Manufacturing method of hollow structure and manufacturing method of hollow package

Abstract

To provide a production method that can stably produce a hollow structure that prevents the deformation of a top plate part due to curing operation and has enhanced strength.SOLUTION: A method for producing a hollow structure 100 includes the steps of: disposing a photosensitive resist film 80 having a negative photosensitive resin film 30; exposing the disposed photosensitive resin film 30; heating the exposed photosensitive resin film 30; developing the heated photosensitive resin film 30A, 30B to form a negative pattern 30A; and further heating the developed negative pattern 30A to cure it, thereby making the hollow structure 100 in which the top plate part is composed of a cured body 40 of the photosensitive resin film. Heating after development is performed by the operation of heating for 10 min. or longer at 150°C or lower and then heating at higher than 150°C, or the operation of applying ultraviolet rays and then heating at 100°C or higher.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for manufacturing a hollow structure and a method for manufacturing a hollow package. [Background technology]

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

[0003] For example, Patent Document 1 discloses a method for manufacturing a hollow package, which includes a process for producing a hollow structure by forming a cavity securing portion to cover Micro Electro Mechanical Systems (MEMS) formed on a substrate, and a process for sealing the entire hollow structure with a sealing layer by transfer molding.

[0004] The cavity securing portion is formed as follows. After applying a photosensitive resin composition around the MEMS, side walls are created by exposing the composition through a photomask, post-exposure baking (PEB), and developing. Next, the cover film is peeled off from the dry film resist, which is made of a base film, a photosensitive resin composition layer, and a cover film laminated in that order, and the resulting film is laminated above the side wall to form a top plate portion. Exposure, PEB, and development are then performed again through a photomask, and unnecessary portions are removed to form a cavity securing portion. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2009 / 151050 Summary of the Invention [Problem to be solved by the invention]

[0006] When producing a hollow structural body, generally, the cavity-reserving portion after development is further subjected to a heat treatment (curing operation) at a high temperature of, for example, 200° C. or higher in order to increase the strength of the cured film of the photosensitive resin composition layer. However, the method for producing a hollow structural body described in Patent Document 1 has a problem in that the film-like top plate portion is easily deformed by the curing operation when the cavity securing portion is formed.

[0007] In addition, as the development of microelectronic devices progresses, there is currently a demand for modules to be made even thinner, and therefore, in the above-mentioned package, it is necessary to miniaturize the hollow structure while ensuring space in the vicinity of the electrodes formed on the wiring substrate. However, when attempting to miniaturize the hollow structure in this manner, the strength of a cured film obtained by curing a conventional negative photosensitive resin composition or photosensitive resist film is insufficient, and it may become difficult to maintain the hollow structure against, for example, the high pressure applied during molding.

[0008] The present invention has been made in consideration of the above-mentioned circumstances, and has an objective of providing a method for manufacturing a hollow structure and a method for manufacturing a hollow package, which suppresses deformation of the top plate due to the curing operation and can stably produce a hollow structure with increased strength. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a method for producing a hollow structural body comprising a recess and a top plate portion that closes an opening of the recess, the method comprising the steps of: preparing a substrate having a recess on its surface; and a photosensitive resist film having a negative photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid upon exposure; arranging the photosensitive resist film so that the surface of the photosensitive resin film of the photosensitive resist film closes the opening of the recess in the substrate; exposing the photosensitive resin film after the step (i); and exposing the photosensitive resin film to light after the step (ii). The method for producing a hollow structure includes: step (iii) of performing a heat treatment; step (iv) of developing the photosensitive resin film after step (iii) to form a negative pattern; and step (v) of further performing a heat treatment on the negative pattern after step (iv) to harden it, thereby obtaining a hollow structure whose top plate portion is made of the hardened photosensitive resin film, characterized in that the heat treatment in step (v) is performed by heating at a temperature of 150°C or less for 10 minutes or more, followed by an operation (x) of further heating at a temperature exceeding 150°C, or an operation (y) of irradiating with ultraviolet light and then heating at a temperature of 100°C or higher.

[0010] A second aspect of the present invention is a method for producing a hollow package, comprising the step of sealing a hollow structure produced by the production method according to the first aspect with a sealing material to obtain a hollow package. Effect of the Invention

[0011] According to the present invention, it is possible to provide a method for manufacturing a hollow structure and a method for manufacturing a hollow package, which can suppress deformation of the top plate due to a curing operation and stably produce a hollow structure with increased strength. [Brief description of the drawings]

[0012] [Figure 1] 1A to 1C are schematic diagrams illustrating a method for manufacturing a hollow structure according to a first embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In this specification and the claims, the term "aliphatic" is a relative concept to aromaticity and is defined as meaning a group or compound that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The term "halogenated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms. The term "fluorinated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The term "optionally substituted" refers to the case where a hydrogen atom (-H) is replaced with a monovalent group, or the case where a methylene group (-CH 2 -) is replaced with a divalent group. The term "exposure" is intended to include any concept including irradiation with radiation.

[0014] (Manufacturing method of hollow structure) The manufacturing method according to the first aspect of the present invention is a method for manufacturing a hollow structural body consisting of a recess and a top plate portion covering the opening of the recess, and includes the following step (0) and steps (i) to (v). In addition, in the manufacturing method according to the first aspect, the heat treatment in step (v) is performed by heating at a temperature of 150°C or less for 10 minutes or more, and then further heating at a temperature exceeding 150°C (x), or by irradiating with ultraviolet light and then heating at a temperature of 100°C or more (y).

[0015] Step (0): A step of preparing a substrate having a recess on its surface and a photosensitive resist film having a negative photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid upon exposure. Step (i): A step of disposing the photosensitive resist film so that a photosensitive resin film surface of the photosensitive resist film covers an opening surface of the recess in the substrate. Step (ii): After step (i), a step of exposing the photosensitive resin film to light. Step (iii): A step of subjecting the photosensitive resin film after step (ii) to a heat treatment. Step (iv): After step (iii), the photosensitive resin film is developed to form a negative pattern. Step (v): A step of hardening the negative pattern after step (iv) by further heating the negative pattern to obtain a hollow structural body in which the top plate portion is made of the hardened product of the photosensitive resin film.

[0016] The hollow structure manufactured by the manufacturing method according to the present embodiment comprises a recess and a top plate portion that closes the opening of the recess. The hollow structure can be suitably used for hollow packages used in SAW filters, MEMS, various sensors, etc.

[0017] [Process(0)] In step (0) of this embodiment, a substrate having a recess on its surface and a photosensitive resist film having a negative photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid upon exposure are prepared.

[0018] <Substrates with concave portions on the surface> Examples of substrates having a recess on their surface include structures in which a pattern is formed on a substrate, stepped substrates, etc. The recess may be made of either an organic material or an inorganic material. Such a substrate having a recess on its surface can be manufactured by a method including, for example, a step of forming a photosensitive resin film on a support using a negative photosensitive resin composition (hereinafter referred to as a "film forming step"), a step of exposing the photosensitive resin film (hereinafter referred to as an "exposure step"), and a step of developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern that becomes the sidewall of the recess (hereinafter referred to as a "development step"). The method for manufacturing such a substrate having a recess on its surface can be carried out as follows.

[0019] Film formation process: First, a negative photosensitive resin composition is applied onto a support by a known method such as spin coating, roll coating, or screen printing, and then baked (post-applied bake (PAB)) for 2 to 60 minutes at a temperature of 50 to 150°C to form a photosensitive resin film. The film-forming step can also be performed by disposing a photosensitive resin composition layer, which has been prepared in advance using a negative photosensitive resin composition, on a support.

[0020] The support is not particularly limited, and any conventionally known support can be used. For example, a substrate for electronic components, a substrate having a predetermined wiring pattern formed thereon, and the like can be mentioned. As substrates for electronic components, more specifically, silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO 3 ), niobium, lithium niobate (LiNbO 3 ), palladium, titanium tungsten, copper, chromium, iron, aluminum, or other metal substrates, and glass substrates are examples of the substrates. The wiring pattern may be made of a material such as copper, aluminum, nickel, or gold.

[0021] The thickness of the photosensitive resin film formed from the negative photosensitive resin composition is not particularly limited, but is preferably about 10 to 100 μm.

[0022] Exposure process: Next, the formed photosensitive resin film is selectively exposed using a known exposure device by exposure through a mask (mask pattern) having a predetermined pattern formed thereon, or by drawing by direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) as necessary at a temperature condition of, for example, 80 to 150° C. for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds.

[0023] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays having a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm), or visible light is selectively irradiated (exposed). As the radiation source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used. Here, radiation means ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc. For example, when an ultra-high pressure mercury lamp is used, it is 100 to 2000 mJ / cm. 2 It is.

[0024] The exposure method for the photosensitive resin film may be a normal exposure method (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion lithography.

[0025] Development process: Next, the photosensitive resin film after the exposure is developed with a developer containing an organic solvent (organic developer). After the development, a rinse treatment is preferably performed. If necessary, a bake treatment (post-bake) may be performed.

[0026] The organic solvent contained in the organic developer can be appropriately selected from known organic solvents, specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0027] 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.

[0028] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples of the lactate include ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate.Among these, the ester solvent is preferably butyl acetate or PGMEA.

[0029] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0030] The organic developer may contain known additives as necessary. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants. The surfactant is preferably a non-ionic surfactant, and more preferably a non-ionic fluorine-based surfactant or a non-ionic silicon-based surfactant. When a surfactant is added, the amount added is usually from 0.001 to 5 mass %, preferably from 0.005 to 2 mass %, and more preferably from 0.01 to 0.5 mass %, based on the total amount of the organic developer.

[0031] The development process can be carried out by a known development method, such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it still for a certain period of time (paddle method), a method of spraying the developer on the surface of the support (spray method), and a method of continuously applying the developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).

[0032] The rinse treatment (cleaning treatment) using a rinse liquid can be carried out by a known rinse method, such as a method of continuously applying the rinse liquid onto a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse liquid for a certain period of time (dip method), or a method of spraying the rinse liquid onto the surface of the support (spray method). The rinsing treatment is preferably carried out using a rinsing liquid containing an organic solvent.

[0033] By the above-mentioned film forming step, exposure step, and development step, a substrate having a recess on its surface (a structure having a pattern formed on a substrate, a stepped substrate) can be manufactured. The thickness (horizontal dimension relative to the support) and height (vertical dimension relative to the support) of the side walls can be set appropriately based on the size of the hollow portion, which is determined according to the type of electronic device to be housed in the recess.

[0034] <About photosensitive resist film> The photosensitive resist film in this embodiment has a negative photosensitive resin film that contains an epoxy group-containing resin (A) (hereinafter referred to as "component (A)") and a photoinitiator (I) (hereinafter referred to as "component (I)") that generates an acid upon exposure to light. The components constituting the photosensitive resist film will be described in detail below.

[0035] When a photosensitive resin film is formed using such a photosensitive resist film and the photosensitive resin film is selectively exposed to light, an acid is generated from the component (I) in the exposed part of the photosensitive resin film, and the epoxy group in the component (A) undergoes ring-opening polymerization due to the action of the acid, and the solubility of the component (A) in a developer containing an organic solvent decreases, while the solubility of the component (A) in a developer containing an organic solvent does not change in the unexposed part of the photosensitive resin film, so that a difference in solubility in a developer containing an organic solvent occurs between the exposed part and the unexposed part of the photosensitive resin film. That is, the photosensitive resin film is negative type. Therefore, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed part is dissolved and removed, and a negative type pattern is formed.

[0036] Here, the negative photosensitive resin film of the photosensitive resist film is typically made of a B-stage (semi-cured) resin material. The photosensitive resist film may be a laminate film in which a photosensitive resin film is laminated on a substrate film.

[0037] Such a photosensitive resist film can be produced by applying a negative photosensitive resin composition in which the components (A) and (I) are dissolved in a solvent onto a substrate film, and then drying the composition to form a photosensitive resin film. The negative photosensitive resin composition may be applied onto the substrate film by a suitable method using an applicator, a blade coater, a lip coater, a comma coater, a film coater or the like. The thickness of the photosensitive resin film is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0038] The substrate film may be a known one, for example, a thermoplastic resin film. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 to 150 μm.

[0039] In the method for producing a hollow structural member according to this embodiment, steps (i) to (v) are carried out using the substrate having a recess on its surface, which is prepared in the above step (0), and a photosensitive resist film. As a method for producing a hollow structural body, for example, a first embodiment and a second embodiment shown below can be mentioned.

[0040] Hereinafter, each embodiment of the method for manufacturing a hollow structural body will be described with reference to the drawings.

[0041] First Embodiment This is a case where, in step (0), a photosensitive resist film consisting of a laminate film in which a photosensitive resin film is laminated on a substrate film is prepared, and steps (i), (ii), (iii), (iv), and (v) are carried out in this order. In addition, the heat treatment in the step (v) is carried out by heating at a temperature of 150°C or less for 10 minutes or more, and then further heating at a temperature exceeding 150°C as an operation (x).

[0042] FIG. 1 is a schematic diagram illustrating a method for producing a hollow structural body according to the first embodiment. 1, a substrate having a recess 15 on its surface is formed by a substrate 10 and a sidewall 20 formed on the substrate 10. The photosensitive resist film used is a laminated film 80 in which a photosensitive resin film 30 is laminated on a base film 50. In this embodiment, the side wall 20 is made of a photosensitive resin material. The photosensitive resin material forming the side wall 20 may be the same material as the photosensitive resin film forming the top plate portion, or may be a different material.

[0043] [Process (i)] In the step (i), the laminated film 80 is disposed so that the surface of the photosensitive resin film 30 of the photosensitive resist film (laminated film 80) covers the opening surface of the recess 15 in the substrate 10. 1, the laminated film 80 is disposed so as to face the substrate 10 via the side wall 20. A hollow sealed space is formed surrounded by the substrate 10, the side wall 20, and the photosensitive resin film 30.

[0044] [Process (D)] In step (D), after step (i), the base film 50 is peeled off from the photosensitive resin film 30 in the laminate film 80.

[0045] [Step (ii)] In the step (ii), the photosensitive resin film 30 is exposed to light. For example, the photosensitive resin film 30 is selectively exposed to light using a known exposure device through a photomask 60 on which a predetermined pattern is formed.

[0046] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays having a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm), or visible light is selectively irradiated (exposed). As the radiation source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used.

[0047] [Step (iii)] In the step (iii), the exposed photosensitive resin film 30 is subjected to a heat treatment, a so-called post-exposure bake (PEB) treatment. The PEB treatment is carried out, for example, at a temperature of 80 to 150° C. for 40 to 600 seconds, preferably 60 to 300 seconds. By the heat treatment in step (iii), the photosensitive resin film 30 after exposure becomes an exposed portion 30A where the epoxy groups in the component (A) have undergone ring-opening polymerization, and an unexposed portion 30B where no change occurs.

[0048] [Step (iv)] In the step (iv), the photosensitive resin film 30 after the PEB treatment is developed to form a negative pattern. The development here can be carried out in the same manner as in the development step in the above-mentioned [Step (0)]. After the development, a rinsing treatment is preferably carried out. By the development in step (iv), the unexposed portion 30B is dissolved and removed, and the exposed portion 30A, which becomes the top plate portion, remains as a negative pattern.

[0049] [Process (v)] In step (v), the developed negative pattern (exposed area 30A) is further hardened by a heat treatment (curing operation) to obtain a hollow structural body 100 whose top plate portion is made of a hardened body 40 of the photosensitive resin film 30. In Fig. 1, the hardened body 40 is formed by hardening the photosensitive resin material forming the side wall 20 and the photosensitive resin film 30, and is integrated with them. The heat treatment in step (v) is carried out by an operation (x) of heating at a temperature of 150° C. or less for 10 minutes or more (first heating) and then further heating at a temperature exceeding 150° C. (second heating).

[0050] Regarding operation (x): The operation (x) is an operation of carrying out a first heating step and then a second heating step.

[0051] The first heating refers to heating at a temperature of 150° C. or less for 10 minutes or more. The temperature and duration of the first heating are preferably 50° C. or higher and 150° C. or lower, more preferably 50° C. or higher and 125° C. or lower, and are preferably 30 minutes or higher and 120 minutes or lower, more preferably 60 minutes or higher and 90 minutes or lower. The heating operation in the first heating may be performed in one step or in two or more steps. For example, when the first heating is performed in two steps, the heating operation in the first heating is preferably performed by heating at a temperature of 50° C. to 90° C. for 30 minutes to 90 minutes, and then further heating at a temperature higher than 90° C. to 150° C. for 10 minutes to 60 minutes.

[0052] The second heating refers to heating at a temperature above 150°C. The temperature and duration of the second heating are preferably higher than 150° C. and not more than 250° C., more preferably 160° C. or higher and 220° C. or lower, and are preferably 30 minutes or higher and 120 minutes or lower, more preferably 60 minutes or higher and 90 minutes or lower. The heating operation in the second heating may be performed in one step or in two or more steps. For example, when the second heating is performed in two steps, the heating operation in the second heating is preferably performed by heating at a temperature higher than 150° C. and lower than 180° C. for 10 minutes or more and lower than 60 minutes, and then further heating at a temperature higher than 180° C. and lower than 220° C. for 30 minutes or more and lower than 90 minutes.

[0053] In the manufacturing method for a hollow structure according to the first embodiment, it is preferable to carry out the above-mentioned operation (x) of heating at a temperature of 50°C or higher and 125°C or lower for 10 minutes or more, and then further heating at a temperature of 160°C or higher for 30 minutes or more, since this inhibits deformation of the top plate portion and makes it easier to increase strength. In addition, in the above operation (x), it is preferable that the first heating is performed in two or more steps, and the second heating is performed in two or more steps. Furthermore, from the viewpoint of productivity (time cycle, etc.), it is more preferable that the above operation (x) is performed in two steps, and the second heating is also performed in two steps.

[0054] In the manufacturing method for hollow structural members according to the first embodiment described above, the heat treatment (curing operation) in step (v) is carried out by heating at a temperature of 150°C or less for 10 minutes or more, and then further heating at a temperature exceeding 150°C as an operation (x). In this way, by heating the developed negative pattern (exposed portion 30A) while increasing the temperature from lower to higher than 150°C, the expansion of air inside the hollow during the curing operation is suppressed more than ever before, and the hardening can be sufficiently advanced while reducing the internal pressure. Therefore, according to the first embodiment, deformation of the top plate due to the curing operation is suppressed, and a hollow structure with increased strength can be stably manufactured.

[0055] <Second embodiment> In step (0), a photosensitive resist film is prepared which is a laminated film in which a photosensitive resin film is laminated on a substrate film, and steps (i), (ii), (iii), (iv), and (v') are carried out in this order. In addition, the heat treatment in the step (v') is carried out by an operation (y) of heating at a temperature of 100°C or higher after irradiation with ultraviolet rays.

[0056] The explanation of steps (i), (ii), (iii) and (iv) in the second embodiment is the same as the explanation of steps (i), (ii), (iii) and (iv) in the first embodiment described above.

[0057] [Process (v')] In the step (v'), the negative pattern (exposed area) after development is further hardened by a heat treatment (curing operation) to obtain a hollow structure having a top plate made of a hardened photosensitive resin film. The heat treatment in step (v') is carried out by irradiating with ultraviolet light, followed by an operation (y) of heating at a temperature of 100°C or higher.

[0058] Regarding operation (y): The operation (y) is an operation of performing heating after irradiating with ultraviolet light. The ultraviolet irradiation is, for example, 1000 to 10000 mJ / cm 2 It is preferable to carry out the irradiation at a dose of 100 nm or less. The heating in the step (y) refers to heating at a temperature of 100° C. or higher. The heating temperature and duration in the step (y) are preferably 100° C. or higher and 200° C. or lower, more preferably 150° C. or higher and 180° C. or lower, and are preferably 15 minutes or higher and 120 minutes or lower, more preferably 30 minutes or higher and 90 minutes or lower. The heating operation in the step (y) may be carried out in one step or in two or more steps.

[0059] In the manufacturing method of the hollow structural member according to the second embodiment, in the above-mentioned step (y), the ultraviolet rays are irradiated at 1000 to 10000 mJ / cm because deformation of the top plate portion is suppressed and the strength is easily increased. 2 After the irradiation, it is preferable to carry out a heating operation at a temperature of 160° C. or higher for 30 minutes or longer.

[0060] In the manufacturing method for a hollow structural body according to the second embodiment described above, the heat treatment (curing operation) in step (v) is performed by an operation (y) of heating at a temperature of 100° C. or higher after irradiation with ultraviolet rays. In this way, by heating the negative pattern (exposed portion) after the development after irradiation with ultraviolet light, the heating temperature for the curing operation can be set to a lower temperature. This makes it possible to suppress the expansion of air inside the hollow more than before, thereby reducing the internal pressure. In addition, it is possible to sufficiently progress the curing of the negative pattern (exposed portion) after the development. Therefore, according to the second embodiment, deformation of the top plate portion due to the curing operation is suppressed, and a hollow structure with increased strength can be stably manufactured.

[0061] <Other embodiments> Regarding the manufacturing method for a hollow structure according to the embodiment described above, a case has been described in which a photosensitive resist film is prepared as a laminate film in which a photosensitive resin film is laminated on a base film. However, this is not limited to this, and it is also possible to prepare, for example, a single layer of photosensitive resin film, or a laminate in which a photosensitive resin film and a cover film are laminated in this order on a base film.

[0062] The cover film may be a known one, such as a polyethylene film, a polypropylene film, etc. The cover film is preferably a film having a smaller adhesive strength with the photosensitive resin film than the base film. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and further preferably 5 to 50 μm. The base film and the cover film may be made of the same film material or different film materials. When in use, for example, the cover film can be peeled off and the resulting laminate film can be made of a photosensitive resin film and a base film.

[0063] Furthermore, in the manufacturing method for hollow structures according to the above-mentioned embodiment, the peeling operation of the base film constituting the photosensitive resist film is performed between the steps (i) and (ii), but this is not limited thereto, and the peeling operation may be performed between the steps (ii) and (iii), or between the steps (iii) and (iv).

[0064] <Ingredients that make up photosensitive resist film> The photosensitive resist film in this embodiment has a negative photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid upon exposure to light.

[0065] Epoxy-containing resin (A): The epoxy group-containing resin (component (A)) is not particularly limited as long as it has a sufficient number of epoxy groups in one molecule to form a pattern by exposure. Examples of the component (A) include novolac type epoxy resins (Anv), bisphenol A type epoxy resins (Abp), bisphenol F type epoxy resins, aliphatic epoxy resins, and acrylic resins (Aac).

[0066] ··Novolac type epoxy resin (Anv) Suitable examples of the novolac epoxy resin (Anv) include resin (A1) (hereinafter also referred to as "component (A1)") represented by the following general formula (A1).

[0067] [ka] [In the formula, R p1 and R p2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 may be the same or different. p2 may be the same or different. 1 is an integer from 1 to 5. EP is an epoxy group-containing group. EP may be the same or different.

[0068] In the formula (A1), R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group, and examples of the cyclic alkyl group include a cyclobutyl group, and a cyclopentyl group. Among them, R p1 , R p2 As the alkyl group, a hydrogen atom or a linear or branched alkyl group is preferable, a hydrogen atom or a linear alkyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable. In formula (A1), a plurality of R p1may be the same or different. p2 may be the same or different from each other.

[0069] In formula (A1), n 1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0070] In formula (A1), R EP is an epoxy group-containing group. R EP The epoxy group-containing group is not particularly limited, and examples thereof include a group consisting of only epoxy groups; a group consisting of only alicyclic epoxy groups; and a group having an epoxy group or an alicyclic epoxy group and a divalent linking group. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically, is a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that is the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. The hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or the alicyclic epoxy group is linked via the divalent linking group bonded to an oxygen atom (—O—) in the formula.

[0071] 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.

[0072] Regarding the optionally substituted divalent hydrocarbon group: Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

[0073] The linear aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH 2 -], ethylene group [-(CH 2 ) 2 -], trimethylene group [-(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6, even more preferably 2 to 4, and most preferably 2 or 3. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc. alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3)CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 -, etc. alkyl ethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, etc.; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0074] Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms are removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0075] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0076] The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent, which may include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.

[0077] The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in the structure as the divalent hydrocarbon group may or may not have a substituent, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Examples of the halogenated alkyl group as the substituent include the alkyl groups in which some or all of the hydrogen atoms of the alkyl groups are substituted with the halogen atoms. In the alicyclic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) 2 -, -S(=O) 2 -O- is preferred.

[0078] In the aromatic hydrocarbon group as a divalent hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the alicyclic hydrocarbon group.

[0079] 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.

[0080] In the divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group); -S-, -S(=O) 2 -, -S(=O) 2 -O-, general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 , -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -, wherein Y 21 and Y 22 each independently represents a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 0 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -Medium, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same ones as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group. Y 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable. Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula − [Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 The group represented by the formula -Y21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH 2 ) a’ -C(=O)-O-(CH 2 ) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0081] Among them, R EP As the epoxy group-containing group in the formula (I), a glycidyl group is preferred.

[0082] Suitable examples of the novolac epoxy resin (Anv) include resins having a structural unit represented by the following general formula (anv1).

[0083] [ka] [In the formula, R EP is an epoxy group-containing group, R a22 , R a23 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.]

[0084] In formula (anv1), R a22 , R a23 The alkyl group having 1 to 5 carbon atoms is represented by R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is the same as that of R a22 , R a23 The halogen atom is preferably a chlorine atom or a bromine atom. In formula (anv1), R EP is R in the formula (A1). EP and a glycidyl group is preferred.

[0085] Specific examples of the constitutional unit represented by the above formula (anv1) are shown below.

[0086] [ka]

[0087] The novolac epoxy resin (Anv) may be a resin consisting of the structural unit (anv1) alone, or may be a resin having the structural unit (anv1) and other structural units. Examples of the other structural units include the structural units represented by the following general formulas (anv2) to (anv3).

[0088] [ka] [In the formula, R a24 R is a hydrocarbon group which may have a substituent. a25 ~R a26 , R a28 ~R a30 R each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. a27 represents an epoxy group-containing group or a hydrocarbon group which may have a substituent.

[0089] In formula (anv2), R a24 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include a linear or branched alkyl group, and a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

[0090] The branched alkyl group preferably has a carbon number of 3 to 10, and more preferably 3 to 5. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.

[0091] R a24 When is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0092] 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, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. R a24Specific examples of the aromatic hydrocarbon group in include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0093] In 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, and the alkyl group having 1 to 5 carbon atoms and the halogen atom are each independently selected from the above R a22 , R a23 is the same as:

[0094] In formula (anv3), R a27 R is an epoxy group-containing group or a hydrocarbon group which may have a substituent. a27 The epoxy group-containing group is represented by R EP is the same as R a27 The optionally substituted hydrocarbon group is R a24 is the same as:

[0095] Specific examples of the structural units represented by the above formulas (anv2) to (anv3) are shown below.

[0096] [ka]

[0097] When the novolac epoxy resin (Anv) has other structural units in addition to the structural unit (anv1), the proportion of each structural unit in the resin (Anv) is not particularly limited, but the total of structural units having an epoxy group relative to the total of all structural units constituting the resin (Anv) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %.

[0098] Bisphenol A epoxy resin (Abp) The bisphenol A type epoxy resin (Abp) includes an epoxy resin having a structure represented by the following general formula (abp1).

[0099] [ka] [In the formula, R EP is an epoxy group-containing group, R a31 , R a32 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 31 is an integer between 1 and 50.

[0100] In formula (abp1), R a31 , R a32 The alkyl group having 1 to 5 carbon atoms is represented by R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is the same as that of R a31 , R a32 is preferably a hydrogen atom or a methyl group. R EP is R in the formula (A1). EP and a glycidyl group is preferred.

[0101] Aliphatic epoxy resin, acrylic resin (Aac) Examples of the aliphatic epoxy resin and acrylic resin (Aac) include resins having epoxy group-containing units represented by the following general formulas (a1-1) and (a1-2), respectively.

[0102] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. 41 is a divalent hydrocarbon group which may have a substituent. 41 is an integer between 0 and 2. a41 , R a42 is an epoxy group-containing group. 42 is 0 or 1. 41 Is (na 43 +1)valent aliphatic hydrocarbon group. 43 is an integer between 1 and 3.

[0103] In the above formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms represented by R is preferably linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferable.

[0104] In the formula (a1-1), Va 41 is a divalent hydrocarbon group which may have a substituent, and R in the formula (A1) EP Examples of the divalent hydrocarbon group which may have a substituent include the same groups as those explained in the above. Among the above, Va 41The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, further preferably a linear aliphatic hydrocarbon group, and particularly preferably a linear alkylene group.

[0105] In formula (a1-1), na 41 is an integer of 0 to 2, and preferably 0 or 1.

[0106] In formulas (a1-1) and (a1-2), R a41 , R a42 is an epoxy group-containing group, and R EP is the same as:

[0107] In formula (a1-2), Wa 41 In (na 43 The aliphatic hydrocarbon group having a valence of +1 means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group in which a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure are combined.

[0108] In formula (a1-2), na 43 is an integer of 1 to 3, preferably 1 or 2.

[0109] Specific examples of the structural unit represented by formula (a1-1) or (a1-2) are shown below.

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] In the above formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R a51 R represents a divalent hydrocarbon group having 1 to 8 carbon atoms. a52 R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. a53 represents a hydrogen atom or a methyl group. 51 is an integer between 0 and 10. R a51 , R a52 , R a53 may be the same or different.

[0115] Furthermore, the acrylic resin (Aac) may have a structural unit derived from another polymerizable compound for the purpose of appropriately controlling the physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; fluoroalkyl esters such as ... Examples of suitable polymerizable compounds include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[0116] When the aliphatic epoxy resin or the acrylic resin (Aac) has other structural units, the content of the epoxy group-containing units in the resin is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and most preferably 15 to 25 mol%.

[0117] Suitable examples of the aliphatic epoxy resin include compounds containing a partial structure represented by the following general formula (m1) (hereinafter also referred to as "component (m1)").

[0118] [ka] [where n 2 is an integer from 1 to 4. * indicates a bond.

[0119] In formula (m1), n 2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0120] The component (m1) may be a compound in which a plurality of partial structures represented by the above general formula (m1) are bonded via a divalent linking group or a single bond. Among these, a compound in which a plurality of partial structures represented by the above general formula (m1) are bonded via a divalent linking group is preferred. The divalent linking group here is not particularly limited, but preferred examples include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, etc. The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are represented by R EP The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are the same as those described in (epoxy group-containing group), and among these, the divalent linking group containing a hetero atom is preferred. 21 A group represented by -C(=O)-O-, -C(=O)-OY 21 A group represented by Y - is more preferred. 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable.

[0121] Further, preferred examples of the aliphatic epoxy resin include the compound represented by the following general formula (m2) (hereinafter also referred to as "component (m2)").

[0122] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different.

[0123] In formula (m2), R EP is an epoxy group-containing group, and R EP is the same as:

[0124] As the component (A), one type may be used alone, or two or more types may be used in combination. The component (A) preferably contains at least one resin selected from the group consisting of novolac epoxy resins (Anv), bisphenol A epoxy resins (Abp), bisphenol F epoxy resins, aliphatic epoxy resins, and acrylic resins (Aac). Among these, it is more preferable that the component (A) contains at least one resin selected from the group consisting of novolac type epoxy resins (Anv), bisphenol A type resins (Abp), aliphatic epoxy resins, and acrylic resins (Aac). Among these, it is more preferable that the component (A) contains at least one resin selected from the group consisting of novolac epoxy resins (Anv), aliphatic epoxy resins, and acrylic resins (Aac), and it is particularly preferable that the component (A) contains at least a novolac epoxy resin (Anv).Of the novolac epoxy resins (Anv), it is preferable to use the component (A1). Furthermore, it is particularly preferable that the component (A) contains two or more resins selected from the group consisting of novolac epoxy resins (Anv), aliphatic epoxy resins, and acrylic resins (Aac).

[0125] When two or more kinds of components (A) are used in combination, it is preferable that the component (A) includes a combination of a novolac epoxy resin (Anv) and an aliphatic epoxy resin, since this improves the film properties (such as lamination properties) and strength when made into a photosensitive resist film. Specific examples of such combinations include a combination of the (A1) component with at least one selected from the group consisting of the (m1) component and the (m2) component (hereinafter referred to as "the (m) component"). Among these, the combination of the (A1) component, the (m1) component and the (m2) component is the most preferred.

[0126] When the (m1) component and the (m2) component are both present, the ratio of the (m1) component to the (m2) component, expressed as the mass ratio (m1) component / (m2) component, is preferably 2 / 8 to 8 / 2, more preferably 3 / 7 to 7 / 3, and even more preferably 4 / 6 to 6 / 4. If the mass ratio is within the above-mentioned preferred range, the film properties (such as lamination properties) and strength are further improved when the photosensitive resist film is formed.

[0127] In particular, the component (A) contains the component (A1), the component (m1), and the component (m2), and from the standpoint of the balance between strength and flexibility of the cured film, the proportion of the total content of the components (m1) and (m2) in the total content of the components (A1), (m1), and (m2) is preferably 15 mass% or more, more preferably 20 mass% or more, even more preferably 25 mass% or more, particularly preferably more than 25 mass%, and most preferably more than 25 mass% but not more than 30 mass%.

[0128] The polystyrene-equivalent weight average molecular weight of the component (A) is preferably 100 to 300000, more preferably 200 to 200000, and even more preferably 300 to 200000. By setting the weight average molecular weight within this range, peeling from the support is less likely to occur, and the strength of the cured film that is formed is sufficiently increased.

[0129] The component (A) preferably has a dispersity of at least 1.05, which leads to improved lithography properties during pattern formation. The degree of dispersion referred to here means a value obtained by dividing the mass average molecular weight by the number average molecular weight.

[0130] Commercially available products of the component (A) include, for example, novolac epoxy resins (Anv), such as JER-152, JER-154, JER-157S70, and JER-157S65 (all manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, and EPICLON HP5000 (all manufactured by DIC Corporation), and EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.).

[0131] Examples of bisphenol A type epoxy resins (Abp) include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (all manufactured by DIC Corporation), and the like.

[0132] Examples of bisphenol F type epoxy resins include JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (all manufactured by DIC Corporation), LCE-21, RE-602S (all manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0133] Examples of aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (manufactured by ADEKA Corporation), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (manufactured by Daicel Corporation), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation), and TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd.).

[0134] The content of the component (A) in the photosensitive resin film of the embodiment may be adjusted according to the film thickness of the photosensitive resin film to be formed, etc.

[0135] Photoinitiators that generate acid upon exposure (I) The photoinitiator (component (I)) is a compound that generates cations when irradiated with active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF or ArF, X-rays, electron beams, etc., and these cations can serve as polymerization initiators.

[0136] The component (I) in the photosensitive resin film of this embodiment is not particularly limited, and examples thereof include a compound represented by the following general formula (I1) (hereinafter referred to as "component (I1)"), a compound represented by the following general formula (I2-1) or (I2-2) (hereinafter referred to as "component (I2)"), and a compound represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "component (I3)"). Among the above, both the component (I1) and the component (I2) generate a relatively strong acid upon exposure to light. Therefore, when a pattern is formed using a photosensitive resin composition containing the component (I), sufficient sensitivity can be obtained and a good pattern can be formed.

[0137] Component (I1) The component (I1) is a compound represented by the following general formula (I1).

[0138] [ka] [In the formula, R b01 ~R b04 Each of Q is independently an aryl group which may have a substituent, or a fluorine atom. q is an integer of 1 or more, q+ are each independently an organic cation having a valence of q.

[0139] Anion section In the formula (I1), R b01 ~R b04 each independently represents an aryl group which may have a substituent, or a fluorine atom. R b01 ~R b04 The aryl group in the formula (I) preferably has a carbon number of 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include a naphthyl group, a phenyl group, and an anthracenyl group, and the phenyl group is preferred because of its easy availability. R b01 ~R b04 The aryl group in may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably having 1 to 5 carbon atoms), or a halogenated alkyl group, more preferably a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms, and particularly preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. When the aryl group has a fluorine atom, the polarity of the anion moiety is increased, which is preferable. Among them, R in formula (I1) b01 ~R b04 As each of these, a fluorinated phenyl group is preferable, and a perfluorophenyl group is particularly preferable.

[0140] A preferred example of the anion portion of the compound represented by formula (I1) is tetrakis(pentafluorophenyl)borate ([B(C 6 F 5 ) 4 ] -);Tetrakis[(trifluoromethyl)phenyl]borate ([B(C 6 H 4 CF 3 ) 4 ] - );Difluorobis(pentafluorophenyl)borate ([(C 6 F 5 ) 2 BF 2 ] - ); Trifluoro(pentafluorophenyl)borate ([(C 6 F 5 )B.F. 3 ] - );Tetrakis(difluorophenyl)borate ([B(C 6 H 3 F 2 ) 4 ] - ) etc. Among them, tetrakis(pentafluorophenyl)borate ([B(C 6 F 5 ) 4 ] - ) is particularly preferred.

[0141] ···Cation part In formula (I1), q is an integer of 1 or more, q+ are each independently a q-valent organic cation. This Q q+ Suitable examples of the cation include a sulfonium cation and an iodonium cation, and the organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0142] [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 , R211 ~R 212 may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO 2 -containing cyclic group. 201 represents -C(=O)- or -C(=O)-O-. 201 each independently represents an arylene group, an alkylene group, or an alkenylene group; x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0143] R 201 ~R 207 , and R 211 ~R 212 The aryl group in may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 , and R 211 ~R 212 The heteroaryl group in the above formula (I) may be one in which a part of the carbon atoms constituting the aryl group is replaced with a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthene; examples of the substituted heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthen-9-one. R 201 ~R 207 , and R 211 ~R 212 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212 Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, and groups represented by the following formulae (ca-r-1) to (ca-r-10).

[0144] [ka] [In the formula, R' 201 each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0145] In the above formulas (ca-r-1) to (ca-r-10), R' 201 each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0146] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0147] 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 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, the carbon number does not include the carbon atoms in the substituent. R' 201 Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in the above include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R' 201 Specific examples of the aromatic hydrocarbon group in the above include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, anthracenyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), a group in which one hydrogen atom has been removed from a ring in which some of the hydrogen atoms constituting the aromatic ring have been substituted with an oxo group or the like (for example, anthraquinone, etc.), and a group in which one hydrogen atom has been removed from an aromatic heterocycle (for example, 9H-thioxanthene, 9H-thioxanthen-9-one, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0148] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) includes an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system, such as a cyclic group having a steroid skeleton.

[0149] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0150] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, specifically, a methylene group [-CH 2 -], ethylene group [-(CH 2 ) 2 -], trimethylene group [-(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] etc. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, specifically, -CH(CH 3)-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc. alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 -, etc. alkyl ethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, etc.; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0151] Optionally substituted chain alkyl groups: R' 201 The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, and a docosyl group. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0152] 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, further 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 above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0153] 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' 201In the above formula, examples include a cyclic group, an alkylcarbonyl group, and a thienylcarbonyl group.

[0154] Among them, R' 201 is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

[0155] R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When they are bonded to each other to form a ring together with the sulfur atom in the formula, they are not included in the heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, as well as in the carbonyl groups, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )-(the R N is an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, in which a ring containing a sulfur atom in the ring skeleton in the formula is a 3- to 10-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0156] In the above 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.

[0157] In the above formula (ca-3), R 210 represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO 2-containing cyclic group. R 210 The aryl group in may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

[0158] In the above formula (ca-4) and formula (ca-5), Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. Y 201 The arylene group in R' 201 Examples of the aromatic hydrocarbon group in the above formula include groups in which one hydrogen atom has been removed from the aryl groups exemplified above. Y 201 The alkylene group and alkenylene group in R' 201 Examples of the chain alkyl group and the chain alkenyl group in the above formula (I) include groups in which one hydrogen atom has been removed from the groups exemplified as the chain alkyl group and the chain alkenyl group in the above formula (I).

[0159] In the above formulas (ca-4) and (ca-5), x is 1 or 2. W 201 is a (x+1)-valent linking group, that is, a divalent or trivalent linking group. W 201 The divalent linking group in the formula (A1) is preferably a divalent hydrocarbon group which may have a substituent. EP The divalent hydrocarbon groups which may have a substituent are preferably the same as those exemplified by W. 201 The divalent linking group in may be linear, branched, or cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting of an arylene group alone is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and the phenylene group is particularly preferred. W 201The trivalent linking group in 201 and a group in which one hydrogen atom has been removed from the divalent linking group represented by the formula: W 201 As the trivalent linking group in the formula (I), a group in which two carbonyl groups are bonded to an arylene group is preferable.

[0160] 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).

[0161] [ka]

[0162] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent. The substituent may be any of the above-mentioned R 201 ~R 207 , and R 210 ~R 212 The substituents are the same as those exemplified as the substituents that may be possessed by the

[0163] As the cation represented by the formula (ca-1), the cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferable.

[0164] [ka]

[0165] [ka] [In the formula, R' 211 is an alkyl group. hal is a hydrogen atom or a halogen atom.

[0166] As the cation represented by the formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-47) are also preferable.

[0167] [ka]

[0168] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0169] 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).

[0170] [ka]

[0171] 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).

[0172] [ka]

[0173] As the cation represented by the formula (ca-5), the cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferable.

[0174] [ka] [In the formula, R' 212 R' is an alkyl group or a hydrogen atom. 211 is an alkyl group.

[0175] Among the above, the cationic part [(Q q+ ) 1 / q ] is preferably a cation represented by general formula (ca-1), more preferably a cation represented by formulas (ca-1-1) to (ca-1-47), and even more preferably a cation represented by formulas (ca-1-25), (ca-1-29), (ca-1-35), and (ca-1-47).

[0176] ·(I2) component The component (I2) is a compound represented by the following general formula (I2-1) or (I2-2).

[0177] [ka] [In the formula, R b05 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b05 may be the same or different. q is an integer of 1 or more, and Q q+ is a q-valent organic cation.

[0178] [ka] [In the formula, R b06 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b06 may be the same or different. q is an integer of 1 or more, and Q q+ is a q-valent organic cation.

[0179] Anion section In the above formula (I2-1), R b05 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b05 may be the same or different from each other. R b05The fluorinated alkyl group in the above formula 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.

[0180] The anion portion of the compound represented by formula (I2-1) is preferably represented by the following general formula (b0-2a).

[0181] [ka] [In the formula, R bf05 is a fluorinated alkyl group which may have a substituent. 1 is an integer from 1 to 5.

[0182] In formula (b0-2a), R bf05 The optionally substituted fluorinated alkyl group in R b05 The substituents are the same as the optionally substituted fluorinated alkyl groups listed under 1. In formula (b0-2a), nb 1 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.

[0183] In the above formula (I2-2), R b06 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b06 may be the same or different from each other. R b06 The fluorinated alkyl group in the above formula 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 group, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a fluorine atom is even more preferable.

[0184] ···Cation part In formula (I2-1) and formula (I2-2), q is an integer of 1 or more, q+ are each independently a q-valent organic cation. This Q q+ Examples of the cations include those represented by formula (I1) above. Among them, the cations represented by general formula (ca-1) are preferred, the cations represented by formulas (ca-1-1) to (ca-1-47) are more preferred, and the cations represented by formulas (ca-1-25), (ca-1-29), (ca-1-35), and (ca-1-47) are even more preferred.

[0185] Component (I3) The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0186] [ka] [In the formula, R b11 ~R b12 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom. m is an integer of 1 or more, and M m+ are each independently an organic cation having a valence of m.

[0187] {Component (I3-1)} Anion section In formula (I3-1), R b12 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and R'201 Among the cyclic groups, chain alkyl groups, and chain alkenyl groups in the explanation of the above, those having no substituent or those having a substituent other than a halogen atom are exemplified. R b12 is preferably a chain alkyl group which may have a substituent other than a halogen atom, or an aliphatic cyclic group which may have a substituent other than a halogen atom. The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably 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); 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 the case where a substituent consists of only halogen atoms, but also excludes the case where a substituent contains at least one halogen atom (for example, the case where the substituent is a fluorinated alkyl group, etc.).

[0188] Preferred specific examples of the anion portion of the component (I3-1) are shown below.

[0189] [ka]

[0190] ···Cation part In formula (I3-1), M m+ is an m-valent organic cation. M m+Suitable examples of the organic cation include the cations represented by the above general formulas (ca-1) to (ca-5), and among these, the cation represented by the above general formula (ca-1) is more preferred. 201 , R 202 , R 203 A sulfonium cation in which at least one of the above is an organic group having 16 or more carbon atoms (aryl group, heteroaryl group, alkyl group, or alkenyl group) which may have a substituent is particularly preferred because it improves the resolution and roughness characteristics. The substituents that the organic group may have are the same as those described above, and include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, and groups represented by the above formulas (ca-r-1) to (ca-r-10). The number of carbon atoms in the organic group (aryl group, heteroaryl group, alkyl group, or alkenyl group) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18. m+ Suitable examples of the organic cation include the cations represented by the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), (ca-1-46), and (ca-1-47).

[0191] {Component (I3-2)} Anion section In formula (I3-2), R b11 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and R' 201 Among the cyclic groups, chain alkyl groups, and chain alkenyl groups in the explanation of the above, those having no substituent or those having a substituent other than a halogen atom are exemplified.

[0192] Among these, R b11As the substituent, an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a chain alkyl group which may have a substituent other than a halogen atom are preferable. The substituent which these groups may have includes a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be connected via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the following general formulas (y-al-1) to (y-al-7).

[0193] [ka] [In the formula, V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms, and V' 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.

[0194] 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.

[0195] V' 101 and V' 102 The alkylene group in may be a straight-chain alkylene group or a branched-chain alkylene group, and is preferably a straight-chain alkylene group. V' 101 and V' 102 Specific examples of the alkylene group in the formula include a methylene group [-CH 2 -];-CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3)(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; ethylene groups [-CH 2 CH 2 -];-CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, etc.; trimethylene group (n-propylene group) [-CH 2 CH 2 CH 2 -];-CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and other alkyl trimethylene groups; tetramethylene groups [-CH 2 CH 2 CH 2 CH 2 -];-CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyl tetramethylene groups; pentamethylene groups [-CH 2 CH 2 CH 2 CH 2 CH 2 -] etc. Also, V' 101 or V' 102 A part of the methylene groups in the alkylene group in the formula (I) may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is represented by R' 201A divalent group in which one hydrogen atom has been further removed from a cyclic aliphatic hydrocarbon group (a monocyclic alicyclic hydrocarbon group, a polycyclic alicyclic hydrocarbon group) such as those mentioned above is preferred, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferred.

[0196] The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group. The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The chain alkyl group preferably has 1 to 10 carbon atoms. Specific examples of the chain alkyl group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0197] R b11 is preferably a cyclic group which may have a substituent other than a halogen atom. Preferred specific examples of the anion portion of the component (I3-2) are shown below.

[0198] [ka]

[0199] ···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:

[0200] In addition, the component (I) is preferably a photoinitiator that generates an acid having a pKa (acid dissociation constant) of -5 or less upon exposure, from the viewpoints of increasing the elasticity of the resin film and facilitating the formation of a fine structure without residue. By using a photoinitiator that generates an acid having a pKa of -6 or less, more preferably a pKa of -8 or less, it is possible to obtain high sensitivity to exposure. The lower limit of the pKa of the acid generated by the component (I) is preferably -15 or more. By using a photoinitiator that generates an acid having such a suitable pKa, it is easy to achieve high sensitivity. Here, "pKa (acid dissociation constant)" refers to a commonly used index indicating the acid strength of a target substance. In this specification, pKa is a value at a temperature condition of 25°C. The pKa value can be determined by measurement using a known method. Alternatively, a calculated value using known software such as "ACD / Labs" (product name, manufactured by Advanced Chemistry Development) can be used.

[0201] Specific examples of suitable components (I) are listed below.

[0202] [ka]

[0203] [ka]

[0204] [ka]

[0205] As the component (I), one type may be used alone, or two or more types may be used in combination. The component (I) preferably contains two or more members selected from the group consisting of the components (I1), (I2), and (I3). Among these, it is more preferable to use the component (I) in combination with the components (I1) and (I2), or it is more preferable to use the component (I) in combination with one or more selected from the group consisting of the components (I1) and (I2), and the component (I3).

[0206] The content of the component (I) is preferably 0.5 to 6.0 parts by mass, more preferably 1.0 to 5.0 parts by mass, and even more preferably 1.0 to 3.0 parts by mass, per 100 parts by mass of the component (A). When the content of the component (I) is equal to or greater than the lower limit of the preferred range, sufficient sensitivity is obtained, and the lithography properties of the pattern are further improved. In addition, the strength of the cured film is further increased. On the other hand, when the content is equal to or less than the upper limit of the preferred range, the sensitivity is appropriately controlled, and a pattern with a good shape is easily obtained.

[0207] Other ingredients The photosensitive resin film of the present embodiment may contain other components, if necessary, in addition to the above-mentioned components (A) and (I). If desired, the photosensitive resin film of the embodiment may appropriately contain miscible additives, such as metal oxides, sensitizer components, silane coupling agents, solvents, additional resins for improving the performance of the film, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and antihalation agents.

[0208] Metal oxides The photosensitive resin film of the present embodiment contains a metal oxide (hereinafter also referred to as "component (M)") in addition to components (A) and (I), thereby obtaining a cured film with increased strength. In addition, a high-resolution pattern with a good shape can be formed. Examples of the (M) component include oxides of metals such as silicon (metallic silicon), titanium, zirconium, hafnium, etc. Among these, oxides of silicon are preferred, and among these, it is more preferred to use silica, and it is particularly preferred to use silica as a filler.

[0209] In addition, the component (M) is preferably in the form of particles. Such particulate (M) component is preferably a particle group having a volume average particle diameter of 5 to 40 nm, more preferably a particle group having a volume average particle diameter of 5 to 30 nm, and even more preferably a particle group having a volume average particle diameter of 10 to 20 nm. When the volume average particle size of component (M) is at least the lower limit of the preferred range, the strength of the cured film tends to be increased, whereas when it is at most the upper limit of the preferred range, residues are less likely to be generated during pattern formation, making it easier to form higher resolution patterns.

[0210] The particle size of the (M) component may be appropriately selected depending on the exposure light source. In general, it is considered that the effect of light scattering is hardly considered for particles having a particle size of 1 / 10 or less of the wavelength of light. For this reason, for example, when forming a fine structure by photolithography using i-line (365 nm), it is preferable to use a particle group (particularly preferably a silica particle group) having a primary particle size (volume average value) of 10 to 20 nm as the (M) component.

[0211] As the component (M), one type may be used alone, or two or more types may be used in combination. The content of the component (M) is preferably 10 to 30 parts by mass, and more preferably 15 to 25 parts by mass, per 100 parts by mass of the component (A). When the content of the (M) component is at least the lower limit of the above-mentioned preferred range, the strength of the cured film is further increased, whereas when the content is at most the upper limit of the above-mentioned preferred range, the flowability of the photosensitive resin composition is easily maintained.

[0212] When the photosensitive resin film of this embodiment contains the (M) component, the content of the (I) component is preferably 1 to 5 parts by mass, more preferably 1.1 to 4 parts by mass, and even more preferably 1.5 to 3 parts by mass, per 100 parts by mass of the total amount of the (A) and (M) components. When the content of component (I) is within the above-mentioned preferred range, the strength of the cured film is further increased, making it easier to form a high-resolution pattern with a good shape.

[0213] In the photosensitive resin film of this embodiment, the proportion of the content of the component (A) in the total content of the components (A), (I), and (M) is preferably 35 to 90 mass%, more preferably 40 to 85 mass%, and even more preferably 45 to 80 mass%. When the content of the component (A) is within the above-mentioned preferred range, the strength of the cured film is increased, and the film properties (such as lamination properties) when formed into a photosensitive resist film are improved.

[0214] Sensitizer component The photosensitive resin film of the embodiment may further contain a sensitizer component. The sensitizer component is not particularly limited as long as it can absorb energy due to exposure and transmit the energy to another substance. Specific examples of the sensitizer component that can be used include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetophene-based photosensitizers, naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, and known photosensitizers such as biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone. The sensitizer component may be used alone or in combination of two or more kinds. When a sensitizer component is added to the photosensitive resin film of the embodiment, the content of the sensitizer component is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of component (A). When the content of the sensitizer component is within the above preferred range, the sensitivity and resolution can be further improved.

[0215] ·Silane coupling agents The photosensitive resin film of the embodiment may further contain an adhesion promoter to improve adhesion to the support, and a silane coupling agent is preferable as the adhesion promoter. Examples of the silane coupling agent include silane coupling agents having reactive substituents such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, etc. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. The silane coupling agents may be used alone or in combination of two or more kinds. When a silane coupling agent is added to the photosensitive resin film of the embodiment, the content of the silane coupling agent is preferably 2.5 to 20 parts by mass, more preferably 3 to 15 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of component (A). When the content of the silane coupling agent is within the above-mentioned preferred range, the strength of the cured film is further increased, and in addition, the adhesion between the cured film and the support is further increased.

[0216] <Solvent> The photosensitive resin film of the embodiment can be produced by dissolving or dispersing a photosensitive material in a solvent (hereinafter referred to as "component (S)"). Examples of the (S) component include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; polyhydric ethers such as monoalkyl ethers, monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the polyhydric alcohols or the compounds having an ester bond, and compounds having an ether bond such as monophenyl ethers. Examples of suitable organic solvents include alcohol derivatives (among which, methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene, and dimethyl sulfoxide (DMSO). The component (S) may be used alone or as a mixed solvent of two or more kinds.

[0217] There are no particular limitations on the amount of component (S) used, and it is set appropriately according to the coating film thickness so long as it is a concentration that allows coating on a substrate or the like. The content of the component (S) in the photosensitive resin composition is preferably from 1 to 25 mass %, and more preferably from 5 to 20 mass %, relative to the total amount (100 mass %) of the photosensitive resin composition.

[0218] (Manufacturing method of hollow package) A manufacturing method according to a second aspect of the present invention is a method for manufacturing a hollow package, comprising a step of sealing the hollow structure manufactured by the manufacturing method according to the first aspect described above with a sealing material to obtain a hollow package.

[0219] As the sealing material, for example, a resin composition can be used. The resin used for the sealing material is not particularly limited as long as it can at least one of seal and insulate the hollow structure, and examples thereof include epoxy-based resins and silicone-based resins. The sealing material may contain other components such as a filler in addition to the resin.

[0220] The method for sealing the hollow structure with a sealing material is not particularly limited, and the heated and melted sealing material is supplied onto the hollow structure so as to cover the hollow structure, and then compression molded to produce a hollow package having a sealing material layer provided on the hollow structure. The sealing material layer has a function of protecting the MEMS, wiring parts, etc. in the hollow structure from the external environment.

[0221] The hollow package manufactured by the manufacturing method according to this embodiment includes the hollow structure 100 manufactured by the manufacturing method according to the first embodiment described above, and therefore the occurrence of defects such as deformation of the hollow structure during sealing, when connecting the conductor pattern and the lead frame together, when separating the substrate by dicing, etc., is suppressed. Therefore, the space inside the hollow structure is reliably maintained, and a highly reliable microdevice can be provided. EXAMPLES

[0222] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the explanation of each production example, "parts" means parts by mass.

[0223] <Preparation of negative type photosensitive resin composition> (Preparation Examples 1 to 4) The components shown in Table 1 were mixed and dissolved, and filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Corporation) to prepare negative photosensitive resin compositions (MEK solutions with solid content of approximately 84 to 86% by mass) for each example.

[0224] [Table 1]

[0225] In Table 1, the abbreviations have the following meanings. The numbers in brackets [ ] indicate the blending amount of each component (parts by mass; solid content equivalent). (A)-1: Epoxy group-containing resin represented by the following chemical formula (A11), product name "JER-157S70", manufactured by Mitsubishi Chemical Corporation.

[0226] [ka]

[0227] (A)-2: A compound represented by the following chemical formula (m1-1). Product name: "Celloxide 8000", manufactured by Daicel Corporation. (A)-3: A compound represented by the following chemical formula (m2-1). Trade name "TEPIC-VL", manufactured by Nissan Chemical Corporation.

[0228] [ka]

[0229] (I)-1: A photoinitiator represented by the following chemical formula (I1-4). Trade name "Irgacure290", manufactured by BASF. (I)-3: A photoinitiator represented by the following chemical formula (I1-1). Product name: “CPI-310B”, manufactured by San-Apro Ltd. (I)-4: A photoinitiator represented by the following chemical formula (I1-3). Product name: “CPI-410B”, manufactured by San-Apro Ltd. (I)-5: Photoinitiator represented by the following chemical formula (I2-1-2). Product name "CPI-410S", manufactured by San-Apro Ltd.

[0230] [ka]

[0231] (I)-2: Photoinitiator represented by the following chemical formula (I3-1-1). Product name "HS-1CS", manufactured by San-Apro Ltd.

[0232] [ka]

[0233] (C)-1: Silica filler. Product name "MEK-EC-2130Y", manufactured by Nissan Chemical Co., Ltd. Primary particle diameter φ=15 nm (volume average value). Methyl ethyl ketone dispersion with a silica component concentration of 31% by mass. (D)-1: Sensitizer. α-naphthol. (E)-1: Silane coupling agent. Product name: "Shin-Etsu Silicone (registered trademark) OFS6040SILANE", manufactured by Shin-Etsu Chemical Co., Ltd. (E)-2: Silane coupling agent, product name "Shin-Etsu Silicone (registered trademark) X-12-967C", manufactured by Shin-Etsu Chemical Co., Ltd. (S)-1: Solvent. Methyl ethyl ketone.

[0234] <Manufacturing method of hollow structure> As the substrate film, a PET film with a silicone-based surface release treatment (product name "A53", manufactured by Teijin Limited) was used.

[0235] Example 1 Process (0): The negative photosensitive resin composition of Preparation Example 1 was applied onto the substrate film using an applicator, and the composition was heated in an oven at 60°C for 5 minutes, and then baked (PAB) at 70°C for 10 minutes to form a photosensitive resin film with a thickness of 30 μm, thereby obtaining a photosensitive resist film (1). In addition, a stepped substrate having a recess on its surface was prepared.

[0236] Process (i): The photosensitive resist film (1) was disposed so that the surface of the photosensitive resin film of the photosensitive resist film (1) covered the opening of the recess in the stepped substrate.

[0237] After the step (i), an operation was carried out to peel off the base film from the photosensitive resin film of the photosensitive resist film (1).

[0238] Step (ii): Then, a Canon PLA-501 ghi line aligner was used to irradiate the photosensitive resin film with 300 mJ / cm 2 (i-line equivalent) was exposed.

[0239] Step (iii): The photosensitive resin film after exposure in the above step (ii) was subjected to a heat treatment on a hot plate at a temperature of 90° C. for 5 minutes.

[0240] Step (iv): The photosensitive resin film after the heat treatment in the above step (iii) was paddle-developed at 23° C. using propylene glycol monomethyl ether acetate as a developer to form a negative pattern that would become the top plate portion.

[0241] Process (v): The negative pattern after step (iv) was further cured by heating in an oven under the Step Cure conditions described below, to obtain a hollow structure (the cross section of the hollow structure in the height direction is rectangular: length (height) 200 μm × width 500 μm) whose top plate is made of a cured photosensitive resin film.

[0242] Step cure conditions: Heat treatment is performed in an oven at 60°C for 60 minutes, then at 100°C for 30 minutes, followed by a further heat treatment in an oven at 160°C for 30 minutes, and then at 200°C for 60 minutes.

[0243] Example 2 In the step (v), ultraviolet light is applied to the negative pattern after the step (iv) at 1000 mJ / cm 2 A hollow structural body was obtained in the same manner as in Example 1, except that after the irradiation, a heat treatment was carried out in an oven at a temperature of 160° C. for 60 minutes.

[0244] Example 3 In the step (v), the amount of ultraviolet light irradiated onto the negative pattern after the step (iv) is 5000 mJ / cm 2 A hollow structure was obtained in the same manner as in Example 2, except that the above-mentioned procedure was changed to the above.

[0245] Example 4 In the step (v), the amount of ultraviolet light irradiated onto the negative pattern after the step (iv) is 10000 mJ / cm 2 A hollow structure was obtained in the same manner as in Example 2, except that the above-mentioned procedure was changed to the above.

[0246] Example 5 A hollow structural body was obtained in the same manner as in Example 1, except that the negative type photosensitive resin composition of Preparation Example 1 was changed to the negative type photosensitive resin composition of Preparation Example 2.

[0247] Example 6 A hollow structural body was obtained in the same manner as in Example 1, except that the negative type photosensitive resin composition of Preparation Example 1 was changed to the negative type photosensitive resin composition of Preparation Example 3.

[0248] Example 7 A hollow structural body was obtained in the same manner as in Example 1, except that the negative type photosensitive resin composition of Preparation Example 1 was changed to the negative type photosensitive resin composition of Preparation Example 4.

[0249] Example 8 A hollow structural body was obtained in the same manner as in Example 2, except that the negative type photosensitive resin composition of Preparation Example 1 was changed to the negative type photosensitive resin composition of Preparation Example 2.

[0250] Example 9 A hollow structural body was obtained in the same manner as in Example 2, except that the negative type photosensitive resin composition of Preparation Example 1 was changed to the negative type photosensitive resin composition of Preparation Example 3.

[0251] Example 10 A hollow structural body was obtained in the same manner as in Example 2, except that the negative type photosensitive resin composition of Preparation Example 1 was changed to the negative type photosensitive resin composition of Preparation Example 4.

[0252] Comparative Example 1 In the step (v), a hollow structural body was obtained in the same manner as in Example 1, except that the negative pattern after the step (iv) was further subjected to a heat treatment at 200° C. for 60 minutes in an oven.

[0253] Comparative Example 2 In the step (v), a hollow structural body was obtained in the same manner as in Example 1, except that the negative pattern after the step (iv) was further subjected to a heat treatment at 160° C. for 60 minutes in an oven.

[0254] Comparative Example 3 A hollow structural body was obtained in the same manner as in Example 5, except that in the step (v), the negative pattern after the step (iv) was further subjected to a heat treatment in an oven at 160° C. for 60 minutes.

[0255] Comparative Example 4 A hollow structural body was obtained in the same manner as in Example 6, except that in the step (v), the negative pattern after the step (iv) was further subjected to a heat treatment in an oven at 160° C. for 60 minutes.

[0256] Comparative Example 5 A hollow structural body was obtained in the same manner as in Example 7, except that in the step (v), the negative pattern after the step (iv) was further subjected to a heat treatment at 160° C. for 60 minutes in an oven.

[0257] <Evaluation> The deformation and strength of the top plate of each of the obtained hollow structures were evaluated. The evaluation was carried out by measuring the swelling of the top plate and the tensile modulus E* of the cured film constituting the top plate as follows.

[0258] [Top bulge] The hollow structure immediately after manufacture was cut in the height direction, and the degree of deformation in the height direction of the hollow structure (bulge of the top plate) was measured using a Dektak surface step gauge. The results are shown in Tables 2 to 4 as "top plate bulge (μm)" according to the following evaluation criteria. The value in parentheses indicates the amount of deformation (μm) at the location of the largest top plate bulge. Evaluation criteria ◯: Deformation in the height direction of the hollow structure was 5 μm or less. ×: Deformation in the height direction of the hollow structure portion exceeded 5 μm.

[0259] [Measurement of tensile modulus E* of cured film] The tensile modulus E* of the cured film constituting the top plate of the hollow structural body obtained in the step (v) was measured as follows. The cured film was peeled off from the silicon wafer, and the tensile modulus E* of the cured film was measured at 175° C. using the following evaluation device and measurement conditions. The results are shown in Tables 2 to 4 as "Tensile modulus E* (GPa)". Evaluation device: Reogel E-4000 (UBM) Measurement conditions: Tensile mode, frequency 1.0Hz, chuck distance 10mm The higher the tensile modulus E*, the higher the strength of the cured film.

[0260] [Table 2]

[0261] [Table 3]

[0262] [Table 4]

[0263] From the results shown in Tables 2 and 4, in comparison with Examples 1 to 4 and Comparative Examples 1 and 2, which share the same negative photosensitive resin composition, it is clear that the hollow structures of Examples 1 to 4 all have low swelling of the top plate caused by the curing operation during their manufacture. In addition, it is clear that the hollow structures of Examples 1 to 4 have sufficient strength. On the other hand, the hollow structure of Comparative Example 1 had sufficient strength, but was found to have a large bulge in the top plate due to the curing operation during its manufacture.The hollow structure of Comparative Example 2 was found to have a large bulge in the top plate due to the curing operation during its manufacture, and was also found to have inferior strength to the hollow structures of Examples 1 to 4.

[0264] From the results shown in Tables 3 and 4, it can be seen that, by comparing Examples 5 and 8, which share a common negative photosensitive resin composition, with Comparative Example 3, the hollow structures of Examples 5 and 8 both had low swelling of the top plate caused by the curing operation during their manufacture. On the other hand, it was found that the hollow structure of Comparative Example 3 had a large swelling of the top plate caused by the curing operation during its manufacture. Moreover, it is clear that the hollow structures of Examples 5 and 8 both have higher strength than the hollow structure of Comparative Example 3.

[0265] From the results shown in Tables 3 and 4, a comparison of Examples 6 and 9 and Comparative Example 4, which share a common negative type photosensitive resin composition, shows that the hollow structures of Examples 6, 9, and Comparative Example 4 all have low top plate swelling caused by the curing operation during their manufacture. A comparison of the two shows that the hollow structures of Examples 6 and 9 have low top plate swelling caused by the curing operation during their manufacture, compared to the hollow structure of Comparative Example 4. Moreover, it is clear that the hollow structures of Examples 6 and 9 both have higher strength than the hollow structure of Comparative Example 4.

[0266] From the results shown in Tables 3 and 4, a comparison of Examples 7 and 10 and Comparative Example 5, which share the same negative type photosensitive resin composition, shows that the hollow structures of Examples 7, 10, and Comparative Example 5 all have low top plate swelling caused by the curing operation during their manufacture. A comparison of the two shows that the hollow structures of Examples 7 and 10 have low top plate swelling caused by the curing operation during their manufacture, compared to the hollow structure of Comparative Example 5. Moreover, it is clear that the hollow structures of Examples 7 and 10 both have higher strength than the hollow structure of Comparative Example 5.

[0267] Therefore, it was confirmed that application of the present invention makes it possible to suppress deformation of the top plate portion due to the curing operation and to stably manufacture a hollow structure having increased strength. [Explanation of symbols]

[0268] 10 substrate, 20 side wall, 30 photosensitive resin film, 40 cured body, 50 base film, 60 photomask, 80 laminated film, 100 hollow structure

Claims

1. A method for manufacturing a hollow structural body including a recess and a top plate portion that closes an opening of the recess, comprising the steps of: A step (0) of preparing a substrate having a recess on its surface and a photosensitive resist film having a negative photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid upon exposure; (i) a step of disposing the photosensitive resist film such that a photosensitive resin film surface of the photosensitive resist film covers an opening surface of the recess in the substrate; After the step (i), a step (ii) of exposing the photosensitive resin film to light; a step (iii) of subjecting the photosensitive resin film after the step (ii) to a heat treatment; (iv) developing the photosensitive resin film to form a negative pattern after the step (iii); and (v) a step of subjecting the negative pattern after the step (iv) to a heat treatment to cure the negative pattern, thereby obtaining a hollow structural body in which the top plate portion is made of a cured body of the photosensitive resin film, The heat treatment in the step (v) is carried out by an operation (y) of irradiating with ultraviolet light and then heating at a temperature of 100° C. or higher; The epoxy group-containing resin (A) contains a resin (A1) represented by the following general formula (A1): The method for producing a hollow structure, wherein the photoinitiator (I) contains at least one compound selected from the group consisting of a compound represented by the following general formula (I1) and a compound represented by the following general formula (I2): 【Chemistry 1】 [In the formula, R ｐ１ and R ｐ２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ｐ１ may be the same or different. ｐ２ may be the same or different. １ is an integer from 1 to 5. ＥＰ is an epoxy group-containing group. ＥＰ may be the same or different. 【Chemistry 2】 [In the formula, R b01 to R b04 are each independently an aryl group which may have a substituent, or a fluorine atom. R b05 is a fluorinated alkyl group which may have a substituent, or a fluorine atom. The multiple R b05 may be the same or different. q is an integer of 1 or more, and each Q q+ is independently a q-valent organic cation.]

2. In the above-mentioned operation (y), ultraviolet rays are irradiated at 1000 to 10000 mJ / cm ２ The method for producing a hollow structural body according to claim 1, further comprising the step of heating the material at a temperature of 160° C. or higher for 30 minutes or longer after the irradiation.

3. A method for manufacturing a hollow structural body including a recess and a top plate portion that closes an opening of the recess, comprising the steps of: A step (0) of preparing a substrate having a recess on its surface and a photosensitive resist film having a negative photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid upon exposure; (i) a step of disposing the photosensitive resist film such that a photosensitive resin film surface of the photosensitive resist film covers an opening surface of the recess in the substrate; After the step (i), a step (ii) of exposing the photosensitive resin film to light; a step (iii) of subjecting the photosensitive resin film after the step (ii) to a heat treatment; (iv) developing the photosensitive resin film to form a negative pattern after the step (iii); and (v) a step of subjecting the negative pattern after the step (iv) to a heat treatment to cure the negative pattern, thereby obtaining a hollow structural body in which the top plate portion is made of a cured body of the photosensitive resin film, The heat treatment in the step (v) is carried out by heating at a temperature of 50° C. or more and 125° C. or less for 10 minutes or more, and then further heating at a temperature of 160° C. or more for 30 minutes or more; The epoxy group-containing resin (A) contains a resin (A1) represented by the following general formula (A1): The method for producing a hollow structure, wherein the photoinitiator (I) contains at least one compound selected from the group consisting of a compound represented by the following general formula (I1) and a compound represented by the following general formula (I2): 【Chemistry 3】 [In the formula, R p1 and R p2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Multiple R p1 s may be the same as or different from each other. Multiple R p2 s may be the same as or different from each other. n 1 is an integer of 1 to 5. R EP is an epoxy group-containing group. Multiple R EP s may be the same as or different from each other.] 【Chemistry 4】 [In the formula, R b01 to R b04 are each independently an aryl group which may have a substituent, or a fluorine atom. R b05 is a fluorinated alkyl group which may have a substituent, or a fluorine atom. The multiple R b05 may be the same or different. q is an integer of 1 or more, and each Q q+ is independently a q-valent organic cation.]

4. A method for producing a hollow package, comprising a step of sealing a hollow structure produced by the method according to any one of claims 1 to 3 with a sealing material to obtain a hollow package.

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