked (PAB) on a hot plate at 90°C for 5 minutes, and dried to form a photosensitive resin film (3) with a thickness of 25 μm as a first resist layer.

[0269] 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 (3), which is the first resist layer, were carried out in the same manner as in Example 3, thereby obtaining a laminate (3) in which the first to fourth resist layers were laminated in this order on the support. The resulting laminate (3) was then subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

[0270] Regarding laminate (3) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 25 μm thick photosensitive resin film (3) Second resist layer: 55 μm thick photosensitive resin film (2b) Third resist layer: 55 μm thick photosensitive resin film (2b) Fourth resist layer: 55 μm thick photosensitive resin film (2b)

[0271] Step of exposing and developing the laminate: Next, the laminate (3) after baking (PAB) was subjected to the steps of exposing the laminate and developing it in the same manner as in Example 3. As a result, the laminate (3) was peeled off and removed from the support, and it was not possible to form a coil-shaped resist pattern.

[0272] In the above <Formation of Cured Pattern>, the state of each pattern after formation was visually evaluated by SEM observation (magnification: 500x). Such evaluation was performed based on the following evaluation criteria, and the results are shown in Table 2. Evaluation criteria A: The formation of a coil-shaped hardened pattern was confirmed. B: No laminate or curing pattern was observed. If the evaluation is A, it can be said that the adhesion between the support and the cured pattern (cured resin film) is strong, and the cured pattern is unlikely to peel off from the support.

[0273] [Table 2]

[0274] From the results shown in Table 2, it was confirmed that the methods for forming cured patterns in Examples 1 to 4 were capable of forming a laminate that can be made into a cured resin film with a high aspect ratio and that is resistant to peeling from a support, and a coil-shaped cured pattern.

[0275] It was confirmed that the photosensitive compositions (4) to (7) used in Examples 1 to 4 were more useful as materials for forming the bottom layer of the laminate than the photosensitive compositions (1) to (3) used in Comparative Examples 1 to 3.

[0276] 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]

[0277] 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. 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 photosensitive composition having a higher sensitivity than the second photosensitive composition is used as the first photosensitive composition; the first photosensitive composition is a photosensitive composition containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1): 【Chemistry 1】 [In the formula, R 1 to R 18 each independently represent a hydrogen atom, a halogen atom, or an organic group; and X represents a divalent linking group or a single bond.]

2. 2. The method for producing a laminate according to claim 1, wherein the second photosensitive composition is a photosensitive composition containing a polyfunctional aromatic epoxy compound and a photoacid generator (excluding those containing the alicyclic epoxy compound).

3. The method for producing a laminate according to claim 1 or 2, wherein the support comprises a substrate containing a bismaleimide triazine resin.

4. A method of 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 photosensitive composition having a higher sensitivity than the second photosensitive composition is used as the first photosensitive composition; The method for producing a laminate, wherein the support comprises a substrate containing a bismaleimide triazine resin.

5. a step of exposing a laminate manufactured by the method for manufacturing a laminate according to any one of claims 1 to 4 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:

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

7. A method for manufacturing 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 first photosensitive composition is a photosensitive composition having higher sensitivity than the second photosensitive composition; and exposing the laminate manufactured by the method for manufacturing a laminate. 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: The method for forming a cured pattern, wherein the cured pattern is a coil-shaped pattern.

8. The method for forming a hardened pattern according to claim 6 or 7, wherein the hardened pattern constitutes an insulating portion of an inductor.

9. A laminate of a first resist layer and a second resist layer, which is produced by the laminate production method according to claim 1, the first resist layer is a layer containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1): The laminate, wherein the second resist layer is a layer containing a polyfunctional aromatic epoxy compound and a photoacid generator (excluding those containing the alicyclic epoxy compound). 【Chemistry 2】 [In the formula, R １ ~R １８ are each independently a hydrogen atom, a halogen atom, or an organic group. X is a divalent linking group or a single bond.

10. a polyfunctional aromatic epoxy compound; a photoacid generator; an alicyclic epoxy compound represented by the following general formula (m1); Contains A photosensitive composition for forming a layer of an insulating portion of an inductor that contacts a support. 【Transformation 3】 [In the formula, R １ ~R １８ are each independently a hydrogen atom, a halogen atom, or an organic group. X is a divalent linking group or a single bond.

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