JP2022021254A - Method for producing hollow structure and method for producing hollow package - Google Patents

Abstract

To provide a production method that can stably produce a hollow structure that prevents the deformation of a top plate part due to PEB operation, and a method for producing a hollow package.SOLUTION: A method for producing a hollow structure 100 includes the steps of: disposing a photosensitive resist film so that the surface of a negative photosensitive resin film 30 closes the opening face of a recess 15; 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 of the exposed photosensitive resin film 30 is performed by heating for 3 min. or longer at 40°C or higher and 70°C or lower.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for manufacturing a hollow structure and a method for manufacturing a hollow package.

In recent years, development of microelectronic devices such as surface acoustic wave (SAW) filters has been promoted. The package encapsulating such an electronic device has a hollow structure for ensuring the propagation of surface acoustic waves and the mobility of movable members of the electronic device.
A photosensitive resin composition is used to form the hollow structure, and a package is manufactured by molding while keeping the hollow on the wiring board on which the electrodes are formed.

For example, Patent Document 1 describes a step of forming a cavity securing portion so as to cover a Micro Electro Electric Mechanical Systems (MEMS) formed on a substrate to form a hollow structure, and a step of forming a hollow structure by transfer molding to seal the entire hollow structure. Disclosed is a method of manufacturing a hollow package having a step of sealing with a waterproof layer.

The cavity securing portion is formed as follows.
After applying the photosensitive resin composition around the MEMS, exposure, post-exposure baking (PEB), and development are performed through a photomask to prepare a side wall.
Next, from the dry film resist in which the base film, the photosensitive resin composition layer, and the cover film are laminated in this order, the cover film is peeled off and laminated on the upper side of the side wall to form the top plate portion, and again. A cavity securing portion is formed by performing exposure, PEB, and development via a photomask and removing unnecessary portions.

International Publication No. 2009/151050

However, in the method for producing the hollow structure described in Patent Document 1, there is a problem that the film-shaped top plate portion is easily deformed by the PEB operation when forming the cavity securing portion.

The present invention has been made in view of the above circumstances, and is a method for manufacturing a hollow structure and a hollow package capable of stably manufacturing a hollow structure by suppressing deformation of the top plate portion due to a PEB operation. The subject is to provide a manufacturing method.

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is a method for manufacturing a hollow structure including a recess, a top plate portion that closes the opening surface of the recess, a substrate having a recess on the surface, and an epoxy group-containing resin. (A) and the step (0) of preparing a photosensitive resist film having a negative-type photosensitive resin film containing a photoinitiator (I) that generates acid by exposure, and the photosensitive of the photosensitive resist film. A step (i) of arranging the photosensitive resist film so that the surface of the resin film closes the opening surface of the recess in the substrate, and a step (ii) of exposing the photosensitive resin film after the step (i). ), The step (iii) of heat-treating the photosensitive resin film after the step (ii), and after the step (iii), the photosensitive resin film is developed to form a negative pattern. The negative pattern after the step (iv) and the step (iv) is further cured by heat treatment to form a hollow structure in which the top plate portion is made of a cured body of the photosensitive resin film. A method for producing a hollow structure, which comprises a step (v) of obtaining the hollow structure, wherein the heat treatment in the step (iii) is performed by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer. be.

A second aspect of the present invention is characterized in that the hollow structure produced by the production method according to the first aspect is sealed with a sealing material to obtain a hollow package. It is a manufacturing method of.

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 stably manufacture a hollow structure by suppressing deformation of the top plate portion due to a PEB operation.

It is a schematic diagram explaining the manufacturing method of the hollow structure which concerns on 1st Embodiment. It is a schematic diagram explaining the manufacturing method of the hollow structure which concerns on 1st (2-1) Embodiment. It is a schematic diagram explaining the manufacturing method of the hollow structure which concerns on the second (2-2) Embodiment. It is a schematic diagram explaining the manufacturing method of the hollow structure which concerns on the second (2-3) Embodiment.

In the present specification and claims, "aliphatic" is a concept relative to aromatics and means a group having no aromaticity, a compound having no aromaticity, or the like. Define.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
"Fluorinated alkyl group" refers to a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a fluorine atom.
The “constituent unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When describing "may have a substituent", a case where a hydrogen atom (-H) is substituted with a monovalent group and a case where a methylene group ( _-CH2- ) is substituted with a divalent group. And both are included.
"Exposure" is a concept that includes general irradiation of radiation.

(Manufacturing method of hollow structure)
The manufacturing method according to the first aspect of the present invention is a manufacturing method of a hollow structure including a recess and a top plate portion that closes the opening surface of the recess, and is the following steps (0) and (i). )-(V). In addition, in the production method according to the first aspect, the heat treatment in the step (iii) is performed by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer.

Step (0): A substrate having a recess on the surface and a photosensitive resist film having a negative type photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates acid by exposure. Step (i): Step of arranging the photosensitive resist film so that the surface of the photosensitive resin film of the photosensitive resist film closes the opening surface of the recess in the substrate Step (ii): After the step (i), the step of exposing the photosensitive resin film Step (iii): The step of heat-treating the photosensitive resin film after the step (ii) Step (iv): The step (iii) After that, a step of developing the photosensitive resin film to form a negative pattern. Step (v): The negative pattern after the step (iv) is further heat-treated to be cured, and then the heavenly pattern is formed. A step of obtaining a hollow structure in which the plate portion is made of a cured body of the photosensitive resin film.

The hollow structure manufactured by the manufacturing method according to this embodiment includes a recess and a top plate portion that closes the opening surface of the recess. The hollow structure can be suitably used for a hollow package used in SAW filters, MEMS, various sensors and the like.

[Step (0)]
In the step (0) in this embodiment, the photosensitive resin film has a substrate having a recess on the surface and a negative type photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid by exposure. Prepare a sex resist film.

≪About the substrate with recesses on the surface≫
Examples of the substrate having a recess on the surface include a structure having a pattern formed on the substrate, a stepped substrate, and the like. The recess may be made of an organic material or an inorganic material.
For such a substrate having recesses on the surface, for example, a step of forming a photosensitive resin film on a support using a negative photosensitive resin composition (hereinafter referred to as “film forming step”) and the above-mentioned photosensitive. The step of exposing the sex resin film (hereinafter referred to as "exposure step") and the post-exposure photosensitive resin film are developed with a developing solution containing an organic solvent to form a negative pattern as a side wall of a recess. It can be manufactured by a method having a process (hereinafter referred to as "development process"). Such a method for manufacturing a substrate having a recess on the surface can be performed as follows.

Membrane formation process:
First, a negative photosensitive resin composition is applied onto the support by a known method such as a spin coating method, a roll coating method, a screen printing method, and a bake (post-apply bake (PAB)) treatment is performed, for example, 50. It is applied at a temperature of about 150 ° C. for 2 to 60 minutes to form a photosensitive resin film.
The film forming step can also be performed by arranging a photosensitive resin composition layer prepared in advance using the negative photosensitive resin composition on the support.

The support is not particularly limited, and conventionally known ones can be used, and examples thereof include a substrate for electronic components and a support having a predetermined wiring pattern formed therein.
More specifically, as a substrate for electronic parts, silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO ₃ ), niobium, lithium niobate (LiNbO ₃ ), palladium, titanium tungsten, copper, chromium, iron. , Metallic substrates such as aluminum, glass substrates and the like.
As the material of the wiring pattern, for example, copper, aluminum, nickel, gold and the like can be used.

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

Exposure process:
Next, the formed photosensitive resin film is exposed to the formed photosensitive resin film through a mask (mask pattern) in which a predetermined pattern is formed, or by direct irradiation of an electron beam without a mask pattern, using a known exposure device. After selective exposure by drawing or the like, baking (post-exposure baking (PEB)) treatment, for example, under a temperature condition of 80 to 150 ° C. for 40 to 1200 seconds, preferably 40 to 1000 seconds, is performed as necessary. It is preferably applied for 60 to 900 seconds.

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

The exposure method of the photosensitive resin film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or an immersion exposure (Liquid Immersion Lithology).

Development process:
Next, the photosensitive resin film after the exposure is developed with a developing solution (organic developing solution) containing an organic solvent. After development, a rinsing treatment is preferably performed. Baking processing (post-baking) may be performed if necessary.

The organic solvent contained in the organic developer can be appropriately selected from known organic solvents. Specific examples thereof include ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, polar solvents such as ether solvents, hydrocarbon solvents and the like.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone and methylethylketone. , Methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, methylamylketone (2-heptanone) and the like. Among these, methylamylketone (2-heptanone) is preferable as the ketone solvent.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy acetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, and the like. 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 mono Ethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 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 formic acid, ethyl formic acid, formic acid Butyl, propyl silicate, 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-ethoxy Examples thereof include propionate and propyl-3-methoxypropionate. Among these, butyl acetate or PGMEA is preferable as the ester solvent.

Examples of the nitrile-based solvent include acetonitrile, propionitril, valeronitrile, butyronitril and the like.

A known additive can be added to the organic developer, if necessary. Examples of the additive include a surfactant. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used.
As the surfactant, a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.% With respect to the total amount of the organic developer. 5% by mass is more preferable.

The developing process can be carried out by a known developing method. For example, a method of immersing a support in a developing solution for a certain period of time (dip method), or a method in which a developing solution is raised on the surface of a support by surface tension for a certain period of time. A method of standing still (paddle method), a method of spraying the developer on the surface of the support (spray method), a method of applying the developer on the support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed. Examples include a method of continuously producing (dynamic dispense method).

The rinsing treatment (cleaning treatment) using the rinsing liquid can be carried out by a known rinsing method. Examples of the rinsing treatment method include a method of continuously spraying the rinsing liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in the rinsing liquid for a certain period of time (dip method), and the like. Examples thereof include a method of spraying a rinse liquid on the surface of the support (spray method).
For the rinsing treatment, it is preferable to use a rinsing liquid containing an organic solvent.

By the film forming step, the exposure step, and the developing step described above, a substrate having recesses on the surface (a structure having a pattern formed on the substrate, a stepped substrate) can be manufactured.
The thickness (horizontal dimension to the support) and height (vertical dimension to the support) of the side wall are determined by the size of the hollow portion depending on the type of electronic device accommodated in the recess. Based on this, it can be set as appropriate.

≪About photosensitive resist film≫
The photosensitive resist film in this embodiment includes an epoxy group-containing resin (A) (hereinafter referred to as “(A) component”) and a photoinitiator (I) that generates acid upon exposure (hereinafter referred to as “(I) component”). It has a negative type photosensitive resin film containing.
Details of the components constituting such a photosensitive resist film will be described later.

When a photosensitive resin film is formed using such a photosensitive resist film and the photosensitive resin film is selectively exposed, acid is generated from the component (I) in the exposed portion of the photosensitive resin film. Then, due to the action of the acid, the epoxy group in the component (A) undergoes ring-opening polymerization, and the solubility of the component (A) in the developing solution containing an organic solvent is reduced, while the photosensitive resin film is formed. Since the solubility of the component (A) in the developing solution containing the organic solvent does not change in the unexposed portion, the developing solution containing the organic solvent is used between the exposed portion and the unexposed portion of the photosensitive resin film. There is a difference in solubility in. That is, the photosensitive resin film is a negative type. Therefore, when the photosensitive resin film is developed with a developing solution containing an organic solvent, the unexposed portion is dissolved and removed, and a negative pattern is formed.

Here, the negative-type photosensitive resin film of the photosensitive resist film is typically composed of a B-stage (semi-cured) resin material.
Examples of the photosensitive resist film include a single layer made of a photosensitive resin film and a laminated film in which a photosensitive resin film is laminated on a base film.

The photosensitive resist film is obtained by applying a negative photosensitive resin composition in which the component (A) and the component (I) are dissolved in a solvent on a base film and drying the film to form a photosensitive resin film. Or, it can be produced by peeling off the base film after forming the photosensitive resin film.
The negative photosensitive resin composition may be applied onto the base film by an appropriate 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, more preferably 5 to 50 μm.

As the base film, a known one can be used, and for example, a thermoplastic resin film or the like is used. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm.

In the method for manufacturing a hollow structure according to this aspect, steps (i) to (v) are performed using the substrate having recesses on the surface and the photosensitive resist film prepared in the above step (0). ..
Examples of the method for manufacturing the hollow structure include the first embodiment and the second embodiment shown below.

About the first embodiment:
In step (0), a single-layered photosensitive resin film is prepared as the photosensitive resist film, and steps 1- (i), 1- (ii), 1- (iii), A form in which step 1- (iv) and step 1- (v) are performed in this order.

Regarding the second embodiment:
In step (0), the photosensitive resist film is prepared from a laminated film in which the photosensitive resin film is laminated on the base film, and the operation of peeling the base film from the photosensitive resin film is developed. A form to be performed before the process.
Preferably, the following embodiment (2-1), (2-2) and (2-3) embodiments are mentioned below.

About the first (2-1) embodiment:
In step (0), as a photosensitive resist film, a film made of a laminated film in which a photosensitive resin film is laminated on a base film is prepared. In step 2-1 (i), the photosensitive resin film is used as a base. A form in which the operation of peeling the material film, step 2-1 (ii), step 2-1 (iii), step 2-1 (iv), and step 2-1 (v) are performed in this order.

About the second (2-2) embodiment:
In step (0), as the photosensitive resist film, a laminated film in which a photosensitive resin film is laminated on a base film is prepared. ii), the operation of peeling the base film from the photosensitive resin film, step 2-2- (iii), step 2-2- (iv), and step 2-2- (v) in this order.

About the second (2-3) embodiment:
In step (0), a photosensitive resist film made of a laminated film in which a photosensitive resin film is laminated on a base film is prepared, and steps 2-3 (i) and 2-3 (). Ii), step 2-3 (iii), the operation of peeling the base film from the photosensitive resin film, step 2-3 (iv), and step 2-3 (v) in this order.

Hereinafter, each embodiment of the method for manufacturing a hollow structure will be described with reference to the drawings.

<First Embodiment>
In step (0), a single-layered photosensitive resin film is prepared as the photosensitive resist film, and steps 1- (i), 1- (ii), 1- (iii), A form in which step 1- (iv) and step 1- (v) are performed in this order.

FIG. 1 is a schematic diagram illustrating a method for manufacturing a hollow structure according to the first embodiment.
In FIG. 1, the substrate 10 and the side wall 20 formed on the substrate 10 constitute a substrate having a recess 15 on the surface thereof. As the photosensitive resist film, a single-layer film made of a photosensitive resin film 30 is used.
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 constituting the top plate portion, or may be a different material.

[Step 1- (i)]
In step 1- (i), the photosensitive resist film is arranged so that the surface of the photosensitive resin film 30 of the photosensitive resist film closes the opening surface of the recess 15 in the substrate 10.
In FIG. 1, the photosensitive resist film is arranged so as to face the substrate 10 via the side wall 20. Then, a hollow closed space surrounded by the substrate 10, the side wall 20, and the photosensitive resin film 30 is formed.

[Step 1- (ii)]
In step 1- (ii), the photosensitive resin film 30 is exposed.
For example, the photosensitive resin film 30 is selectively exposed via a photomask 60 on which a predetermined pattern is formed by using a known exposure device.

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

[Step 1- (iii)]
In step 1- (iii), the photosensitive resin film 30 after exposure is subjected to heat treatment, so-called post-exposure baking (PEB) treatment.
In the method for producing a hollow structure according to the first embodiment, the heat treatment in step 1- (iii) is performed by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer.
The temperature of the heat treatment in step 1- (iii) is 40 ° C. or higher and 70 ° C. or lower, preferably 40 ° C. or higher and 60 ° C. or lower, and more preferably 50 ° C. or higher and 60 ° C. or lower.
The duration of the heat treatment in step 1- (iii) is 3 minutes or more, preferably 5 minutes or more and 60 minutes or less, and more preferably 10 minutes or more and 30 minutes or less.

The heat treatment in step 1- (iii) is performed by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer (first heating), and then continuing from the temperature after this heating at a temperature of 90 ° C. or higher. It is preferable to carry out by heating for 3 minutes or more (second heating).
The temperature and the duration thereof in the first heating are preferably 50 ° C. or higher and 70 ° C. or lower, more preferably 50 ° C. or higher and 60 ° C. or lower, preferably 5 minutes or longer and 60 minutes or lower, and more preferably 5 minutes or longer and 30 minutes. It is as follows.
The temperature and the duration thereof in the second heating are preferably 90 ° C. or higher and 120 ° C. or lower, more preferably 90 ° C. or higher and 100 ° C. or lower, preferably 3 minutes or longer and 30 minutes or shorter, and more preferably 3 minutes or longer and 10 minutes. It is as follows.
Further heating (second heating) from the temperature after the first heating promotes ring-opening polymerization of the epoxy group in the component (A) in the exposed portion of the photosensitive resin film 30, and the top plate. The strength of the part is improved. In addition, the expansion of the air in the hollow is suppressed, and the deformation of the top plate portion due to the PEB operation is easily suppressed.

For example, the heat treatment in step 1- (iii) is preferably carried out by heating at a temperature of 40 ° C. or higher and 60 ° C. or lower for 10 minutes or longer and 30 minutes or shorter.

Further, for example, the heat treatment in step 1- (iii) is carried out by heating at a temperature of 50 ° C. or higher and 70 ° C. or lower for 5 minutes or longer and 30 minutes or lower, and continuously from the temperature after this heating, 90 ° C. or higher and 100 ° C. A form in which heating is performed at the following temperature for 3 minutes or more and 10 minutes or less is preferable.

By the heat treatment in step 1- (iii), the photosensitive resin film 30 after exposure becomes an exposed portion 30A in which the epoxy group in the component (A) is ring-opened and polymerized, and an unexposed portion 30B in which there is no change.

[Step 1- (iv)]
In step 1- (iv), the photosensitive resin film 30 (30A, 30B) after the PEB treatment is developed to form a negative pattern (exposed portion 30A).
The development here can be performed in the same manner as the development step in the above-mentioned [Step (0)]. After development, a rinsing treatment is preferably performed.
By the development in step 1- (iv), the unexposed portion 30B is dissolved and removed, and the exposed portion 30A serving as the top plate portion remains as a negative pattern.

[Step 1- (v)]
In step 1- (v), the negative pattern (exposed portion 30A) after development is further cured by heat treatment, and the top plate portion is a hollow structure made of a cured body 40 of the photosensitive resin film 30. Get body 100. In FIG. 1, in the cured body 40, the photosensitive resin material forming the side wall 20 and the photosensitive resin film 30 are cured and integrated.
The temperature of the heat treatment in step 1- (v) is, for example, 100 ° C. or higher, preferably 100 ° C. or higher and 250 ° C. or lower, and more preferably 150 ° C. or higher and 200 ° C. or lower.
The duration of the heat treatment in step 1- (v) is, for example, 30 minutes or more, preferably 30 minutes or more and 120 minutes or less, and more preferably 30 minutes or more and 90 minutes or less.

In the method for producing a hollow structure according to the first embodiment described above, the heat treatment in step 1- (iii) is performed by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer. As a result, during the PEB operation, the expansion of the air in the hollow is suppressed as compared with the conventional case, and the ring-opening polymerization of the epoxy group of the component (A) can be promoted while reducing the internal pressure. Therefore, according to the first embodiment, the deformation of the top plate portion due to the PEB operation is suppressed, and the hollow structure can be stably manufactured.

<First (2-1) Embodiment>
In step (0), as a photosensitive resist film, a film made of a laminated film in which a photosensitive resin film is laminated on a base film is prepared. In step 2-1 (i), the photosensitive resin film is used as a base. Operation to peel off the material film (step 2-1 (D)), step 2-1 (iii), step 2-1 (iii), step 2-1 (iv), step 2-1 ( A form in which v) is performed in this order.

FIG. 2 is a schematic diagram illustrating a method for manufacturing a hollow structure according to the first (2-1) embodiment.
In FIG. 2, the substrate 10 and the side wall 20 formed on the substrate 10 form a substrate having a recess 15 on the surface thereof. As the photosensitive resist film, a film made of a laminated film 80 in which a photosensitive resin film 30 is laminated on a base film 50 is used.

[Step 2-1 (i)]
In step 2-1 (i), the laminated film 80 is arranged so that the surface of the photosensitive resin film 30 of the photosensitive resist film (laminated film 80) closes the opening surface of the recess 15 in the substrate 10.
In FIG. 2, the laminated film 80 is arranged so as to face the substrate 10 via the side wall 20. Then, a hollow closed space surrounded by the substrate 10, the side wall 20, and the photosensitive resin film 30 is formed.

[Step 2-1 (D)]
In the first (2-1) embodiment, the operation of peeling the base film 50 from the photosensitive resin film 30 is performed between the step (i) and the step (ii). That is, in step 2-1 (D), after step 2-1 (i), the base film 50 is peeled off from the photosensitive resin film 30 in the laminated film 80.

[Step 2-1 (ii)] to [Step 2-1 (v)]
In step 2-1 (ii), the photosensitive resin film 30 is exposed.
In step 2-1 (iii), the photosensitive resin film 30 after exposure is subjected to heat treatment, so-called post-exposure baking (PEB) treatment.
In step 2-1 (iv), the photosensitive resin film 30 (30A, 30B) after the PEB treatment is developed to form a negative pattern (exposed portion 30A).
In step 2-1 (v), the negative pattern (exposed portion 30A) after development is further cured by heat treatment, and the top plate portion is made of a cured body 40 of the photosensitive resin film 30. A hollow structure 100 is obtained.
The description of the operations of the steps 2-1 (ii), 2-1 (iii), 2-1 (iv) and 2-1 (v) is the step in the first embodiment described above. It is the same as the description about the operation of 1- (ii), step 1- (iii), step 1- (iv) and step 1- (v), respectively.

In the method for producing a hollow structure according to the first embodiment described above, the heat treatment in step 2-1 (iii) is carried out by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer. conduct. As a result, during the PEB operation, the expansion of the air in the hollow is suppressed as compared with the conventional case, and the ring-opening polymerization of the epoxy group of the component (A) can be promoted while reducing the internal pressure.
In addition, in the first (2-1) embodiment, the operation of peeling the base film 50 of the laminated film 80 is performed in steps 2-1 (i) and 2-1 (ii) prior to the PEB step. Do it during. This prevents problems due to thermal expansion of the base film due to heating during the PEB operation.
For the above, according to the first embodiment, the deformation of the top plate portion due to the PEB operation is suppressed, and the hollow structure can be stably manufactured.

The problem due to the thermal expansion of the base film due to heating during the PEB operation is that the photosensitive resin film that is stretched by the thermal expansion of the base film and is laminated with the base film follows this and is photosensitive. It means that a pattern shift of the sex resin film occurs. When the pattern shift of the photosensitive resin film occurs, there is a problem that the peripheral end portion of the top plate portion is deformed and the strength of the hollow structure is lowered.

<First (2-2) Embodiment>
In step (0), as the photosensitive resist film, a laminated film in which a photosensitive resin film is laminated on a base film is prepared. ii), operation of peeling the base film from the photosensitive resin film (step 2-2- (D)), step 2-2- (iii), step 2-2- (iv), step 2-2-( A form in which v) is performed in this order.

FIG. 3 is a schematic diagram illustrating a method for manufacturing a hollow structure according to the second embodiment (2-2).
In FIG. 3, the substrate 10 and the side wall 20 formed on the substrate 10 constitute a substrate having a recess 15 on the surface thereof. As the photosensitive resist film, a film made of a laminated film 80 in which a photosensitive resin film 30 is laminated on a base film 50 is used.

[Step 2-2- (i)]
In step 2-2- (i), the laminated film 80 is arranged so that the surface of the photosensitive resin film 30 of the photosensitive resist film (laminated film 80) closes the opening surface of the recess 15 in the substrate 10.
In FIG. 3, the laminated film 80 is arranged so as to face the substrate 10 via the side wall 20. Then, a hollow closed space surrounded by the substrate 10, the side wall 20, and the photosensitive resin film 30 is formed.

[Step 2-2- (ii)]
In step 2-2- (ii), the photosensitive resin film 30 is exposed via the base film 50.
For example, the photosensitive resin film 30 is selectively exposed to the photosensitive resin film 30 via the photomask 60 on which a predetermined pattern is formed by transmitting the substrate film 50 through a known exposure device.

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

[Step 2-2- (D)]
In the second (2-2) embodiment, the operation of peeling the base film 50 from the photosensitive resin film 30 after exposure is performed between the step (ii) and the step (iii). That is, in step 2-2- (D), after step 2-2- (ii), the base film 50 is peeled off from the photosensitive resin film 30 in the laminated film 80.

[Step 2-2- (iii)] to [Step 2-2- (v)]
In step 2-2- (iii), the photosensitive resin film 30 after exposure is subjected to heat treatment, so-called post-exposure baking (PEB) treatment.
In step 2-2- (iv), the photosensitive resin film 30 (30A, 30B) after the PEB treatment is developed to form a negative pattern (exposed portion 30A).
In step 2-2- (v), the negative pattern (exposed portion 30A) after development is further cured by heat treatment, and the top plate portion is made of a cured body 40 of the photosensitive resin film 30. A hollow structure 100 is obtained.
The description of the operations of the steps 2-2- (iii), the step 2-2- (iv) and the step 2-2- (v) is described in the above-described first embodiment of the steps 1- (iii) and 1-. It is the same as the description about the operation of (iv) and step 1- (v), respectively.

In the method for producing a hollow structure according to the second embodiment described above, the heat treatment in step 2-2- (iii) is carried out by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer. conduct. As a result, during the PEB operation, the expansion of the air in the hollow is suppressed as compared with the conventional case, and the ring-opening polymerization of the epoxy group of the component (A) can be promoted while reducing the internal pressure.
In addition, in the second (2-2) embodiment, the operation of peeling the base film 50 of the laminated film 80 is performed in steps 2-2- (ii) and 2-2- (iii) prior to the PEB step. Do it during. This prevents problems due to thermal expansion of the base film due to heating during the PEB operation.
Therefore, according to the first (2-2) embodiment, the deformation of the top plate portion due to the PEB operation is suppressed, and the hollow structure can be stably manufactured.

<First (2-3) Embodiment>
In step (0), a photosensitive resist film made of a laminated film in which a photosensitive resin film is laminated on a base film is prepared, and steps 2-3 (i) and 2-3 (). ii), step 2-3 (iii), operation of peeling the base film from the photosensitive resin film (step 2-3 (D)), step 2-3 (iv), step 2-3 ( A form in which v) is performed in this order.

FIG. 4 is a schematic diagram illustrating a method for manufacturing a hollow structure according to the second (2-3) embodiment.
In FIG. 4, the substrate 10 and the side wall 20 formed on the substrate 10 constitute a substrate having a recess 15 on the surface thereof. As the photosensitive resist film, a film made of a laminated film 80 in which a photosensitive resin film 30 is laminated on a base film 50 is used.

[Step 2-3 (i)]
In step 2-3 (i), the laminated film 80 is arranged so that the surface of the photosensitive resin film 30 of the photosensitive resist film (laminated film 80) closes the opening surface of the recess 15 in the substrate 10.
In FIG. 4, the laminated film 80 is arranged so as to face the substrate 10 via the side wall 20. Then, a hollow closed space surrounded by the substrate 10, the side wall 20, and the photosensitive resin film 30 is formed.

[Step 2-3 (ii)]
In step 2-3 (ii), the photosensitive resin film 30 is exposed via the base film 50.
For example, the photosensitive resin film 30 is selectively exposed to the photosensitive resin film 30 via the photomask 60 on which a predetermined pattern is formed by transmitting the substrate film 50 through a known exposure device.

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

[Step 2-3 (iii)]
In step 2-3 (iii), the photosensitive resin film 30 after exposure is subjected to PEB treatment.
The description of the operation of step 2-3 (iii) is the same as the description of the operation of step 1- (iii) in the first embodiment described above.
By the heat treatment in step 2-3 (iii), the photosensitive resin film 30 after exposure becomes an exposed portion 30A in which the epoxy group in the component (A) is ring-opened and polymerized, and an unexposed portion 30B without change. ..

[Step 2-3 (D)]
In the first (2-3) embodiment, the operation of peeling the base film 50 from the photosensitive resin film 30 (30A, 30B) after the PEB treatment is performed between the step (iii) and the step (iv). .. That is, in step 2-3 (D), after step 2-3 (iii), the base film 50 is peeled off from the photosensitive resin film 30 in the laminated film 80.

[Step 2-3 (iv)]-[Step 2-3 (v)]
In step 2-3 (iv), the photosensitive resin film 30 (30A, 30B) after the PEB treatment is developed to form a negative pattern (exposed portion 30A).
In step 2-3 (v), the negative pattern (exposed portion 30A) after development is further cured by heat treatment, and the top plate portion is made of a cured body 40 of the photosensitive resin film 30. A hollow structure 100 is obtained.
The description of the operation of the step 2-3 (iv) and the operation of the step 2-3 (v) is the description of the operation of the step 1- (iv) and the step 1- (v) in the above-mentioned first embodiment. The same is true for each.

In the method for producing a hollow structure according to the first (2-3) embodiment described above, the heat treatment in step 2-3 (iii) is carried out by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer. conduct. As a result, during the PEB operation, the expansion of the air in the hollow is suppressed as compared with the conventional case, and the ring-opening polymerization of the epoxy group of the component (A) can be promoted while reducing the internal pressure.
In addition, in the first (2-3) embodiment, the operation of peeling the base film 50 of the laminated film 80 is performed by the steps 2-3 (iii) and 2-3 (iv) after the PEB step. Do it in the meantime. In the first (2-3) embodiment, although the base film 50 is heated by the PEB operation, it is controlled to be heated at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer. As a result, thermal expansion of the base film 50 is unlikely to occur, and the occurrence of pattern shift of the photosensitive resin film is suppressed.
Therefore, according to the second (2-3) embodiment, the deformation of the top plate portion due to the PEB operation is suppressed, and the hollow structure can be stably manufactured.

<Other embodiments>
Regarding the method for producing the hollow structure according to the above-described embodiment, as the photosensitive resist film, a single-layer film made of a photosensitive resin film or a laminated film in which a photosensitive resin film is laminated on a base film is used. The case of preparing the film has been described, but the present invention is not limited to these, and for example, a case may be prepared in which a photosensitive resin film and a cover film are laminated in this order on a base film.

As the cover film, a known one can be used, and for example, a polyethylene film, a polypropylene film, or the like is used. As the cover film, a film having a smaller adhesive force with the photosensitive resin film than the base film is preferable.
The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm.
The base film and the cover film may be the same film material or may be different film materials.
In use, for example, it can be used as a laminated film of a photosensitive resin film / base film while peeling off the cover film.

<< About the components that make up the photosensitive resist film >>
The photosensitive resist film in this embodiment has a negative type photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid upon exposure.

-Epoxy group-containing resin (A):
The epoxy group-containing resin (component (A)) is not particularly limited as long as it is a resin having a sufficient epoxy group in one molecule to form a pattern by exposure.
Examples of the component (A) include a novolak type epoxy resin (Av), a bisphenol A type epoxy resin (Abp), a bisphenol F type epoxy resin, an aliphatic epoxy resin, and an acrylic resin (Aac).

・ ・ Novolac type epoxy resin (Anv)
As the novolak type epoxy resin (Anv), a resin (A1) represented by the following general formula (A1) (hereinafter, also referred to as “(A1) component”) is preferably mentioned.

［式中、Ｒ^ｐ１及びＲ^ｐ２は、それぞれ独立に、水素原子又は炭素数１～５のアルキル基である。複数のＲ^ｐ１は、互いに同一であってもよく異なっていてもよい。複数のＲ^ｐ２は、互いに同一であってもよく異なっていてもよい。ｎ_１は、１～５の整数である。Ｒ^ＥＰは、エポキシ基含有基である。複数のＲ^ＥＰは、互いに同一であってもよく異なっていてもよい。］

[In the formula, R ^p1 and R ^p2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. The plurality of R ^p1s may be the same as or different from each other. The plurality of R ^p2s 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. The plurality of R ^EPs may be the same as or different from each other. ]

In the formula (A1), the alkyl group having 1 to 5 carbon atoms of R ^p1 and R ^p2 is, for example, a linear, branched chain, 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, a neopentyl group and the like. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group.
Among them, as R ^p1 and R ^p2 , 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 the formula (A1), the plurality of R ^p1s may be the same as or different from each other. The plurality of R ^p2s may be the same as or different from each other.

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

In formula (A1), R ^EP is an epoxy group-containing group.
The epoxy group-containing group of ^REP is not particularly limited, and is a group consisting only of an epoxy group; a group consisting only of an alicyclic epoxy group; an epoxy group or an alicyclic epoxy group and a divalent linking group. A group having and can be mentioned.
The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a 3-membered ring ether, and specifically, a group having an alicyclic group and an oxacyclopropane structure.
The alicyclic group which 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, a cyclooctyl group and the like. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like. Further, 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, the epoxy group or the alicyclic epoxy group is via a divalent linking group bonded to an oxygen atom (—O—) in the formula. It is preferable that the groups are bonded.

Here, the divalent linking group is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like are preferable.

For divalent hydrocarbon groups that may have substituents:
The 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 includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -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. Alkyl methylene 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. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- , and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

As the aliphatic hydrocarbon group containing a ring in the structure, an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from the alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. 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 two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n + 2) π electrons, and may be a monocyclic type or a polycyclic type. 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; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group from which two hydrogen atoms have been removed (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Hydrogen from an aryl group in an arylalkyl group such as a group substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.) A group from which one atom is further removed) and the like can be mentioned. The carbon number of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

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. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group and the like.

The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in the structure as a divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are preferable, and a methoxy group is preferable. Groups and ethoxy groups are most preferred.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
In the alicyclic hydrocarbon group, a part of the carbon atom constituting the ring structure may be substituted with a substituent containing a heteroatom. As the substituent containing the heteroatom, —O—, —C (= O) —O—, —S—, —S (= O) _2- , —S (= O) ₂ -O— are preferable.

As 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, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
Examples of the alkoxy group, the halogen atom and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the alicyclic hydrocarbon group.

About divalent linking groups containing heteroatoms:
The hetero atom in the divalent linking group including the hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

Among the divalent linking groups containing a hetero atom, the preferred linking groups are -O-, -C (= O) -O-, -C (= O)-, and -OC (= O). -O-; -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-(H is a substitution of an alkyl group, an acyl group, etc.) It may be substituted with a 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) -O-Y ²¹ ,-[Y ²¹ -C (= O) -O] _{m "} -Y ²² -or- Group represented by Y ²¹ -OC (= O) -Y ^22- [In the formula, Y ²¹ and Y ²² are divalent hydrocarbon groups which may have independent substituents. , O is an oxygen atom, and m "is an integer of 0 to 3. ] And so on.
When the divalent linking group containing the hetero atom is -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)- The H may be substituted with a substituent such as an alkyl group or an acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Equations-Y ²¹ -O-Y 22-, -Y ^{21-O-, -Y 21 -} C (= O) -O-, -C ^{(= O) -O-Y 21-,-[Y 21 - C} (= O) -O] _{m "} -Y ²² -or -Y ²¹ -OC (= O) -Y ^22- , Y ²¹ and Y ²² each independently have a substituent. It is also a good divalent hydrocarbon group. As the divalent hydrocarbon group, the "divalent hydrocarbon group which may have a substituent may have a substituent" mentioned in the above description as the divalent linking group. The same thing can be mentioned.
As ^Y21 , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. 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.
In the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- , m" is an integer of 0 to 3, preferably an integer of 0 to 2, and 0. Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula- [Y ²¹ -C ⁽ = O) -O] _{m "} -Y ^22- is represented by the formula -Y ²¹ -C (= O) -OY 22-. A group is particularly preferable. Among them, a group represented by the formula- (CH ₂ ) _a' -C (= O) -O- (CH ₂ ) b'-is preferable. In the formula, _a'is 1 to 1 to. It is an integer of 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 and 1 to 8. Is preferred, an integer of 1 to 5 is more preferred, 1 or 2 is even more preferred, and 1 is most preferred.

Of these, the glycidyl group is preferable as the epoxy group-containing group in ^REP .

Further, as the novolak type epoxy resin (Anv), a resin having a structural unit represented by the following general formula (anv1) is also preferably mentioned.

［式中、Ｒ^ＥＰは、エポキシ基含有基であり、Ｒ^ａ２２、Ｒ^ａ２３は、それぞれ独立に水素原子、炭素数１～５のアルキル基又はハロゲン原子である。］

[In the formula, R ^EP is an epoxy group-containing group, and Ra ²² and Ra ²³ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or halogen atoms, respectively. ]

In the formula ( ^anv1 ), the alkyl groups having 1 to 5 carbon atoms of Ra 22 and Ra ^{23 are the same as the alkyl groups having 1 to 5 carbon atoms of R p1 and} R ^p2 in the formula (A1). The halogen atom of R ^a22 and R ^a23 is preferably a chlorine atom or a bromine atom.
In the formula (anv1), the R ^EP is the same as the R ^EP in the formula (A1), and a glycidyl group is preferable.

A specific example of the structural unit represented by the above formula (anv1) is shown below.

The novolak type epoxy resin (Anv) may be a resin composed of only the constituent unit (anv1), or may be a resin having the constituent unit (anv1) and another constituent unit. Examples of other structural units include structural units represented by the following general formulas (anv2) to (anv3).

［式中、Ｒ^ａ２４は、置換基を有していてもよい炭化水素基である。Ｒ^ａ２５～Ｒ^ａ２６、Ｒ^ａ２８～Ｒ^ａ３０は、それぞれ独立に水素原子、炭素数１～５のアルキル基又はハロゲン原子である。Ｒ^ａ２７は、エポキシ基含有基又は置換基を有していてもよい炭化水素基である。］

[In the formula, ^Ra24 is a hydrocarbon group which may have a substituent. R ^a25 to ^Ra26 and R ^a28 to ^Ra30 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or halogen atoms, respectively. ^Ra27 is a hydrocarbon group which may have an epoxy group-containing group or a substituent. ]

In formula (anv2), ^Ra24 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 or a cyclic hydrocarbon group.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. 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.

The branched-chain alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.

When ^Ra24 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.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When the cyclic hydrocarbon group of ^Ra24 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 a monocyclic type or a polycyclic type. 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; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group in ^Ra24 is a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle; and includes two or more aromatic rings. A group obtained by removing one hydrogen atom from an aromatic compound (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or the aromatic heterocycle is substituted with an alkylene group (for example, a benzyl group, etc.). Examples thereof include an arylalkyl group such as a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group). The carbon number of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the formulas (anv2) and (anv3), ^Ra25 to ^Ra26 and ^Ra28 to ^Ra30 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms or halogen atoms, and have 1 to 5 carbon atoms, respectively. The alkyl group and the halogen atom are the same as those of Ra ²² and Ra ²³ , respectively.

In formula (anv3), ^Ra27 is a hydrocarbon group which may have an epoxy group-containing group or a substituent. The epoxy group-containing group of ^{Ra 27} is the same as R ^EP in the above formula (A1), and the hydrocarbon group which may have a substituent of ^{Ra 27} is the same as Ra 24.

Specific examples of the structural units represented by the above equations (anv2) to (anv3) are shown below.

When the novolak type epoxy resin (Anv) has other structural units in addition to the structural unit (anv1), the ratio of each structural unit in the resin (Anv) is not particularly limited, but the resin (Anv). ), The total of the constituent units having an epoxy group is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%, based on the total of all the constituent units constituting the above.

・ ・ Bisphenol A type epoxy resin (Abp)
Examples of the bisphenol A type epoxy resin (Abp) include epoxy resins having a structure represented by the following general formula (abp1).

［式中、Ｒ^ＥＰは、エポキシ基含有基であり、Ｒ^ａ３１、Ｒ^ａ３２はそれぞれ独立に、水素原子又は炭素数１～５のアルキル基であり、ｎａ^３１は１～５０の整数である。］

[In the ^formula , R ^EP is an epoxy group-containing group, Ra 31 and Ra ³² are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and na ³¹ is an integer of 1 to 50. ]

In the formula ( ^abp1 ), the alkyl groups having 1 to 5 carbon atoms of Ra 31 and Ra ³² are the same as the alkyl groups having 1 to 5 carbon atoms in R ^p1 and R ^p2 in the formula (A1). Of these, as R ^a31 and R ^a32 , a hydrogen atom or a methyl group is preferable.
The R ^EP is the same as the R ^EP in the above formula (A1), and a glycidyl group is preferable.

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

［式中、Ｒは水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基である。Ｖａ^４１は、置換基を有していてもよい２価の炭化水素基である。ｎａ^４１は０～２の整数である。Ｒ^ａ４１、Ｒ^ａ４２はエポキシ基含有基である。ｎａ^４２は０又は１である。Ｗａ^４１は（ｎａ^４３＋１）価の脂肪族炭化水素基である。ｎａ^４３は１～３の整数である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Va ⁴¹ is a divalent hydrocarbon group which may have a substituent. na ⁴¹ is an integer of 0 to 2. R ^a41 and R ^a42 are epoxy group-containing groups. na ⁴² is 0 or 1. Wa ⁴¹ is an aliphatic hydrocarbon group having a (na ⁴³ +1) valence. na ⁴³ is an integer of 1 to 3. ]

In the formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms of R is preferably linear or branched, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl. Examples include a group, a pentyl group, an isopentyl group, a neopentyl group and the like.
The halogenated alkyl group having 1 to 5 carbon atoms of R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

In the formula (a1-1), Va ⁴¹ is a divalent hydrocarbon group which may have a substituent and has a substituent described in ^REP in the formula (A1). Examples thereof include groups similar to divalent hydrocarbon groups which may be present.
Among the above, the hydrocarbon group of Va ⁴¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, and further preferably a linear aliphatic hydrocarbon group. Linear alkylene groups are particularly preferred.

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

In the formulas (a1-1) and (a1-2), R ^a41 and R ^a42 are epoxy group-containing groups and are the same as R ^EP in the above formula (A1).

In the formula (a1-2), the (na ⁴³ +1) valent aliphatic hydrocarbon group in Wa ⁴¹ means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated. It is also good, usually preferably saturated. The aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a linear or branched aliphatic hydrocarbon group. And a group combining an aliphatic hydrocarbon group containing a ring in the structure can be mentioned.

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

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

In the above formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.
R ^a51 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. R ^a52 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R ^a53 represents a hydrogen atom or a methyl group. na ⁵¹ is an integer of 0 to 10.
R ^a51 , R ^a52 , and R ^a53 may be the same or different from each other.

Further, the acrylic resin (Aac) may have a structural unit derived from another polymerizable compound for the purpose of appropriately controlling physical and chemical properties. Examples of such a polymerizable compound include known radically polymerizable compounds and anionic 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; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Methacrylic acid derivatives having carboxyl groups and ester bonds such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth). ) (Meta) acrylic acid alkyl esters such as acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl ( (Meta) Acrylic acid aryl esters such as acrylates; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α- Vinyl group-containing aromatic compounds such as methylhydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugate diolefins such as butadiene and isoprene; nitrile groups such as acrylonitrile and methacrylonitrile Containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylic amide; and the like.

When the aliphatic epoxy resin and the acrylic resin (Aac) have other structural units, the content ratio of the epoxy group-containing unit in the resin is preferably 5 to 40 mol%, preferably 10 to 30 mol%. Is more preferable, and most preferably 15 to 25 mol%.

Further, as the aliphatic epoxy resin, a compound containing a partial structure represented by the following general formula (m1) (hereinafter, also referred to as “(m1) component”) is also preferably mentioned.

［式中、ｎ_２は、１～４の整数である。＊は結合手を示す。］

[In the formula, n ₂ is an integer of 1 to 4. * Indicates a bond. ]

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

Examples of the component (m1) include compounds 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 preferable.
The divalent linking group here is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. For the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom, the substituent described in ^REP (epoxy group-containing group) in the above formula (A1) is used. It is the same as the divalent hydrocarbon group which may have and the divalent linking group containing a hetero atom, and among them, the divalent linking group containing a hetero atom is preferable, and —Y ²¹ −C (= O). More preferably, a group represented by —O— and a group represented by —C (= O) —O—OY ²¹ −. As ^Y21 , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.

Further, as the aliphatic epoxy resin, a compound represented by the following general formula (m2) (hereinafter, also referred to as “(m2) component”) is also preferably mentioned.

［式中、Ｒ^ＥＰは、エポキシ基含有基である。複数のＲ^ＥＰは、互いに同一であってもよく異なっていてもよい。］

[In the formula, ^REP is an epoxy group-containing group. The plurality of R ^EPs may be the same as or different from each other. ]

In the formula (m2), the R ^EP is an epoxy group-containing group and is the same as the R ^EP in the formula (A1).

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

The polystyrene-equivalent mass average molecular weight of the component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and further preferably 300 to 200,000. By setting such a mass average molecular weight, peeling from the support is less likely to occur, and the strength of the formed cured film is sufficiently increased.

Further, the component (A) preferably has a dispersity of 1.05 or more. With such a degree of dispersion, the lithography characteristics are further improved in pattern formation.
The degree of dispersion here means a value obtained by dividing the mass average molecular weight by the number average molecular weight.

Commercially available products of the component (A) include, for example, as novolak type epoxy resin (Anv), JER-152, JER-154, JER-157S70, 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 , EPICLON HP5000 (above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Corporation) and the like.

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. (The above is manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above, manufactured by DIC Corporation) and the like.

Bisphenol F type epoxy resins include JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, DIC Corporation). , LCE-21, RE-602S (all manufactured by Nippon Kayaku Corporation) and the like.

Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), celoxide 2021P, celoxide 2081, celoxside 2083, celoxside 2085, celoxside 8000, celoxside 8010, and EHPE. -3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Co., Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, Nagase Chemtex shares) (Manufactured by the company), TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd.) and the like.

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 and the like.

-Light initiator (I) that generates acid by exposure
The photoinitiator (component (I)) is irradiated with ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF and ArF, and active energy rays such as X-rays and electron beams to generate cations, and the cations initiate polymerization. It is a compound that can be used as an agent.

The component (I) in the photosensitive resin film of the present embodiment is not particularly limited, and for example, a compound represented by the following general formula (I1) (hereinafter referred to as “component (I1)”) and the following general formula (I2). A compound represented by -1) or (I2-2) (hereinafter referred to as "(I2) component"), or a compound represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "(I3)). "Ingredients").
Among the above, since both the component (I1) and the component (I2) generate a relatively strong acid by exposure, when a pattern is formed by using a photosensitive resin composition containing the component (I). In addition, sufficient sensitivity is obtained and a good pattern is formed.

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

［式中、Ｒ^ｂ０１～Ｒ^ｂ０４は、それぞれ独立に、置換基を有していてもよいアリール基、又はフッ素原子である。ｑは１以上の整数であって、Ｑ^ｑ＋は、それぞれ独立に、ｑ価の有機カチオンである。］

[In the formula, R ^b01 to R ^b04 are aryl groups or fluorine atoms which may independently have a substituent. q is an integer of 1 or more, and Q ^{q +} is an independently q-valent organic cation. ]

... Anion portion In the above formula (I1), R ^b01 to R ^b04 are aryl groups or fluorine atoms which may independently have a substituent.
The aryl group in R ^b01 to R ^b04 preferably has 5 to 30 carbon atoms, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples thereof include a naphthyl group, a phenyl group, an anthrasenyl group and the like, and a phenyl group is preferable because it is easily available.
The aryl group in R ^b01 to R ^b04 may have a substituent. The substituent is not particularly limited, but is a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably 1 to 5 carbon atoms), and an alkyl halide group. Is preferable, a halogen atom or an alkyl halide group having 1 to 5 carbon atoms is more preferable, and a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is particularly preferable. It is preferable that the aryl group has a fluorine atom because the polarity of the anion portion is increased.
Among them, as R ^b01 to R ^b04 of the formula (I1), a fluorinated phenyl group is preferable, and a perfluorophenyl group is particularly preferable.

Preferred specific examples of the anion moiety of the compound represented by the formula (I1) are tetrakis (pentafluorophenyl) borate ([B _{(C6 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) 2 BF 2]-); C ₆ F ₅ ) BF ₃ ] ^- ); Tetrakiss (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ) and the like.
Of these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ) is particularly preferable.

... In the cation part equation (I1), q is an integer of 1 or more, and Q ^{q +} is an organic cation having a q valence independently.
Sulfonium cations and iodonium cations are preferably mentioned as the Q ^{q +} , and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferable.

［式中、Ｒ^２０１～Ｒ^２０７、およびＲ^２１１～Ｒ^２１２は、それぞれ独立に、置換基を有していてもよいアリール基、ヘテロアリール基、アルキル基またはアルケニル基を表す。Ｒ^２０１～Ｒ^２０３、Ｒ^２０６～Ｒ^２０７、Ｒ^２１１～Ｒ^２１２は、相互に結合して、式中のイオウ原子と共に環を形成してもよい。Ｒ^２０８～Ｒ^２０９は、それぞれ独立に、水素原子または炭素数１～５のアルキル基を表す。Ｒ^２１０は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、又は置換基を有していてもよい－ＳＯ_２－含有環式基である。Ｌ^２０１は、－Ｃ（＝Ｏ）－または－Ｃ（＝Ｏ）－Ｏ－を表す。Ｙ^２０１は、それぞれ独立に、アリーレン基、アルキレン基またはアルケニレン基を表す。ｘは、１または２である。Ｗ^２０１は、（ｘ＋１）価の連結基を表す。］

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

Examples of the aryl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
Examples of the heteroaryl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include those in which a part of the carbon atom constituting the aryl group is replaced with a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Examples of the heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and examples of the substituted heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthene-9-one.
The alkyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² preferably has 2 to 10 carbon atoms.
Examples of the substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have include an alkyl group, a halogen atom, an alkyl halide group, a carbonyl group, a cyano group, an amino group, and an oxo group (=). Examples thereof include O), an aryl group, and a group represented by the following formulas (ca-r-1) to (ca-r-10), respectively.

［式中、Ｒ’^２０１は、それぞれ独立に、水素原子、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、又は置換基を有していてもよい鎖状のアルケニル基である。］

[In the formula, ^R'201 independently has a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group that may be present. ]

In the above formulas (ca-r-1) to (ca-r-10), ^R'201 independently has a hydrogen atom and a cyclic group and a substituent which may have a substituent. It is a chain-like alkyl group which may be present, or a chain-like alkenyl group which may have a substituent.

Cyclic group which may have a substituent:
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. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group in ^R'201 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the carbon number does not include the carbon number in the substituent.
Specifically, as the aromatic ring of the aromatic hydrocarbon group in ^R'201 , benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings is substituted with a heteroatom. Examples thereof include aromatic heterocycles, or rings in which a part of hydrogen atoms constituting these aromatic rings or aromatic heterocycles is substituted with an oxo group or the like. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specifically, as the aromatic hydrocarbon group in ^R'201 , a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, an anthracenyl group, etc.), a hydrogen atom of the aromatic ring. A group in which one of the groups is substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), A group obtained by removing one hydrogen atom from a ring in which a part of the hydrogen atom constituting the aromatic ring is substituted with an oxo group or the like (for example, anthraquinone), an aromatic heterocycle (for example, 9H-thioxanthene, 9H-thioxanthene). A group obtained by removing one hydrogen atom from -9-on, etc.) can be mentioned. The carbon number of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

Examples of the cyclic aliphatic hydrocarbon group in ^R'201 include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable. 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 is preferably one having 7 to 30 carbon atoms. Among them, the polycycloalkane is a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecan; a fused ring system such as a cyclic group having a steroid skeleton. Polycycloalkanes having a polycyclic skeleton of are more preferred.

Among them, as the cyclic aliphatic hydrocarbon group in ^R'201 , a group in which one or more hydrogen atoms are removed from monocycloalkane or polycycloalkane is preferable, and a group in which one hydrogen atom is removed from polycycloalkane is preferable. More preferably, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

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, and 1 to 4 carbon atoms. Is more preferable, and 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -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. Alkyl methylene 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. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- , and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Chain-like alkyl group which may have a substituent:
The chain-like alkyl group of ^R'201 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. Specifically, for example, 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 and a tetradecyl group. Examples thereof include a 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-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples thereof include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

Chain alkenyl group which may have a substituent:
The chain alkenyl group of ^R'201 may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5, and even more preferably 2 to 4. 3 is particularly preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.
Among the above, as the chain alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

Examples of the substituent in the cyclic group, chain-like alkyl group or alkenyl group of ^R'201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group and an oxo group. Examples thereof include a cyclic group, an alkylcarbonyl group and a thienylcarbonyl group in ^R'201 .

Among them, ^R'201 is preferably a cyclic group which may have a substituent and a chain alkyl group which may have a substituent.

When R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ²¹² are bonded to each other to form a ring together with the sulfur atom in the formula, heteroatoms such as sulfur atom, oxygen atom, and nitrogen atom, and heteroatoms such as sulfur atom and nitrogen atom are formed. Carbonyl group, -SO-, -SO _2- , -SO _3- , -COO-, -CONH- or _-N (RN)-(the _RN is an alkyl group having 1 to 5 carbon atoms), etc. It may be bonded via a functional group of. As the ring to be formed, one ring containing a sulfur atom in its ring skeleton, including the sulfur atom, is preferably a 3- to 10-membered ring, and particularly preferably a 5- to 7-membered ring. preferable. Specific examples of the formed ring include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxatiin ring, tetrahydro. Examples thereof include a thiophenium ring and a tetrahydrothiopyranium ring.

In the above formula (ca-3), R ²⁰⁸ to R ²⁰⁹ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. In the case of, they may be bonded to each other to form a ring.

In the above formula (ca-3), R ²¹⁰ is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an alkenyl group which may have a substituent. It is a _—SO2 -containing cyclic group which may have a substituent.
Examples of the aryl group in R ²¹⁰ include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
The alkyl group in R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group in R ²¹⁰ preferably has 2 to 10 carbon atoms.

In the above formulas (ca-4) and (ca-5), Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene group, respectively.
Examples of the arylene group in Y ²⁰¹ include a group obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group in ^R'201 .
Examples of the alkylene group and the alkaneylene group in Y ²⁰¹ include a chain-like alkyl group in ^R'201 and a group in which one hydrogen atom is removed from the group exemplified as the chain-like alkenyl group.

In the above formula (ca-4) and formula (ca-5), x is 1 or 2.
W ²⁰¹ is a (x + 1) valence, i.e., a divalent or trivalent linking group.
As the divalent linking group in W ²⁰¹ , a divalent hydrocarbon group which may have a substituent is preferable, and a substituent exemplified by ^REP in the above formula (A1) may be contained. Groups similar to divalent hydrocarbon groups are preferred. The divalent linking group in W ²⁰¹ may be linear, branched or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group or a group consisting of only an arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
Examples of the trivalent linking group in W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ , and a group in which the divalent linking group is further bonded to the divalent linking group. Can be mentioned. As the trivalent linking group in W ²⁰¹ , a group in which two carbonyl groups are bonded to an arylene group is preferable.

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

［式中、Ｒ”^２０１は、水素原子又は置換基である。該置換基としては、前記Ｒ^２０１～Ｒ^２０７、およびＲ^２１０～Ｒ^２１２が有していてもよい置換基として挙げたものと同様である。］

[In the formula, R " ²⁰¹ is a hydrogen atom or a substituent. As the substituent, those listed as the substituents that the R ²⁰¹ to R ²⁰⁷ and the R ²¹⁰ to R ²¹² may have. The same is true.]

Further, as the cation represented by the above formula (ca-1), the cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferable.

［式中、Ｒ’^２１１はアルキル基である。Ｒ^ｈａｌは、水素原子又はハロゲン原子である。］

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

Further, as the cation represented by the above formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-47) are also preferable.

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

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

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

Further, as the cation represented by the above formula (ca-5), the cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferable.

［式中、Ｒ’^２１２はアルキル基又は水素原子である。Ｒ’^２１１はアルキル基である。］

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

Among the above, the cation portion [(Q ^{q +} ) _{1 / q} ] is preferably a cation represented by the general formula (ca-1), and is represented by the formulas (ca-1-1) to (ca-1-47), respectively. The represented cations are more preferred and are represented by the formulas (ca-1-25), (ca-1-26), (ca-1-29), (ca-1-35) and (ca-1-47), respectively. The represented cation is more preferred.

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

［式中、Ｒ^ｂ０５は、置換基を有していてもよいフッ素化アルキル基、又はフッ素原子である。複数のＲ^ｂ０５は、互いに同一であってもよく異なっていてもよい。ｑは１以上の整数であって、Ｑ^ｑ＋は、ｑ価の有機カチオンである。］

[In the formula, R ^b05 is a fluorinated alkyl group or a fluorine atom which may have a substituent. The plurality of R ^b05s may be the same as or different from each other. q is an integer of 1 or more, and Q ^{q +} is a q-valent organic cation. ]

［式中、Ｒ^ｂ０６は、置換基を有していてもよいフッ素化アルキル基、又はフッ素原子である。複数のＲ^ｂ０６は、互いに同一であってもよく異なっていてもよい。ｑは１以上の整数であって、Ｑ^ｑ＋は、ｑ価の有機カチオンである。］

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

... Anion part In the above formula (I2-1), R ^b05 is a fluorinated alkyl group or a fluorine atom which may have a substituent. The plurality of R ^b05s may be the same as or different from each other.
The fluorinated alkyl group in R ^b05 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specifically, in the alkyl group having 1 to 5 carbon atoms, a group in which a part or all of a hydrogen atom is replaced with a fluorine atom can be mentioned.
Among them, as R ^b05 , 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, a trifluoromethyl group or a pentafluoro is preferable. Ethyl groups are more preferred.

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

［式中、Ｒ^ｂｆ０５は、置換基を有していてもよいフッ素化アルキル基である。ｎｂ^１は、１～５の整数である。］

[In the formula, R ^bf05 is a fluorinated alkyl group which may have a substituent. nb ¹ is an integer of 1 to 5. ]

In the formula (b0-2a), the fluorinated alkyl group which may have a substituent in R ^bf05 is the same as the fluorinated alkyl group which may have a substituent described in R ^b05 . be.
In the 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.

In the formula (I2-2), R ^b06 is a fluorinated alkyl group or a fluorine atom which may have a substituent. The plurality of R ^b06 may be the same as or different from each other.
The fluorinated alkyl group in R ^b06 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specifically, in the alkyl group having 1 to 5 carbon atoms, a group in which a part or all of a hydrogen atom is replaced with a fluorine atom can be mentioned.
Among them, as R ^b06 , 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 further preferable.

... Cation part In formulas (I2-1) and (I2-2), q is an integer of 1 or more, and Q ^{q +} is an organic cation having a q valence independently.
As the Q ^{q +} , the same as the above formula (I1) can be mentioned, and among them, the cation represented by the general formula (ca-1) is preferable, and the formulas (ca-1-1) to (ca-1) are preferable. The cations represented by −47) are more preferable, and the formulas (ca-1-25), (ca-1-26), (ca-1-29), (ca-1-35), and (ca-1) are more preferable. The cations represented by −47) are more preferable.

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

［式中、Ｒ^ｂ１１～Ｒ^ｂ１２は、ハロゲン原子以外の置換基を有していてもよい環式基、ハロゲン原子以外の置換基を有していてもよい鎖状のアルキル基、又はハロゲン原子以外の置換基を有していてもよい鎖状のアルケニル基である。ｍは１以上の整数であって、Ｍ^ｍ＋はそれぞれ独立にｍ価の有機カチオンである。］

[In the formula, R ^b11 to R ^b12 are 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 halogen atom. It is a chain alkenyl group which may have a substituent other than the above. m is an integer of 1 or more, and M ^{m +} is an independently m-valent organic cation. ]

{(I3-1) component}
... In the anion part formula (I3-1), R ^b12 is a cyclic group which may have a substituent other than a halogen atom, and a chain-like group which may have a substituent other than a halogen atom. A chain alkenyl group which may have a substituent other than an alkyl group or a halogen atom, and is a cyclic group, a chain alkyl group, or a chain alkenyl group in the above description of ^R'201 . Among them, those having no substituent or those having a substituent other than the halogen atom can be mentioned.
The 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-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. As the aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecan, etc. (may have a substituent other than a halogen atom); It is more preferable that the group is obtained by removing one or more hydrogen atoms from the above.
The hydrocarbon group of R ^b12 may have a substituent other than the halogen atom, and the substituent may be a hydrocarbon group (aromatic hydrocarbon group, aliphatic group) in R ^b11 of the above formula (I3-2). Examples thereof include substituents other than the halogen atom which the cyclic group (cyclic group, chain alkyl group) may have.
The term "may have a substituent other than a halogen atom" as used herein means not only excluding the case of having a substituent consisting of only a halogen atom but also the case of having a substituent containing at least one halogen atom. (For example, when the substituent is a fluorinated alkyl group, etc.) is excluded.

A preferable specific example of the anion portion of the component (I3-1) is shown below.

... In the cation part equation (I3-1), M ^{m +} is an m-valent organic cation.
As the organic cation of M ^{m +} , the same cations as those represented by the above general formulas (ca-1) to (ca-5) are preferably mentioned, and among these, the above general formula (ca-1) is used. The cation represented by is more preferable. Among these, at least one of R ²⁰¹ , R ²⁰² , and R ²⁰³ in the above general formula (ca-1) may have a substituent and may have an organic group having 16 or more carbon atoms (aryl group, heteroaryl). A sulfonium cation (group, alkyl group or alkenyl group) is particularly preferable because it improves resolution and roughness characteristics.
The substituents that the organic group may have are the same as above, and are an alkyl group, a halogen atom, an alkyl halide group, a carbonyl group, a cyano group, an amino group, an oxo group (= O), and an aryl. Groups and groups represented by the above formulas (ca-r-1) to (ca-r-10) can be mentioned.
The organic group (aryl group, heteroaryl group, alkyl group or ^alkenyl group) preferably has 16 to 25 carbon atoms, more preferably 16 to 20 carbon atoms, and particularly preferably 16 to 18 carbon atoms. Examples of the organic cations of the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), and the like. Preferred examples thereof include cations represented by (ca-1-46) and (ca-1-47), respectively.

{(I3-2) component}
... In the anion part formula (I3-2), R ^b11 is a cyclic group which may have a substituent other than a halogen atom, and a chain-like group which may have a substituent other than a halogen atom. A chain alkenyl group which may have a substituent other than an alkyl group or a halogen atom, and is a cyclic group, a chain alkyl group, or a chain alkenyl group in the above description of ^R'201 . Among them, those having no substituent or those having a substituent other than the halogen atom can be mentioned.

Among these, as R ^b11 , 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 halogen. A chain alkyl group which may have a substituent other than an atom is preferable. Examples of the substituent that these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof.
When an ether bond or an ester bond is contained as a substituent, an alkylene group may be used as a substituent. In this case, the substituents are shown in the following general formulas (y-al-1) to (y-al-7), respectively. The linking group to be added is preferable.

［式中、Ｖ’^１０１は単結合または炭素数１～５のアルキレン基であり、Ｖ’^１０２は炭素数１～３０の２価の飽和炭化水素基である。］

[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. ]

The divalent saturated hydrocarbon group in ^V'102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 5 carbon atoms. Is more preferable.

The alkylene group in ^V'101 and ^V'102 may be a linear alkylene group or a branched chain alkylene group, and a linear alkylene group is preferable.
Specific examples of the alkylene group in ^V'101 and ^V'102 are methylene groups [-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 -etc. Alkyl methylene groups; ethylene Group [-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 ) Alkylethylene groups such as CH _2- ; trimethylene group (n-propylene group) [-CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) Alkyltrimethylene groups such as CH _2- ; 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 Alkyltetramethylene groups such as CH _2- ; pentamethylene groups [-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ] and the like can be mentioned.
Further, a part of the methylene group in the alkylene group in ^V'101 or ^V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic ring-type group is obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group of ^R'201 (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group). A divalent group is preferable, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferable.

As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is more preferable.
The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The chain-like alkyl group preferably has 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Linear alkyl groups such as nonyl group and decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl Examples thereof include branched alkyl groups such as a group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

As R ^b11 , a cyclic group which may have a substituent other than a halogen atom is preferable.
A preferable specific example of the anion portion of the component (I3-2) is shown below.

... In the cation part formula (I3-2), M ^{m +} is an m-valent organic cation, which is the same as M ^{m +} in the above formula (I3-1).

Further, the component (I) is a photoinitiator that generates an acid having a pKa (acid dissociation constant) of -5 or less by exposure because of the high elasticity of the resin film and the tendency to form a fine structure without residue. Is preferable. High sensitivity to exposure can be obtained by using a photoinitiator that generates an acid having a pKa of -6 or less, more preferably -8 or less. (I) The lower limit of pKa of the acid generated by the component is preferably -15 or more. By using such a photoinitiator that generates a suitable pKa acid, high sensitivity can be easily achieved.
Here, "pKa (acid dissociation constant)" refers to a substance generally used as an index indicating the acid strength of the target substance. In addition, pKa in this specification is a value under the temperature condition of 25 degreeC. Further, the pKa value can be measured and obtained by a known method. Further, calculated values using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development) can also be used.

Specific examples of the suitable component (I) are given below.

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 kinds selected from the group consisting of the component (I1), the component (I2) and the component (I3).
Among these, it is more preferable that the component (I) is used in combination with one or more selected from the group consisting of the component (I1) and the component (I2) and the component (I3).

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 with respect to 100 parts by mass of the component (A). , 1.0 to 3.0 parts by mass is more preferable.
When the content of the component (I) is at least the lower limit of the above-mentioned preferable range, sufficient sensitivity is obtained and the lithography characteristics of the pattern are further improved. In addition, the strength of the cured film is further increased. On the other hand, when it is not more than the upper limit of the above-mentioned preferable range, the sensitivity is appropriately controlled, and it becomes easy to obtain a pattern having a good shape.

-Other components The photosensitive resin film of the present embodiment may contain other components in addition to the above-mentioned components (A) and (I), if necessary.
The photosensitive resin film of the embodiment may optionally include a miscible additive, such as a sensitizer component, a silane coupling agent, a metal oxide, a solvent, an additional resin for improving the performance of the film. A dissolution inhibitor, a basic compound, a plasticizer, a stabilizer, a colorant, an antihalation agent and the like can be appropriately added and contained.

-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 from exposure and transfer the energy to other substances.
Specific examples of the sensitizer component include benzophenone-based photosensitizers such as benzophenone and p, p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetphen-based photosensitizers, and 1,5-dihydroxynaphthalene. Naphthalene-based photosensitizers such as, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, and known photosensitizers such as biacetyl, eosin, rosebengal, pyrene, phenothiazine, and antron. Can be used.
As the sensitizer component, one type may be used alone, or two or more types may be used in combination.
When the 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 with respect to 100 parts by mass of the component (A). It is more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass.
When the content of the sensitizer component is in the above-mentioned preferable range, the sensitivity and the resolvability are further enhanced.

-Silane coupling agent The photosensitive resin film of the embodiment may further contain an adhesive auxiliary in order to improve the adhesiveness with the support. As the adhesive aid, a silane coupling agent is preferable.
Examples of the silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, and an epoxy group. Specific examples include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl). Examples thereof include ethyltrimethoxysilane.
One type of silane coupling agent may be used alone, or two or more types may be used in combination.
When the 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 with respect to 100 parts by mass of the component (A). It is more preferably 3 to 15 parts by mass, and even more preferably 3 to 10 parts by mass.
When the content of the silane coupling agent is in the above-mentioned preferable range, the strength of the cured film is further increased. In addition, the adhesiveness between the cured film and the support is further strengthened.

-Metal oxide The photosensitive resin film of the present embodiment has strength by having a metal oxide (hereinafter, also referred to as "(M) component") in addition to the component (A) and the component (I). An enhanced cured film is obtained. In addition, a high-resolution pattern can be formed with a good shape.
Examples of the component (M) include oxides of metals such as silicon (metal silicon), titanium, zirconium, and hafnium. Among these, an oxide of silicon is preferable, and among these, silica is particularly preferable.

Further, the shape of the component (M) is preferably particulate.
As the particle-like (M) component, those having a volume average particle diameter of 5 to 40 nm are preferable, those having a volume average particle diameter of 5 to 30 nm are more preferable, and those having a volume average particle diameter of 5 to 30 nm are more preferable. A particle group having a particle size of 10 to 20 nm is more preferable.
When the volume average particle size of the component (M) is at least the lower limit of the above-mentioned preferable range, the strength of the cured film is likely to be increased. On the other hand, when it is not more than the upper limit of the above-mentioned preferable range, residue is less likely to be generated in the formation of the pattern, and a pattern having a higher resolution is more likely to be formed.

The particle size of the component (M) may be appropriately selected according to the exposure light source. Generally, it is said that the influence of light scattering is almost negligible for particles having a particle diameter of 1/10 or less with respect to the wavelength of light. Therefore, for example, when a fine structure is formed by photolithography with i-line (365 nm), the (M) component is a particle group having a primary particle diameter (volume average value) of 10 to 20 nm (particularly preferably a silica particle group). ) Is preferably used.

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, more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the component (A).
When the content of the component (M) is at least the lower limit of the above-mentioned preferable range, the strength of the cured film is further increased. On the other hand, when it is not more than the upper limit of the above-mentioned preferable range, the fluidity of the photosensitive resin composition is easily maintained.

≪Solvent≫
The photosensitive resin film of the embodiment can be produced by dissolving or dispersing the photosensitive material in a solvent (hereinafter referred to as "component (S)").
Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; ethylene glycol and diethylene glycol. , Polyhydric alcohols such as propylene glycol and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyvalent alcohols or the esters. Derivatives of polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monoalkyl ether such as monobutyl ether, or compounds having an ether bond such as monophenyl ether [among these, methoxybutyl Acetates, propylene glycol monomethyl ether acetates (PGMEA), propylene glycol monomethyl ethers (PGME) are preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, Esters such as methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentyl Examples thereof include aromatic organic solvents such as benzene, isopropylbenzene, toluene, xylene, simene and mesityrene, and dimethylsulfoxide (DMSO).
As the component (S), one type may be used alone, or two or more types may be used as a mixed solvent.

The amount of the component (S) used is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like.
The content of the component (S) in the photosensitive resin composition is preferably 1 to 25% by mass, more preferably 5 to 20% by mass, based on the total amount (100% by mass) of the photosensitive resin composition.

(Manufacturing method of hollow package)
The manufacturing method according to the second aspect of the present invention comprises 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. It is a manufacturing method of.

As the sealing material, for example, a resin composition can be used. The resin used for the encapsulant is not particularly limited as long as the hollow structure can be sealed and insulated at least, and examples thereof include epoxy resins and silicone resins.
The encapsulant may contain other components such as a filler in addition to the resin.

The method of sealing the hollow structure with a sealing material is not particularly limited, and the heat-melted sealing material is supplied onto the hollow structure so as to cover the hollow structure and is compression-molded to form a hollow structure. A hollow package having a sealing material layer on the structure is produced.
The encapsulant layer has a function of protecting the MEMS, wiring portion, etc. in the hollow structure from the external environment.

Since the hollow package manufactured by the manufacturing method according to this aspect includes the hollow structure 100 manufactured by the manufacturing method according to the first aspect described above, the conductor pattern and the lead frame are collectively used at the time of sealing. The occurrence of problems such as deformation of the hollow structure at the time of connection or separation of the substrate by dicing or the like is suppressed. Therefore, the space inside the hollow structure is reliably maintained, and a highly reliable microdevice can be provided.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. "Parts" in the description of each production example means parts by mass.

<Preparation of negative photosensitive resin composition>
(Preparation Examples 1 to 4)
Each component shown in Table 1 was mixed and dissolved, filtered using a PTFE filter (pore diameter 1 μm, manufactured by PALL), and the negative photosensitive resin composition of each example (MEK having a solid content of about 84% by mass) was used. Solutions) were prepared respectively.

In Table 1, each abbreviation has the following meaning. The numerical value in [] is the blending amount (part by mass; solid content conversion) of each component.
(A) -1: Epoxy group-containing resin represented by the following chemical formula (A11). Product name "JER-157S70", manufactured by Mitsubishi Chemical Corporation.

(I) -1: Photoinitiator represented by the following chemical formula (I2-2-1). Product name "ADEKA PTOMA-SP172", manufactured by ADEKA CORPORATION.
(I) -3: Photoinitiator represented by the following chemical formula (I1-4). Product name "Irgacure 290", manufactured by BASF.
(I) -4: Photoinitiator represented by the following chemical formula (I1-1). Product name "CPI-310B", manufactured by Sun Appro Co., Ltd.
(I) -5: Photoinitiator represented by the following chemical formula (I1-3). Product name "CPI-410B", manufactured by Sun Appro Co., Ltd.
(I) -6: Photoinitiator represented by the following chemical formula (I2-1-2). Product name "CPI-410S", manufactured by Sun Appro Co., Ltd.

(I) -2: Photoinitiator represented by the following chemical formula (I3-1-1). Product name "HS-1CS", manufactured by Sun Appro Co., Ltd.

(C) -1: Sensitizer. α-Naphthol.
(D) -1: Silane coupling agent. Product name "Shin-Etsu Silicone (registered trademark) OFS6040SILANE", manufactured by Shin-Etsu Chemical Co., Ltd.
(D) -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.

<Manufacturing method of hollow structure>
As the base film, a silicone-based surface release-treated PET film (trade name "A53", manufactured by Teijin Limited) was used.

(Example 1)
Step (0):
The negative photosensitive resin composition of Preparation Example 1 is applied onto the base film using an applicator, heated at a temperature of 60 ° C. for 5 minutes in an oven, and then baked at 70 ° C. for 10 minutes (PAB). ) To form a photosensitive resin film having a thickness of 30 μm to obtain a photosensitive resist film (1).
In addition, a stepped substrate having a recess on the surface was prepared.

Step (i):
The photosensitive resist film (1) was arranged so that the surface of the photosensitive resin film of the photosensitive resist film (1) closed the opening surface of the recess in the stepped substrate.

After the step (i), an operation of peeling the base film from the photosensitive resin film of the photosensitive resist film (1) was performed.

Step (ii):
Then, using a Canon PLA-501 ghi line aligner, the photosensitive resin film was exposed to 300 mJ / cm ² (i-line conversion).

Step (iii):
The photosensitive resin film after exposure in the step (ii) was heat-treated in an oven at a temperature of 50 ° C. for 3 minutes.

Step (iv):
The photosensitive resin film after the heat treatment in the step (iii) was paddle-developed at 23 ° C. using propylene glycol monomethyl ether acetate as a developing solution to form a negative pattern to be a top plate portion.

Step (v):
The negative pattern after the step (iv) is further cured by heat treatment at a temperature of 200 ° C. for 60 minutes in an oven, and the top plate portion is hollow made of a cured body of a photosensitive resin film. A structure (the cross section of the hollow structure portion in the height direction is rectangular: length (height) 200 μm × width 500 μm) was obtained.

(Example 2)
The operation of peeling the base film from the photosensitive resin film of the photosensitive resist film (1) is performed between the step (iii) and the step (iv).
In the step (iii), a hot plate is heat-treated at a temperature of 60 ° C. for 10 minutes, and the temperature after heating is 60 ° C., and further, a hot plate is heat-treated at a temperature of 90 ° C. for 3 minutes. A hollow structure was obtained in the same manner as in Example 1.

(Example 3)
In the step (iii), a hot plate is heat-treated at a temperature of 60 ° C. for 10 minutes, and the temperature after heating is 60 ° C., and further, a hot plate is heat-treated at a temperature of 90 ° C. for 3 minutes. A hollow structure was obtained in the same manner as in Example 1.

(Example 4)
The operation of peeling the base film from the photosensitive resin film of the photosensitive resist film (1) was the same as in Example 1 except that the operation was performed between the step (iii) and the step (iv). Obtained a hollow structure.

(Example 5)
The operation of peeling the base film from the photosensitive resin film of the photosensitive resist film (1) is performed between the step (ii) and the step (iii).
In the step (iii), a hollow structure was obtained in the same manner as in Example 1 except that the hot plate was heat-treated at a temperature of 50 ° C. for 30 minutes.

(Example 6)
A hollow structure was obtained in the same manner as in Example 4 except that the negative photosensitive resin composition of Preparation Example 1 was changed to the negative photosensitive resin composition of Preparation Example 2.

(Example 7)
A hollow structure was obtained in the same manner as in Example 4 except that the negative photosensitive resin composition of Preparation Example 1 was changed to the negative photosensitive resin composition of Preparation Example 3.

(Example 8)
A hollow structure was obtained in the same manner as in Example 4 except that the negative photosensitive resin composition of Preparation Example 1 was changed to the negative photosensitive resin composition of Preparation Example 4.

(Example 9)
A hollow structure was obtained in the same manner as in Example 2 except that the negative photosensitive resin composition of Preparation Example 1 was changed to the negative photosensitive resin composition of Preparation Example 2.

(Example 10)
A hollow structure was obtained in the same manner as in Example 2 except that the negative photosensitive resin composition of Preparation Example 1 was changed to the negative photosensitive resin composition of Preparation Example 3.

(Example 11)
A hollow structure was obtained in the same manner as in Example 2 except that the negative photosensitive resin composition of Preparation Example 1 was changed to the negative photosensitive resin composition of Preparation Example 4.

(Comparative Example 1)
In the step (iii), a hollow structure was obtained in the same manner as in Example 1 except that the hot plate was heat-treated at a temperature of 90 ° C. for 5 minutes.

(Comparative Example 2)
In the step (iii), a hollow structure was obtained in the same manner as in Example 2 except that the hot plate was heat-treated at a temperature of 90 ° C. for 5 minutes.

(Comparative Example 3)
In the step (iii), a hollow structure was obtained in the same manner as in Example 5 except that the hot plate was heat-treated at a temperature of 90 ° C. for 5 minutes.

(Comparative Example 4)
In the step (iii), a hollow structure was obtained in the same manner as in Example 1 except that the heat treatment was performed in an oven at a temperature of 80 ° C. for 20 minutes.

(Comparative Example 5)
A hollow structure was obtained in the same manner as in Comparative Example 1 except that the negative photosensitive resin composition of Preparation Example 1 was changed to the negative photosensitive resin composition of Preparation Example 2.

<Evaluation>
The deformation of the top plate portion in the hollow structure of each obtained example was evaluated.
In this evaluation, the degree of swelling of the top plate portion and the degree of pattern shift of the photosensitive resin film constituting the top plate portion were evaluated as follows.

[Swelling of the top plate]
The hollow structure immediately after production was cut in the height direction, and the degree of deformation (bulging of the top plate portion) in the height direction of the hollow structure portion was measured using a Dektak surface step meter.
Then, according to the following evaluation criteria, this result is shown in Tables 2 to 4 as "top plate bulge (μm)". The numerical value in parentheses indicates the amount of deformation (μm) of the portion where the bulge of the top plate portion is the largest.
Evaluation Criteria 〇: The deformation of the hollow structure portion in the height direction was 5 μm or less.
X: The deformation of the hollow structure portion in the height direction exceeded 5 μm.

[Pattern shift of photosensitive resin film]
The hollow structure immediately after production is cut in the height direction, and the hollow structure portion is observed from the side surface to check the degree of deformation (pattern shift of the photosensitive resin film) of the peripheral end portion of the top plate portion by Olympus MX-50. And measured using a length measuring system manufactured by Frobel.
Then, according to the following evaluation criteria, the results are shown in Tables 2 to 4 as "pattern shift (μm)". The numerical value in () indicates the amount of deformation (μm) of the portion where the pattern shift is the largest.
Evaluation Criteria 〇: Deformation of the peripheral end of the top plate was 5 μm or less.
X: The deformation of the peripheral end of the top plate exceeded 5 μm.

From the results shown in Tables 2 to 4, in the hollow structures of Examples 1 to 11, both the swelling of the top plate portion due to the PEB operation at the time of manufacturing the hollow structure and the pattern shift of the photosensitive resin film constituting the top plate portion are both. It can be seen that it is kept low.

On the other hand, in the hollow structures of Comparative Examples 1 and 3 to 5, it was found that the swelling of the top plate portion due to the PEB operation during the production thereof was large. Further, in the hollow structure of Comparative Example 2, it was also confirmed that the pattern shift of the photosensitive resin film constituting the top plate portion was large.

Therefore, it was confirmed that by applying the present invention, the deformation of the top plate portion due to the PEB operation is suppressed and the hollow structure can be stably manufactured.

10 substrate, 20 side walls, 30 photosensitive resin film, 40 cured product, 50 base film, 60 photomask, 80 laminated film, 100 hollow structure

Claims (7)

It is a method of manufacturing a hollow structure including a recess and a top plate portion that closes the opening surface of the recess.
A step of preparing a substrate having a recess on the surface and a photosensitive resist film having a negative type photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates an acid by exposure ( 0) and
The step (i) of arranging the photosensitive resist film so that the surface of the photosensitive resin film of the photosensitive resist film closes the opening surface of the recess in the substrate.
After the step (i), the step of exposing the photosensitive resin film (ii) and
The step (iii) of heat-treating the photosensitive resin film after the step (iii),
After the step (iii), a step (iv) of developing the photosensitive resin film to form a negative pattern,
The step (v) of obtaining a hollow structure in which the top plate portion is made of a cured body of the photosensitive resin film by further performing a heat treatment on the negative pattern after the step (iv). Have,
A method for producing a hollow structure, wherein the heat treatment in the step (iii) is performed by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer. The photosensitive resist film in the step (0) is a laminated film in which the photosensitive resin film is laminated on a base film.
The method for producing a hollow structure according to claim 1, wherein the operation of peeling the base film from the photosensitive resin film is performed between the step (i) and the step (ii). The photosensitive resist film in the step (0) is a laminated film in which the photosensitive resin film is laminated on a base film.
The method for manufacturing a hollow structure according to claim 1, wherein the operation of peeling the base film from the photosensitive resin film is performed between the step (ii) and the step (iii). The photosensitive resist film in the step (0) is a laminated film in which the photosensitive resin film is laminated on a base film.
The method for producing a hollow structure according to claim 1, wherein the operation of peeling the base film from the photosensitive resin film is performed between the step (iii) and the step (iv). The heat treatment in the step (iii)
It is carried out by heating at a temperature of 40 ° C. or higher and 70 ° C. or lower for 3 minutes or longer, and then continuously from the temperature after this heating, further by heating at a temperature of 90 ° C. or higher for 3 minutes or longer.
The method for manufacturing a hollow structure according to any one of claims 1 to 4. The method for producing a hollow structure according to any one of claims 1 to 5, wherein the epoxy group-containing resin (A) contains a resin (A1) represented by the following general formula (A1).

[In the formula, R ^p1 and R ^p2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. The plurality of R ^p1s may be the same as or different from each other. The plurality of R ^p2s 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. The plurality of R ^EPs may be the same as or different from each other. ] A method for manufacturing a hollow package, comprising a step of sealing the hollow structure manufactured by the manufacturing method according to any one of claims 1 to 6 with a sealing material to obtain a hollow package.

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