Method for manufacturing a hollow encapsulation and method for providing a photosensitive composition

Abstract

A method for manufacturing a hollow package includes: a step of forming sidewalls on a substrate having aluminum wiring; and a step of forming a top plate portion on the aforementioned sidewalls to fabricate the aforementioned hollow structure housing the aforementioned aluminum wiring, wherein the photosensitive composition forming the aforementioned sidewalls and / or the aforementioned top plate portion comprises an anion represented by the general formula (I1-an), in which A is a heteroatom; X is a halogen atom; R is a monovalent organic group; k is an integer from 1 to 6; m is an integer from 0 to 5; n is an integer from 1 to 3; and m / (k+m) is 0 or more and less than 0.7. [Chemical Formula 1]

Description

Technical Field

[0001] This invention relates to a method for manufacturing a hollow encapsulation and a method for providing a photosensitive composition.

[0002] This application claims priority based on Japanese Patent Application No. 2020-192768, filed in Japan on November 19, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] The hollow encapsulation of the electronic device using a surface elastic wave (SAW) filter has a hollow structure for ensuring the propagation of surface elastic waves and the mobility of the movable parts of the electronic device (see Patent Document 1).

[0004] The hollow package is formed by molding a hollow structure, which maintains a hollow state on a wiring substrate where electrodes are formed, using a photosensitive material. Patent Document 2 describes the use of aluminum alloy as the SAW filter in the hollow structure.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2020 / 137610

[0008] Patent Document 2: Japanese Patent Application Publication No. 2012-209817 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, the inventors of this application discovered through research that when aluminum wiring using aluminum alloy is actually included in a hollow structure, the aluminum wiring may corrode.

[0011] Therefore, the present invention was made in view of the above circumstances, and the object is to provide a method for manufacturing a hollow package capable of suppressing corrosion of the aluminum wiring constituting the hollow package and a method for providing a photosensitive composition.

[0012] Methods for solving problems

[0013] To address the aforementioned issues, the present invention employs the following configuration.

[0014] The first aspect of the present invention is a method for manufacturing a hollow package, wherein the hollow package has a hollow structure for housing the aluminum wiring on a substrate having aluminum wiring. The manufacturing method is characterized by comprising: a step of forming a sidewall surrounding the aluminum wiring on the substrate having aluminum wiring; and a step of forming a top plate portion on the sidewall to manufacture the hollow structure for housing the aluminum wiring, wherein the sidewall and / or the top plate portion is formed of a photosensitive composition, the photosensitive composition containing a cationic polymerization initiator formed by a cationic portion and anionic portion, the anionic portion containing an anion represented by the following general formula (I1-an).

[0015] [Chemical Formula 1]

[0016]

[0017] [In the formula, A is a heteroatom selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic, antimony, and bismuth. X is a halogen atom. R is a monovalent organic group. k is an integer from 1 to 6. Where k is 2 or higher, multiple Rs can be linked to form a divalent or higher organic group coordinated with A. m is an integer from 0 to 5. n is an integer from 1 to 3. m / (k+m) is 0 or higher and less than 0.7.]

[0018] The second aspect of the present invention is a method for providing a photosensitive composition, wherein the aforementioned photosensitive composition is provided to a production line performing the manufacturing method of the hollow package according to the first aspect.

[0019] Invention Effects

[0020] According to the present invention, a method for manufacturing a hollow package capable of suppressing corrosion of aluminum wiring constituting the hollow package and a method for providing a photosensitive composition can be provided. Attached Figure Description

[0021] [ Figure 1 This is a flowchart illustrating a method for manufacturing a hollow package according to an embodiment of the present invention.

[0022] [ Figure 2 This is a schematic diagram illustrating the manufacturing method of the hollow package according to an embodiment of the present invention.

[0023] [ Figure 3 [A diagram illustrating whether or not corrosion occurred after a HAST test of the embodiments of the present invention.]

[0024] [ Figure 4 [A diagram illustrating whether or not corrosion occurred after a PCT test in an embodiment of the present invention.] Detailed Implementation

[0025] In this specification and claims, the term "aliphatic" is a relative concept compared to aromatic, and is defined as a group or compound that does not have aromatic properties.

[0026] Unless otherwise specified, "alkyl" includes monovalent saturated hydrocarbon groups that are straight-chain, branched, or cyclic. The same applies to alkyl groups in alkoxy groups.

[0027] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0028] "Halogenated alkyl" is a group in which some or all of the hydrogen atoms of an alkyl group are replaced by halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0029] "Fluoroalkyl" refers to a group in which some or all of the hydrogen atoms of an alkyl group are replaced by fluorine atoms.

[0030] The term "structural unit" refers to the monomer unit that constitutes a polymer compound (resin, polymer, copolymer).

[0031] The cases described as "may have substituents" include both cases where a hydrogen atom (-H) is replaced by a monovalent group and cases where a methylene group (-CH2-) is replaced by a divalent group.

[0032] "Exposure" is a concept that includes all forms of radiation exposure.

[0033] (Manufacturing method of hollow package)

[0034] The method for manufacturing a hollow package according to this embodiment is a method for manufacturing a hollow package having a hollow structure for housing the aforementioned aluminum wiring on a substrate having aluminum wiring. The method is characterized by comprising: a step of forming a sidewall surrounding the aforementioned aluminum wiring on the aforementioned substrate having aluminum wiring; and a step of forming a top plate portion on the aforementioned sidewall to manufacture the aforementioned hollow structure for housing the aforementioned aluminum wiring, wherein the aforementioned sidewall and / or the aforementioned top plate portion are formed of a specific photosensitive composition.

[0035] Specifically, the method for manufacturing the hollow package in the embodiment includes: a step of forming a sidewall surrounding the aluminum wiring on a substrate having aluminum wiring (first step (S1)); and a step of forming a top plate portion on the sidewall to manufacture the hollow structure that houses the aluminum wiring (second step (S2)).

[0036] The following is for reference Figure 1 and Figure 2 An embodiment of a method for manufacturing a hollow package with sidewalls and top plate formed of a photosensitive composition will be described.

[0037] Figure 1 This is a flowchart illustrating a method for manufacturing a hollow package according to an embodiment of the present invention.

[0038] Figure 2 This is a schematic diagram illustrating the second step (S2) described later in the method for manufacturing the hollow package of the embodiment.

[0039] [First Process]: S1

[0040] In the first step of this embodiment, a sidewall 20 surrounding the aluminum wiring is formed on a substrate 10 having aluminum wiring.

[0041] The first step S1 of this embodiment may include a film forming step S11, an exposure step S12, and a development step S13, as follows.

[0042] [[Membrane Formation Process]]: S11

[0043] First, the photosensitive composition described later is coated onto the support (substrate 10) using known methods such as spin coating, roller coating, or screen printing. Then, a baking (pre-baking (PAB)) treatment is performed at a temperature of, for example, 50 to 150°C for 2 to 60 minutes to form a photosensitive resin film.

[0044] The support (substrate 10) is not particularly limited and can be any conventionally known support, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. More specifically, substrates made of metals such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium, tungsten, copper, chromium, iron, and aluminum, as well as glass substrates, can be used. For example, copper, aluminum, nickel, and gold can be used as the material for the wiring pattern.

[0045] In this embodiment, aluminum wiring is used for the wiring pattern. "Aluminum wiring" includes not only wiring formed of aluminum alloys, but also wiring formed of alloys of aluminum and other metals. In terms of the alloy constituting the wiring that can be used as aluminum wiring, aluminum alloys, aluminum-copper alloys, etc. are preferred.

[0046] The thickness of the photosensitive resin film formed from the photosensitive composition is not particularly limited, but is preferably about 10 to 100 μm.

[0047] [Exposure Process]: S12

[0048] Next, selective exposure is performed on the formed photosensitive resin film using a known exposure apparatus, either by exposure through a mask (mask pattern) with a predetermined pattern formed on it, or by drawing using direct electron beam irradiation without the mask pattern.

[0049] After the aforementioned selective exposure, a baking (post-exposure baking (PEB)) process is performed as needed, for example at a temperature of 80–150°C for 40–1200 seconds, preferably 40–1000 seconds, and more preferably 60–900 seconds.

[0050] There is no particular limitation on the wavelength used for exposure; selective irradiation (exposure) can be performed using radiation, such as ultraviolet light with wavelengths of 300–500 nm, i-rays (wavelength 365 nm), or visible light. Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc., can be used as the source of these radiations.

[0051] Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the film thickness, etc. For example, when using an ultra-high pressure mercury lamp, it ranges from 100 to 2000 mJ / cm². 2 .

[0052] The exposure method for photosensitive resin films can be either conventional exposure (dry exposure) in inert gases such as air or nitrogen, or liquid immersion lithography.

[0053] The photosensitive resin film after the exposure process has high transparency; for example, the haze value when irradiated with i-ray (wavelength 365nm) is preferably less than 3%, and more preferably 1.0 to 2.7%.

[0054] Thus, the photosensitive resin film formed using the photosensitive composition in the above embodiments has high transparency. Therefore, during exposure in pattern formation, the high light transmittance makes it easy to obtain negative patterns with good photolithographic properties.

[0055] The haze value of the photosensitive resin film after the exposure process was determined in accordance with the method of JIS K 7136 (2000).

[0056] [Developing Process]: S13

[0057] Next, the exposed photosensitive resin film is developed using a developer containing an organic solvent (organic developer). After development, rinsing is preferably performed. Baking (post-baking) may be performed as needed.

[0058] As for the organic solvent contained in the organic-based developer, it is only necessary to be able to dissolve component (A) (the component (A) before exposure), and it can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents, can be cited.

[0059] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone-based acetone, ionone, diacetone alcohol, acetylethanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methylpentyl ketone (2-heptanone). Among these, methylpentyl ketone (2-heptanone) is preferred as a ketone solvent.

[0060] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy, ethyl ethoxy, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, etc. 4-Ethoxybutyl acetate, 4-Propoxybutyl acetate, 2-Methoxypentyl acetate, 3-Methoxypentyl acetate, 4-Methoxypentyl acetate, 2-Methyl-3-Methoxypentyl acetate, 3-Methyl-3-Methoxypentyl acetate, 3-Methyl-4-Methoxypentyl acetate, 4-Methyl-4-Methoxypentyl acetate, Propylene glycol diacetate, Methyl formate, Ethyl formate, Butyl formate, Propyl formate, Ethyl lactate Butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc. Among these, butyl acetate or PGMEA is preferred as an ester solvent.

[0061] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0062] Organic developers may incorporate known additives as needed. Examples of such additives include surfactants. There are no particular limitations on the surfactant; for example, ionic, nonionic fluorinated, and / or silicone surfactants may be used.

[0063] As a surfactant, a nonionic surfactant is preferred, and a nonionic fluorinated surfactant or a nonionic silicone surfactant is more preferred.

[0064] When a surfactant is used, its amount relative to the total amount of the organic developer is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0065] The developing process can be carried out using known developing methods, such as immersing the support in the developer for a certain time (immersion method), paddle method (using surface tension to accumulate the developer on the surface of the support and letting it stand for a certain time), spraying the developer onto the surface of the support (spraying method), and continuously discharging the developer while the developer nozzle scans the support rotating at a certain speed (dynamic dispense method), etc.

[0066] The rinsing process (cleaning process) using rinsing solution can be carried out using known rinsing methods. Examples of such rinsing methods include continuously discharging rinsing solution onto a support rotating at a certain speed (rotation coating method), immersing the support in rinsing solution for a certain time (immersion method), and spraying rinsing solution onto the surface of the support (spraying method).

[0067] The rinsing process preferably uses a rinsing solution containing organic solvents.

[0068] Through the aforementioned film formation, exposure, and development processes, sidewalls 20 surrounding the aluminum wiring can be formed on the substrate 10 having aluminum wiring. The substrate 10 obtained in the first process, with sidewalls 20 formed, is equivalent to... Figure 2 The substrate shown in [process (0)]. For example... Figure 2 As shown in [process (0)], a recess 15 is formed by the sidewall 20 surrounding the aluminum wiring and the substrate 10.

[0069] [Second Process]: S2

[0070] In the second step of this embodiment, an exposure portion 30A, which becomes a top plate portion, is formed on the side wall 20 formed in the first step, and the aforementioned hollow structure for housing the aforementioned aluminum wire is manufactured.

[0071] The second step in this embodiment has the following steps (0), (i), (ii), (iii), (iv), and (v).

[0072] Step (0): The step of preparing the substrate 10 with sidewalls 20 and the photosensitive resist film 30F with photosensitive resin film 30 obtained in the first step.

[0073] Step (i): The photosensitive resist film 30F is disposed such that the opening surface of the recess 15 (which is formed by the sidewall 20 surrounding the aluminum wiring and the substrate 10) is blocked by the aforementioned photosensitive resist film 30F, and the aforementioned substrate film is peeled off from the photosensitive resin film 30 constituting the aforementioned photosensitive resist film 30F.

[0074] Step (ii): A step of exposing the aforementioned photosensitive resin film 30 after step (i).

[0075] Step (iii): A step of heat-treating the aforementioned photosensitive resin film 30 after step (ii).

[0076] Step (iv): After step (iii), the aforementioned photosensitive resin film 30 is developed to form a negative pattern (exposure section 30A) that blocks the opening of the recess 15 formed by the sidewall 20 formed in the first step and the recess formed by the substrate 10.

[0077] Step (v): The negative pattern (exposure section 30A) after step (iv) is further heated to cure it, resulting in a hollow structure 100 formed by the cured body 40 of the photosensitive resin film of the exposure section 30A that becomes the top plate.

[0078] [[Process (0)]]: S20

[0079] In step (0) of this embodiment, a substrate 10 with sidewalls 20 formed in the first step and a photosensitive resist film 30F having a photosensitive resin film are prepared.

[0080] exist Figure 2 In this, a substrate having a recess 15 on its surface is formed by a substrate 10 and a sidewall 20 formed on the substrate 10.

[0081] Regarding photosensitive resist films

[0082] The photosensitive resist film 30F in this embodiment, for example, has a negative photosensitive resin film 30, which contains an epoxy-containing resin (component (A)) and a cationic polymerization initiator (component (I)). The photosensitive resin film 30 can be formed from the negative photosensitive composition described later.

[0083] The photosensitive resin film 30 constituting the exposure portion 30A of the top plate portion can be the same material as the photosensitive resin material forming the sidewall 20, or it can be a different material.

[0084] When a photosensitive resin film 30 is formed using the aforementioned photosensitive resist film 30F, and this photosensitive resin film 30 is selectively exposed, acid is generated from component (I) in the exposed portion 30A of the photosensitive resin film 30. Under the action of this acid, the epoxy groups in component (A) undergo ring-opening polymerization, reducing the solubility of component (A) in the developer containing organic solvent. On the other hand, in the unexposed portion 30B of the photosensitive resin film 30, the solubility of component (A) in the developer containing organic solvent remains unchanged. Therefore, a difference in solubility in the developer containing organic solvent arises between the exposed portion 30A and the unexposed portion 30B of the photosensitive resin film 30. That is, the photosensitive resin film 30 is negative. Therefore, when the photosensitive resin film 30 is developed using a developer containing organic solvent, the unexposed portion 30B is dissolved and removed, forming a negative pattern.

[0085] Here, the negative photosensitive resin film 30 of the photosensitive resist film 30F is typically composed of a B-stage (semi-cured) resin material.

[0086] As a photosensitive resist film 30F, an example is a film formed by laminating a photosensitive resin film 30 onto a substrate film. In this embodiment, the photosensitive resist film 30F is preferably a laminated film formed by laminating a photosensitive resin film 30 onto a substrate film.

[0087] The photosensitive resist film 30F can be manufactured by coating a negative photosensitive composition, which is formed by dissolving component (A) and component (I) in a solvent, onto a substrate film and drying it to form a photosensitive resin film 30.

[0088] For coating negative photosensitive compositions onto a substrate film, appropriate methods based on applicators, blade coaters, lip coaters, comma coaters, film coaters, etc., can be used.

[0089] The thickness of the photosensitive resin film 30 is preferably less than 100 μm, and more preferably 5 to 50 μm.

[0090] Known substrate films can be used as the substrate film, such as thermoplastic resin films. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 to 150 μm.

[0091] Using the substrate with sidewalls prepared in the first step above and the photosensitive resist film prepared in step (0) above, the following steps (i) to (v) are performed.

[0092] [[Process(i)]]: S21

[0093] In step (i), the photosensitive resist film 30F is disposed such that the opening surface of the recess 15 formed by the sidewall 20 and the substrate 10 is blocked by the surface of the photosensitive resin film 30 constituting the photosensitive resist film 30F. Then, the substrate film is peeled off from the photosensitive resin film 30 constituting the photosensitive resist film 30F.

[0094] exist Figure 2 In this arrangement, the photosensitive resin film 30 constituting the photosensitive resist film 30F is positioned opposite the substrate 10 with respect to the sidewall 20. Thus, a hollow, sealed space (cavity) is formed, surrounded by the substrate 10, the sidewall 20, and the photosensitive resin film 30.

[0095] [[Process (ii)]]: S22

[0096] In step (ii), the photosensitive resin film 30 is exposed.

[0097] For example, a known exposure device is used to selectively expose the photosensitive resin film 30 through a photomask 60 with a predetermined pattern.

[0098] There are no particular restrictions on the wavelength used for exposure; selective irradiation (exposure) can be performed using radiation, such as ultraviolet light with wavelengths of 300–500 nm, i-rays (wavelength 365 nm), or visible light. Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc., can be used as the source of these radiations.

[0099] [[Process (iii)]]: S23

[0100] In step (iii), the exposed photosensitive resin film 30 is subjected to heat treatment, a so-called post-exposure baking (PEB) treatment.

[0101] PEB treatment is performed, for example, at a temperature of 80–150°C for 40–600 seconds, preferably 60–300 seconds.

[0102] Through the heat treatment in step (iii), the exposed photosensitive resin film 30 becomes the exposed part 30A and the unexposed part 30B obtained by ring-opening polymerization of epoxy groups in component (A).

[0103] [[Process (iv)]]: S24

[0104] In step (iv), the photosensitive resin film 30 (exposed part 30A, unexposed part 30B) after PEB treatment is developed to form a negative pattern (exposed part 30A).

[0105] The development process here can be performed in the same way as the [development process] described above. After development, rinsing is preferably performed.

[0106] Through development in process (iv), the unexposed portion 30B is dissolved and removed, leaving the exposed portion 30A of the top plate portion (the top cover (Roof) that blocks the opening of the wall portion) as a negative pattern residue.

[0107] [[Process (v)]]: S25

[0108] In process (v), the developed negative pattern (exposure section 30A) is further heated (curing operation) to cure it, thereby obtaining a hollow structure 100 formed by the cured body 40 of the photosensitive resin film 30 in the top plate section.

[0109] exist Figure 2 In the cured body 40, the photosensitive resin material forming the sidewall 20 and the photosensitive resin film 30 are cured and integrated.

[0110] In addition, Figure 2 In this embodiment, the hollow structure 100 includes: a substrate 10 having aluminum wiring; and a solidified body 40.

[0111] (Negative photosensitizing composition)

[0112] The negative photosensitive composition (hereinafter, sometimes simply referred to as "photosensitive composition") used in the manufacturing method of the hollow package in this embodiment contains a cationic polymerization initiator (I) formed by a cationic portion and an anionic portion.

[0113] Specifically, the negative photosensitive composition used in the manufacturing method of the hollow package in this embodiment contains a cationic polymerization initiator (I) and an epoxy-containing compound (A) as a resin.

[0114] Hereinafter, the component of the cationic polymerization initiator (I) will be referred to as "(I) component" and the epoxy-containing compound (A) will be referred to as "(A) component".

[0115] When a photosensitive resin film is formed using the above-described photosensitive composition and selectively exposed, the cationic fraction of component (I) in the exposed portion of the film decomposes to generate acid. Under the action of this acid, the epoxy groups in component (A) undergo ring-opening polymerization, reducing the solubility of component (A) in a developer containing organic solvents. Conversely, in the unexposed portion of the film, the solubility of component (A) in a developer containing organic solvents remains unchanged. Therefore, a difference in solubility in a developer containing organic solvents arises between the exposed and unexposed portions of the photosensitive resin film. Consequently, when the photosensitive resin film is developed using a developer containing organic solvents, the unexposed portions are dissolved and removed, forming a negative pattern.

[0116] <Catonic Polymerization Initiator (I)>

[0117] Cationic polymerization initiators (component I) are compounds that generate cations when irradiated by active energy rays such as ultraviolet light, far ultraviolet light, KrF, ArF, excimer lasers, X-rays, and electron beams, and these cations can become polymerization initiators.

[0118] In the case of the negative photosensitive composition used in the method for manufacturing the hollow package of this embodiment, the anionic portion of the cationic polymerization initiator (I) contains an anion represented by the following general formula (I1-an).

[0119] [Chemical Formula 2]

[0120]

[0121] [In the formula, A is a heteroatom selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic, antimony, and bismuth. X is a halogen atom. R is a monovalent organic group. k is an integer from 1 to 6. Where k is 2 or higher, multiple Rs can be linked to form a divalent or higher organic group coordinated with A. m is an integer from 0 to 5. n is an integer from 1 to 3. m / (k+m) is 0 or higher and less than 0.7.]

[0122] In formula (I1-an), A is a heteroatom selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic, antimony, and bismuth. These heteroatoms are composed of metals from groups 13 and 15. Among these heteroatoms, the heteroatom selected as A is preferably boron, aluminum, gallium, phosphorus, and antimony, more preferably boron and phosphorus, and even more preferably boron. One heteroatom or two or more heteroatoms may be selected.

[0123] In formula (I1-an), R is a monovalent organic group. In formula (I1-an), with regard to R, when k is 2 or more, there are multiple Rs that can be linked to become divalent or more organic groups coordinated with A.

[0124] "Organic groups" refer to groups that contain carbon atoms, but may contain atoms other than carbon atoms (such as hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms (fluorine atoms, chlorine atoms, etc.)).

[0125] R is preferably a monovalent hydrocarbon group containing a halogen atom, and particularly preferably a monovalent hydrocarbon group containing a fluorine atom. The hydrocarbon group containing the halogen atom can be any of straight-chain, branched, or cyclic, and the number of carbon atoms is preferably 1 to 15, more preferably 1 to 10, and particularly preferably 1 to 8.

[0126] R may not contain halogen atoms (fluorine atoms, chlorine atoms, etc.).

[0127] Specific examples of organic groups with R being monovalent include fluoroalkyl groups, fluorinated aryl groups, pentafluorophenyl groups, 3,5-bis(trifluoromethyl)phenyl groups, alkoxylates, nonafluorotert-butylalkoxylates ((CF3)3C-O-), etc.

[0128] Specific examples of organic groups with R being divalent include catechol, compounds having 2,2-Prime dihydroxyphenyl, succinic acid, oxalic acid, etc.

[0129] In formula (I1-an), m / (k+m) is 0 or higher and less than 0.7. The upper limit of m / (k+m) is preferably less than 0.6, more preferably less than 0.5, and particularly preferably less than 0.5. The value of m / (k+m) is an indicator of the direct bonding between the halogen atom and the heteroatom. A lower value of m / (k+m) is better. Therefore, the most preferred value of m / (k+m) is 0.

[0130] The photosensitive composition (I) used in the manufacturing method of the hollow package of this embodiment preferably contains one or more compounds selected from the group consisting of compounds represented by the following general formula (I1) (hereinafter referred to as "(I1) component") and compounds represented by the following general formula (I2) (hereinafter referred to as "(I2) component"). The photosensitive composition (I) used in the manufacturing method of the hollow package of this embodiment may further contain compounds represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "(I3) component").

[0131] Among the above, both component (I1) and component (I2) produce strong acids upon exposure. Therefore, when using a photosensitive composition containing component (I) to form a pattern, sufficient sensitivity is obtained, resulting in a good pattern.

[0132] 《(I1)Component》

[0133] (I1) is a compound represented by the following general formula (I1).

[0134] [Chemical Formula 3]

[0135]

[0136] [In the formula, R] b01 ~R b04 Each atom can be an aryl group or a fluorine atom, which may have substituents. Specifically, the relationship between the number of fluorine atoms (m) and the number of aryl groups (k) that may have substituents holds, where m / (k+m) is 0 or greater and less than 0.7. q is an integer greater than or equal to 1. q+ Each is an organic cation with an independent valence of q.

[0137] • Anion section

[0138] In the aforementioned equation (I1), R b01 ~R b04 Each can be an aryl group or a fluorine atom that can have substituents.

[0139] R b01 ~R b04 The aryl group preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specifically, naphthyl, phenyl, anthracene, etc. can be cited as examples, and phenyl is preferred from the perspective of easy availability.

[0140] R b01 ~R b04 The aryl group may have substituents. There are no particular limitations on the substituent, but halogen atoms, hydroxyl groups, alkyl groups (preferably straight-chain or branched alkyl groups, preferably with 1 to 5 carbon atoms), haloalkyl groups are preferred, halogen atoms or haloalkyl groups with 1 to 5 carbon atoms are more preferred, and fluorine atoms or fluoroalkyl groups with 1 to 5 carbon atoms are particularly preferred. Having a fluorine atom in the aryl group increases the polarity of the anionic portion, which is preferable.

[0141] Among them, R is the expression in equation (I1). b01 ~R b04 Each is preferably a fluorinated phenyl group, and more preferably a perfluorophenyl group.

[0142] As a preferred specific example of the anionic portion of the compound represented by formula (I1), the following can be cited:

[0143] Tetra(pentafluorophenyl)borate ([B(C6F5)4)) - );

[0144] Tetra[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4) - );

[0145] Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2) - ); Tetrafluorophenyl)borate ([B(C6H3F2)4] - )wait.

[0146] Of particular preference is tetra(pentafluorophenyl)borate ([B(C6F5)4)). - ).

[0147] Among the above anions, the anion with "0" fluorine atoms directly bonded to borane ([B(C6F5)4]) is the only one. - ), ([B(C6H4CF3)4] - ), ([B(C6H3F2)4] - ), ([B(C6F5)4] - In the equation relating the number of fluorine atoms (m) to the number of fluoroalkyl groups (k) that can have substituents, m / (k+m) is 0.

[0148] Among the above anions, the anion with two fluorine atoms directly bonded to borane ([(C6F5)2BF2]) is the only one. - In the formula, m / (k+m) is 0.5.

[0149] It should be noted that the anion with 3 fluorine atoms directly bonded to borane ([(C6F5)BF3]) - In the case of such compounds, the formula m / (k+m) becomes 0.75.

[0150] • Cation section

[0151] In equation (I1), q is an integer greater than or equal to 1, and Q q+ Each is an organic cation with an independent valence of q.

[0152] As the Q q+ Examples of preferred cations include sulfonium cations and iodonium cations, with particular preference given to organic cations represented by the general formulas (ca-1) to (ca-5) below.

[0153] [Chemical Formula 4]

[0154]

[0155] [In the formula, R] 201 ~R 207 and R 211 ~R 212 Each can independently represent an aryl, heteroaryl, alkyl, or alkenyl group that may have substituents. R 201 ~R 203 R206 ~R 207 R 211 ~R 212 They can bond with each other and form a ring together with the sulfur atoms in the formula. R 208 ~R 209 Each can independently represent an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a cyclic group containing -SO2- that may have a substituent. L 201 This represents -C(=O)- or -C(=O)-O-. Y 201 Each can independently represent an arylene, alkylene, or alkenyl group. x is 1 or 2. W 201 [This represents a linking group with a valence of (x+1).]

[0156] As R 201 ~R 207 and R 211 ~R 212 The aryl group in the formula can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0157] As R 201 ~R 207 and R 211 ~R 212 The heteroaryl group in the text can be exemplified by a group in which a portion of the carbon atom constituting the aforementioned aryl group is replaced by a heteroatom. Examples of heteroatoms include oxygen, sulfur, and nitrogen atoms. Examples of such heteroaryl groups include those formed by removing one hydrogen atom from 9H-thioxanthone; examples of substituted heteroaryl groups include those formed by removing one hydrogen atom from 9H-thioxanthone-9-one. As R... 201 ~R 207 and R 211 ~R 212 The alkyl group in the formula is preferably a chain-like or cyclic alkyl group with 1 to 30 carbon atoms.

[0158] As R 201 ~R 207 and R 211 ~R 212 The alkenyl group in the form of carbon atoms preferably has a carbon number of 2 to 10.

[0159] As R 201 ~R 207 and R 210 ~R 212 The substituents that may be present include, for example, alkyl, halogen atom, haloalkyl, carbonyl, cyano, amino, oxo (=O), aryl, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

[0160] [Chemical Formula 5]

[0161]

[0162] [In the formula, R'] 201 Each group can be an independent hydrogen atom, a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents.

[0163] In the aforementioned equations (ca-r-1) to (ca-r-10), R' 201 Each can be an independent hydrogen atom, a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents.

[0164] Cyclic groups that may have substituents:

[0165] The cyclic group is preferably a cyclic hydrocarbon group, which can be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group can be saturated or unsaturated, but is generally preferred to be saturated.

[0166] R' 201 The aromatic hydrocarbon group in the form is a hydrocarbon group having an aromatic ring. The number of carbon atoms in this aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents.

[0167] As R' 201 The aromatic rings contained in aromatic hydrocarbon groups can be specifically exemplified by benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles formed by replacing a portion of the carbon atoms constituting these aromatic rings with heteroatoms, or rings formed by replacing a portion of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles with oxo groups, etc. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0168] As R' 201The aromatic hydrocarbon group in the group can specifically include groups formed by removing one hydrogen atom from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, anthracene, etc.), groups formed by substituting one hydrogen atom of the aforementioned aromatic ring with an alkylene group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups), groups formed by removing one hydrogen atom from a ring formed by substituting a portion of the hydrogen atoms constituting the aforementioned aromatic ring with an oxo group or the like (for example, anthraquinone), and groups formed by removing one hydrogen atom from an aromatic heterocycle (for example, 9H-thioxanth, 9H-thioxanth-9-one, etc.). The number of carbon atoms in the aforementioned alkylene group (alkyl chain in arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0169] R' 201 Examples of cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain rings in their structure.

[0170] Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups formed by removing one hydrogen atom from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups located in the middle of a straight-chain or branched aliphatic hydrocarbon group.

[0171] The number of carbon atoms in the aforementioned alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0172] The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group formed by removing one or more hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms; specifically, cyclopentane and cyclohexane are examples. As a polycyclic alicyclic hydrocarbon group, it is preferably a group formed by removing one or more hydrogen atoms from a polycyclic alkane; as the polycyclic alkane, it is preferably a polycyclic alkane with 7 to 30 carbon atoms. Among these, more preferably, polycyclic alkanes with a cross-linked ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycyclic alkanes with a fused ring system such as a cyclic group possessing a steroidal skeleton are also preferred.

[0173] Among them, as R' 201 The cyclic aliphatic hydrocarbon group in the form is preferably a group formed by removing one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane, more preferably a group formed by removing one hydrogen atom from a polycyclic alkane, particularly preferably adamantyl or norbornyl, and most preferably adamantyl.

[0174] The number of carbon atoms in the aliphatic hydrocarbon group that can bond with the alicyclic hydrocarbon group, whether straight-chain or branched, is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3.

[0175] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc.

[0176] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkane with 1 to 5 carbon atoms.

[0177] Alkyl groups that may have substituents:

[0178] As R' 201 The alkyl group can be either straight-chain or branched.

[0179] As a straight-chain alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotriadecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, and dodecyl.

[0180] As a branched alkyl group, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0181] Alkenyl groups that may have substituents in a chain-like structure:

[0182] As R' 201 The chain-like alkenyl group can be either straight-chain or branched, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of straight-chain alkenyl groups include vinyl, allyl, and butenyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0183] As a chain-like alkenyl group, the linear alkenyl group is preferred, more preferably vinyl or propenyl, and particularly preferably vinyl.

[0184] As R' 201 Substituents in cyclic groups, chain-like alkyl or alkenyl groups, for example, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, amino, oxo, and the above R' 201 The cyclic groups, alkyl carbonyl groups, thiophene carbonyl groups, etc.

[0185] Among them, R' 201 Preferably, it is a cyclic group that may have substituents or a chain alkyl group that may have substituents.

[0186] R 201 ~R 203 R 206 ~R 207 R 211 ~R 212 When bonds are formed between the atoms and together with the sulfur atom in the formula to form a ring, the ring can be formed by heteroatoms such as sulfur, oxygen, and nitrogen, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R). N )-(the R N The ring is bonded to functional groups such as alkyl groups having 1 to 5 carbon atoms. The ring structure containing the sulfur atom in the formula is preferably a three- to ten-membered ring, and particularly preferably a five- to seven-membered ring. Specific examples of the formed ring include thiophene rings, thiazole rings, benzothiophene rings, thiathracene rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthene rings, thioxanone rings, thiathracene rings, phenoxathia rings, tetrahydrothiophenonium rings, and tetrahydrothiaran rings.

[0187] In the aforementioned equation (ca-3), R 208 ~R 209 Each alkyl group independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. When they are alkyl groups, they can bond with each other to form a ring.

[0188] In the aforementioned equation (ca-3), R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a cyclic group containing -SO2- that may have a substituent.

[0189] As R 210 The aryl group in the formula can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0190] As R 210 The alkyl group in the form of the alkyl group is preferably a chain-like or cyclic alkyl group with 1 to 30 carbon atoms.

[0191] As R 210 The alkenyl group in the form of carbon atoms preferably has a carbon number of 2 to 10.

[0192] In the aforementioned equations (ca-4) and (ca-5), Y 201 Each can be independently represented as arylene, alkylene, or alkenyl.

[0193] Y 201 The aryl group in R' can be cited as an example. 201 The aromatic hydrocarbon group in the example is a group formed by removing one hydrogen atom from the aryl group.

[0194] Y 201 Examples of alkylene and alkenylene groups in R' are derived from... 201 The chain alkyl group or chain alkenyl group in the example group is formed by removing one hydrogen atom.

[0195] In the aforementioned equations (ca-4) and (ca-5), x is 1 or 2.

[0196] W 201 It is a (x+1) valence, that is, a divalent or trivalent linking group.

[0197] As W 201 The divalent linking group in the above formula (abp1) is preferably a divalent hydrocarbon group that may have substituents, and is preferably related to R in the above formula (abp1). EP The example can be a divalent hydrocarbon group with substituents. W 201 The divalent linking group can be any of straight-chain, branched, or cyclic, preferably cyclic. Preferably, it is a group formed by combining two carbonyl groups at both ends of the arylene, or a group formed solely by the arylene. Examples of arylene groups include phenylene and naphthylene, with phenylene being particularly preferred.

[0198] As W 201 The trivalent linker group in W can be cited as an example. 201Groups formed by removing one hydrogen atom from a divalent linking group, and groups formed by further bonding a divalent linking group to the aforementioned divalent linking group, etc. As W 201 The trivalent linking group in the group is preferably a group formed by bonding two carbonyl groups to an arylene group.

[0199] As preferred cations represented by the aforementioned formula (ca-1), examples include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0200] [Chemical Formula 6]

[0201]

[0202] [Chemical Formula 7]

[0203]

[0204] [In the formula, R”] 201 It is a hydrogen atom or a substituent. As this substituent, it is related to the aforementioned R... 201 ~R 207 and R 210 ~R 212 The groups that can have substituents are the same as those listed above.

[0205] Furthermore, as the cation represented by the aforementioned formula (ca-1), the cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferred.

[0206] [Chemical Formula 8]

[0207]

[0208] [Chemical Formula 9]

[0209]

[0210] [In the formula, R'] 211 It is an alkyl group. R hal It can be a hydrogen atom or a halogen atom.

[0211] Furthermore, as the cation represented by the aforementioned formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are also preferred.

[0212] [Chemical Formula 10]

[0213]

[0214] Preferred cations represented by the aforementioned formula (ca-2) include, specifically, diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc.

[0215] As preferred cations represented by the aforementioned formula (ca-3), examples include cations represented by formulas (ca-3-1) to (ca-3-6) respectively.

[0216] [Chemical Formula 11]

[0217]

[0218] As preferred cations represented by the aforementioned formula (ca-4), examples include cations represented by formulas (ca-4-1) to (ca-4-2) respectively.

[0219] [Chemical Formula 12]

[0220]

[0221] Furthermore, the cation represented by the aforementioned formula (ca-5) is preferably the cation represented by each of the following general formulas (ca-5-1) to (ca-5-3).

[0222] [Chemical Formula 13]

[0223]

[0224] [In the formula, R'] 212 It consists of an alkyl group or a hydrogen atom. R' 211 It is an alkyl group.

[0225] Of the above, the cation portion [(Q q+ ) 1 / q The preferred cation is one represented by the general formula (ca-1), more preferably one represented by each of the formulas (ca-1-1) to (ca-1-48), even more preferably one represented by each of the formulas (ca-1-25), (ca-1-35), and (ca-1-48), and particularly preferably one represented by each of the formulas (ca-1-25) and (ca-1-48).

[0226] The following are specific examples of preferred (I1) components.

[0227] In the anion of the compound shown in the specific example, the relationship between the number of fluorine atoms (m) and the number of aryl groups that can have substituents (k), m / (k+m) is 0.

[0228] [Chemical Formula 14]

[0229]

[0230] (I2) Components

[0231] (I2) is a compound represented by the following general formula (I2).

[0232] [Chemical Formula 15]

[0233]

[0234] [In the formula, R] b05 It can be a fluoroalkyl group or a fluorine atom that may have substituents. Multiple R b05 They can be the same or different. Specifically, the relationship between the number of fluorine atoms (m) and the number of fluoroalkyl groups that can have substituents (k) holds, where m / (k+m) is 0 or greater and less than 0.7. q is an integer greater than or equal to 1. q+ Each is an organic cation with an independent valence of q.

[0235] • Anion section

[0236] In the aforementioned equation (I2), R b05 It can be a fluoroalkyl group or a fluorine atom that may have substituents. Multiple R b05 They can be the same or different. R b05 The fluoroalkyl group in the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. Specifically, among the alkyl groups with 1 to 5 carbon atoms, those formed by replacing some or all of the hydrogen atoms with fluorine atoms can be cited.

[0237] Among them, as R b05 Preferably, it is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and even more preferably a fluorine atom, trifluoromethyl or pentafluoroethyl.

[0238] The anionic portion of the compound represented by formula (I2) is preferably an anion represented by the following general formula (b0-2a).

[0239] [Chemical Formula 16]

[0240]

[0241] [In the formula, R] bf05 It is a fluoroalkyl group that can have substituents. 1 It is an integer between 2 and 6.

[0242] In equation (b0-2a), R is... bf05 The fluoroalkyl group that may have substituents, and the aforementioned R b05 The same applies to fluoroalkyl groups that can have substituents.

[0243] Among them, as R bf05 Preferably, it is a fluoroalkyl group having 1 to 5 carbon atoms, more preferably a perfluoroalkyl group having 1 to 5 carbon atoms, and even more preferably trifluoromethyl or pentafluoroethyl.

[0244] In equation (b0-2a), nb 1 The preferred value is an integer from 2 to 4, and the most preferred value is 3.

[0245] As a preferred specific example of the anionic portion of the compound represented by formula (I2), (CF3CF2)2PF4 can be cited. - (CF3CF2)3PF3 - 、((CF3)2CF)2PF4 - 、((CF3)2CF)3PF3 - (CF3CF2CF2)2PF4 - (CF3CF2CF2)3PF3 - 、((CF3)2CFCF2)2PF4 - 、((CF3)2CFCF2)3PF3 - (CF3CF2CF2CF2)2PF4 - and (CF3CF2CF2CF2)3PF3 - The anions represented, etc.

[0246] The preferred option is ((CF3)2CF)3PF3. - .

[0247] Among the above anions, nb in the above general formula (b0-2a) 1 In the anion with a denominator of “2”, the relationship between the number of fluorine atoms (m) and the number of fluoroalkyl groups that can have substituents (k) is expressed as m / (k+m) = 0.667.

[0248] Among the above anions, nb in the above general formula (b0-2a) 1 For anions with a value of "3", m / (k+m) is 0.5.

[0249] • Cation section

[0250] In equation (I2), q is an integer greater than or equal to 1, Q q+ Each is an organic cation with an independent valence of q.

[0251] As the Q q+Examples of organic cations similar to the above formula (I1) can be given, wherein the cation represented by the general formula (ca-1) is preferred, the cation represented by each of the formulas (ca-1-1) to (ca-1-47) is more preferred, and the cation represented by each of the formulas (ca-1-35) and (ca-1-47) is even more preferred.

[0252] The following are specific examples of preferred (I2) components.

[0253] In the anion of the compound shown in the specific example, the relationship between the number of fluorine atoms (m) and the number of fluoroalkyl groups that may have substituents (k) is m / (k+m), which is 0.5.

[0254] [Chemical Formula 17]

[0255]

[0256] The content of component (I) is preferably 0.5 to 5 parts by mass relative to 100 parts by mass of component (A), more preferably 0.8 to 4.5 parts by mass, and particularly preferably 1 to 4 parts by mass.

[0257] (I) When the content of the component is above or below the lower limit of the aforementioned preferred range, corrosion of the aluminum wiring constituting the hollow package can be sufficiently suppressed. Furthermore, sufficient sensitivity is obtained, and the photolithographic properties of the pattern are further improved. In addition, the strength of the cured film is further improved. On the other hand, when the content is below or below the upper limit of the aforementioned preferred range, the sensitivity can be appropriately controlled, and a pattern with a good shape can be easily obtained.

[0258] "(I3)Ingredient"

[0259] (I3) refers to compounds represented by the following general formula (I3-1) or (I3-2).

[0260] [Chemical Formula 18]

[0261]

[0262] [In the formula, R] b11 ~R b12 It can be a cyclic group having substituents other than halogen atoms, a chain-like alkyl group having substituents other than halogen atoms, or a chain-like alkenyl group having substituents other than halogen atoms. m is an integer greater than or equal to 1, M m+ Each is an organic cation with an independent valence of m.

[0263] {(I3-1)Component}

[0264] • Anion section

[0265] In equation (I3-1), R b12R' can be a cyclic group having substituents other than halogen atoms, a chain-like alkyl group having substituents other than halogen atoms, or a chain-like alkenyl group having substituents other than halogen atoms; examples of R' are mentioned above. 201 The description includes cyclic groups, chain alkyl groups, chain alkenyl groups, groups without substituents, and groups with substituents other than halogen atoms.

[0266] As R b12 Preferably, it is a chain alkyl group that may have substituents other than halogen atoms, or an aliphatic cyclic group that may have substituents other than halogen atoms. As a chain alkyl group, it is preferably 1 to 10 carbon atoms, more preferably 3 to 10. As an aliphatic cyclic group, it is more preferably a group formed by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents other than halogen atoms); or a group formed by removing one or more hydrogen atoms from camphor, etc.

[0267] R b12 The hydrocarbon group may have substituents other than halogen atoms. Examples of such substituents include R in the aforementioned formula (I3-2). b11 The hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) can have the same substituents as the halogen atom.

[0268] The phrase "may have substituents other than halogen atoms" here excludes not only cases with substituents formed solely of halogen atoms, but also cases with substituents containing halogen atoms (even if only one) (e.g., cases where the substituent is a fluoroalkyl group).

[0269] The following shows a preferred example of the anionic portion of component (I3-1).

[0270] [Chemical Formula 19]

[0271]

[0272] • Cation section

[0273] In equation (I3-1), M m+ It is an organic cation with an m valence.

[0274] As M m+ The organic cations are preferably the same as those represented by the general formulas (ca-1) to (ca-5) described above, with the cation represented by the general formula (ca-1) being more preferred. From the perspective of improved resolution and roughness characteristics, R in the general formula (ca-1) is preferred. 201 R 202 R 203At least one of them is a sulfonium cation containing an organic group (aryl, heteroaryl, alkyl, or alkenyl) having 16 or more carbon atoms that may have substituents. As mentioned above, examples of substituents that may be present in the aforementioned organic group include alkyl, halogen atom, haloalkyl, carbonyl, cyano, amino, oxo (=O), aryl, and groups represented by each of the formulas (ca-r-1) to (ca-r-10).

[0275] The aforementioned organic group (aryl, heteroaryl, alkyl, or alkenyl) preferably has 16 to 25 carbon atoms, more preferably 16 to 20, and particularly preferably 16 to 18, as M m+ Organic cations, for example, preferably cations represented by each of the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), (ca-1-46), and (ca-1-47), with the cation represented by formula (ca-1-29) being particularly preferred.

[0276] {(I3-2)Component}

[0277] • Anion section

[0278] In equation (I3-2), R b11 R' can be a cyclic group having substituents other than halogen atoms, a chain-like alkyl group having substituents other than halogen atoms, or a chain-like alkenyl group having substituents other than halogen atoms; examples of R' are mentioned above. 201 The description includes cyclic groups, chain alkyl groups, chain alkenyl groups, groups without substituents, and groups with substituents other than halogen atoms.

[0279] Among these, as R b11 Preferably, the substituents are aromatic hydrocarbon groups having substituents other than halogen atoms, aliphatic cyclic groups having substituents other than halogen atoms, or chain alkyl groups having substituents other than halogen atoms. Examples of substituents that may be present in these groups include hydroxyl groups, oxo groups, alkyl groups, aryl groups, lactone-containing cyclic groups, ether bonds, ester bonds, or combinations thereof.

[0280] When ether or ester bonds are included as substituents, an alkylene group may be present. In this case, the substituents are preferably the linking groups represented by the following general formulas (y-al-1) to (y-al-7).

[0281] [Chemical Formula 20]

[0282]

[0283] [In the formula, V'] 101It is a single bond or an alkylene group having 1 to 5 carbon atoms, V' 102 It is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms.

[0284] V' 102 The divalent saturated hydrocarbon group is preferably an alkylene group with 1 to 30 carbon atoms, more preferably an alkylene group with 1 to 10 carbon atoms, and even more preferably an alkylene group with 1 to 5 carbon atoms.

[0285] As V' 101 and V' 102 The alkylene groups in the form can be straight-chain alkylene groups or branched alkylene groups, with straight-chain alkylene groups being preferred.

[0286] As V' 101 and V' 102 Specifically, examples of alkylene groups include methylene [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; ethylene [-CH2CH2-]; alkylmethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -C H(CH2CH3)CH2- and other alkyl ethylides; trimethylene (n-propylidene) [-CH2CH2CH2-]; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2- and other alkyl trimethylenes; tetramethylene [-CH2CH2CH2CH2-]; -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkyl tetramethylenes; pentamethylene [-CH2CH2CH2CH2CH2-], etc.

[0287] Additionally, V' 101 or V' 102 In this embodiment, a portion of the methylene group in the aforementioned alkylene group can be replaced by a divalent aliphatic cyclic group having 5 to 10 carbon atoms. This aliphatic cyclic group is preferably derived from R... ’201 The divalent group formed by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group), more preferably cyclohexylene, 1,5-adamantylene or 2,6-adamantylene.

[0288] The aforementioned aromatic hydrocarbon group is more preferably phenyl or naphthyl.

[0289] More preferably, the aliphatic cyclic group is a group formed by removing one or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0290] As for the aforementioned chain-like alkyl group, it is preferred that the number of carbon atoms is 1 to 10. Specifically, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and branched-chain alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0291] As R b11 Preferably, it is a cyclic group that may have substituents other than halogen atoms.

[0292] The following shows a preferred example of the anionic portion of component (I3-2).

[0293] [Chemical Formula 21]

[0294]

[0295] • Cation section

[0296] In equation (I3-2), M m+ An organic cation with a valence of m, and M in the aforementioned formula (I3-1) m+ same.

[0297] The following are specific examples of the preferred (I3) component.

[0298] [Chemical Formula 22]

[0299]

[0300] As component (I), one type may be used alone, or two or more types may be used together. Specifically, component (I) includes one or more types selected from the group consisting of components (I1) and (I2), and may also include component (I3).

[0301] Furthermore, considering the high elasticity of the resin film, the absence of residue, and the ease of forming a fine structure, component (I) is preferably a cationic polymerization initiator that produces an acid with a pKa (acid dissociation constant) of -5 or less through exposure. By using a cationic polymerization initiator that produces an acid with a more preferably pKa of -6 or less, and even more preferably a pKa of -8 or less, high sensitivity to exposure can be obtained. The lower limit of the pKa of the acid produced by component (I) is preferably -15 or more. High sensitivity can be easily achieved by using a cationic polymerization initiator that produces an acid with the aforementioned preferred pKa.

[0302] The term "pKa (acid dissociation constant)" used here refers to a constant commonly used as an indicator of the acid strength of a substance. It should be noted that the pKa values ​​in this specification are values ​​under temperature conditions of 25°C. Furthermore, pKa values ​​can be determined using known methods. Alternatively, values ​​calculated using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development Co., Ltd.) can also be used.

[0303] <Compounds containing epoxy groups (A)>

[0304] The epoxy-containing compound ((A) component) used in the photosensitive composition of this embodiment may include a compound represented by the following general formula (A1) (hereinafter referred to as "(A1) component") and a compound represented by the following general formula (A2) (hereinafter referred to as "(A2) component").

[0305] "(A1) Ingredient"

[0306] As a component (A1), for example, an epoxy resin with a structure represented by the following general formula (abp1) can be cited.

[0307] [Chemical Formula 23]

[0308]

[0309] [In the formula, R] EP R is a group containing an epoxy group. a31 R a32 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, na 31 Integers from 1 to 50.

[0310] In the aforementioned equation (abp1), R EP It is a group containing an epoxy group.

[0311] As R EP The epoxy group is not particularly limited, but can be exemplified by: groups formed solely of epoxy groups; groups formed solely of alicyclic epoxy groups; and groups having an epoxy group or alicyclic epoxy group and a divalent linking group.

[0312] Alicyclic epoxy groups refer to alicyclic groups that have an oxacyclopropane structure as a three-membered cyclic ether. Specifically, they are groups that possess both an alicyclic group and an oxacyclopropane structure. The alicyclic group forming the basic skeleton of an alicyclic epoxy group can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. Furthermore, the hydrogen atoms in these alicyclic groups can be substituted with alkyl, alkoxy, or hydroxyl groups.

[0313] In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferred that the epoxy group or the alicyclic epoxy group is bonded by a divalent linking group that is bonded to the oxygen atom (-O-) in the formula.

[0314] Here, there is no particular limitation on the divalent linking group. Preferred groups include divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms.

[0315] Regarding divalent hydrocarbon groups that can have substituents:

[0316] The divalent hydrocarbon group can be either an aliphatic or aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group can be saturated or unsaturated, but is usually preferred to be saturated.

[0317] More specifically, examples of this aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0318] The aforementioned linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. As a linear aliphatic hydrocarbon group, a linear alkylene group is preferred; specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], and pentamethylene [-(CH2)5-].

[0319] The number of carbon atoms in the aforementioned branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and most preferably 2 or 3. As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0320] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned structure include: alicyclic hydrocarbon groups (groups formed by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups formed by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is located in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of straight-chain or branched aliphatic hydrocarbon groups are the same hydrocarbon groups as those described above.

[0321] The number of carbon atoms in the aforementioned alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0322] The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group formed by removing two hydrogen atoms from a monocyclic alkane. As for the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. are examples.

[0323] The polycyclic alicyclic hydrocarbon group is preferably a group formed by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms. Examples include adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0324] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system with (4n+2) π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include benzene, naphthalene, anthracene, phenanthrene, and other aromatic hydrocarbon rings; and aromatic heterocycles formed by replacing a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0325] Specifically, examples of aromatic hydrocarbon groups include groups formed by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (aryl or heteroaryl); groups formed by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); groups formed by replacing one hydrogen atom of an aryl group (aryl or heteroaryl) with an alkylene group (e.g., groups formed by further removing one hydrogen atom from an aryl group of arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The alkylene group bonded to the aforementioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0326] A divalent hydrocarbon group may have substituents.

[0327] The divalent hydrocarbon group, whether straight-chain or branched, may or may not have substituents. Examples of substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms substituted by fluorine atoms, and carbonyl groups.

[0328] Alicyclic hydrocarbon groups, which are divalent hydrocarbon groups and contain a ring in their structure, may or may not have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and carbonyl groups.

[0329] Regarding the alkyl group used as the aforementioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0330] Regarding the alkoxy group used as the aforementioned substituent, it is preferably an alkoxy group having 1 to 5 carbon atoms, preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and most preferably methoxy or ethoxy.

[0331] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine being the preferred option.

[0332] Regarding the alkyl halogroups that are the aforementioned substituents, examples can be given of groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are replaced by the aforementioned halogen atoms.

[0333] In the case of alicyclic hydrocarbon groups, a portion of the carbon atoms constituting the ring structure can be replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0334] In the case of an aromatic hydrocarbon group that is divalent, the hydrogen atom in the aromatic hydrocarbon group can be replaced by a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group can be replaced by a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, and hydroxyl groups.

[0335] Regarding the alkyl group used as the aforementioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0336] Regarding the alkoxy, halogen atom, and haloalkyl groups that are the aforementioned substituents, examples of substituents that replace the hydrogen atoms present in the aforementioned alicyclic hydrocarbon groups can be given.

[0337] Regarding divalent linking groups containing heteroatoms:

[0338] In a divalent linker containing heteroatoms, heteroatoms refer to atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0339] Among the divalent linking groups containing heteroatoms, preferred linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H can be substituted by alkyl, acyl, or other substituents); -S-, -S(=O)2-, -S(=O)2-O-, and general formula -Y. 21 -OY 22 -、-Y 21 -O-、-Y 21 -C(=O)-O-、-C(=O)-OY 21 -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y22 - represents a group [where Y is a group that represents ... 21 and Y 22 Each can be an independent divalent hydrocarbon group that may have substituents, where O is an oxygen atom and m” is an integer from 0 to 3, etc.

[0340] When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, its H can be replaced by substituents such as alkyl or acyl groups. The number of carbon atoms in the substituent (alkyl, acyl, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0341] Formula-Y 21 -OY 22 -、-Y 21 -O-、-Y 21 -C(=O)-O-、-C(=O)-OY 21 -、-[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -Medium,Y 21 and Y 22 Each is an independent divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include the same hydrocarbon groups that are listed above as "divalent hydrocarbon groups that may have substituents" in the description of divalent linking groups.

[0342] As Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0343] As Y 22 Preferably, it is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl.

[0344] In the formula -[Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m” is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as in formula -[Y 21 -C(=O)-O] m” -Y 22 - represents a group, particularly preferably of the formula -Y21 -C(=O)-OY 22 - represents a group. Preferably, it is of the formula -(CH2). a’ -C(=O)-O-(CH2) b’ - represents a group. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1.

[0345] Among them, as R EP The epoxy group in it is preferably a glycidyl group.

[0346] In the aforementioned equation (abp1), R a31 R a32 Each is independently an alkyl group having 1 to 5 hydrogen atoms or carbon atoms.

[0347] R a31 R a32 The alkyl group having 1 to 5 carbon atoms is, for example, a straight-chain, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Examples of cyclic alkyl groups include cyclobutyl, cyclopentyl, etc.

[0348] Among them, as R a31 R a32 Preferably, it is a hydrogen atom or a straight-chain or branched alkyl group, more preferably a hydrogen atom or a straight-chain alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0349] In the aforementioned formula (abp1), na 31 It is an integer from 1 to 50, preferably an integer from 4 to 50, more preferably an integer from 4 to 15, and even more preferably an integer from 5 to 8.

[0350] As a preferred (A1) component, examples include epoxy resins with structures represented by the following general formula (a1-01) or the following general formula (a1-02).

[0351] [Chemical Formula 24]

[0352]

[0353] [In the formula, R] EP Na is a group containing an epoxy group. 31 [Integers between 4 and 50.]

[0354] [Chemical Formula 25]

[0355]

[0356] [In the formula, R] EP Na is a group containing an epoxy group. 31 [Integers between 4 and 50.]

[0357] In the aforementioned equation (a1-01) and equation (a1-02), R EP It is an epoxy group, which is related to R in the aforementioned formula (abp1). EP The explanation is the same. Among them, as R... EP The epoxy group in it is preferably a glycidyl group.

[0358] In the aforementioned equation (a1-01) and equation (a1-02), na 31 Each is an integer from 4 to 50, preferably an integer from 4 to 15, and more preferably an integer from 5 to 8.

[0359] From the viewpoint of easily suppressing the stress inside the cured film, the epoxy resin with the structure represented by the above general formula (a1-01) is preferred.

[0360] From the perspective of easily improving mold resistance, epoxy resins with the structure represented by the above general formula (a1-02) are preferred.

[0361] Commercially available products that can be used as (A1) ingredients include JER-806, JER-807, JER-4004, JER-4005, JER-4007, and JER-4010 (all manufactured by Mitsubishi Chemical Corporation); EPICLON830, EPICLON835, EPICLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (all manufactured by DIC Corporation); and LCE-21 and RE-602S (all manufactured by Nippon Kayaku Co., Ltd.).

[0362] As a component (A1), one type can be used alone, or two or more types can be used together.

[0363] In the photosensitive composition of this embodiment, the content of component (A1) is 60 to 100 parts by mass relative to the total mass (100% by mass) of component (A), preferably 70 to 100 parts by mass, and more preferably 50 to 100 parts by mass.

[0364] (A2) Ingredients

[0365] Component (A2) is an epoxy resin represented by the following general formula (A2-1) with an epoxy equivalent less than that of component (A1). That is, component (A2) uses a Novolac type epoxy resin (Anv).

[0366] Component (A2) can be any epoxy resin whose epoxy equivalent is relatively small compared to that of component (A1).

[0367] [Chemical Formula 26]

[0368]

[0369] [In the formula, R] p1 and R p2 Each is independently an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. Multiple R p1 They can be the same or different. Multiple Rs p2 They can be the same or different. n1 is an integer from 1 to 5. R EP It is a group containing an epoxy group. Multiple R EP They can be the same or different.

[0370] In the aforementioned formula (A2-1), R p1 R p2 Alkyl groups having 1 to 5 carbon atoms are, for example, straight-chain, branched, or cyclic alkyl groups having 1 to 5 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl; examples of cyclic alkyl groups include cyclobutyl and cyclopentyl. Among these, R... p1 R p2 Preferably, it is a hydrogen atom or a straight-chain or branched alkyl group, more preferably a hydrogen atom or a straight-chain alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0371] In formula (A2-1), multiple R p1 They can be the same or different. Multiple Rs p2 They can be the same or different.

[0372] In formula (A2-1), n1 is an integer from 1 to 5, preferably 2 or 3, and more preferably 2.

[0373] In equation (A2-1), R EP It is an epoxy group, which is related to R in the aforementioned formula (abp1). EP The explanation is the same. Among them, as R... EP The epoxy group in it is preferably a glycidyl group.

[0374] Commercially available products that can be used as epoxy resins represented by the above general formula (A2-1) include, for example, jER-152, jER-154, jER-157S70, and jER-157S65 (all manufactured by Mitsubishi Chemical Corporation).

[0375] As a component (A2), one type can be used alone, or two or more types can be used together.

[0376] In the photosensitive composition of this embodiment, the content of component (A2) is 15 to 60% by mass relative to the total mass (100% by mass) of component (A), preferably 20 to 55% by mass, and more preferably 25 to 50% by mass.

[0377] Other (A) ingredients

[0378] In the photosensitive composition of this embodiment, in addition to components (A1) and (A2), component (A) may also contain an epoxy-containing compound (hereinafter also referred to as "component (A3)").

[0379] As a component (A3), for example, Novolac-type epoxy resins (Anv) having structural units represented by the following general formula (anv1) can be cited.

[0380] [Chemical Formula 27]

[0381]

[0382] [In the formula, R] EP R is a group containing an epoxy group. a22 R a23 Each atom is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0383] In equation (anv1), R a22 R a23 Alkyl groups having 1 to 5 carbon atoms and R in the aforementioned formula (A2-1) p1 R p2 The same applies to alkyl groups with 1 to 5 carbon atoms. a22 R a23 The halogen atom is preferably a chlorine atom or a bromine atom.

[0384] In equation (anv1), R EP R in the aforementioned equation (abp1) EP Similarly, glycidyl groups are preferred.

[0385] The following shows a specific example of the structural unit represented by the aforementioned formula (anv1).

[0386] [Chemical Formula 28]

[0387]

[0388] Novolac type epoxy resin (Anv) can be a resin containing only the aforementioned structural unit (anv1), or a resin having structural unit (anv1) and other structural units. As other structural units, for example, the structural units represented by the following general formulas (anv2) to (anv3) can be cited.

[0389] [Chemical Formula 29]

[0390]

[0391] [In the formula, R] a24 R is a hydrocarbon group that can have substituents. a25 ~R a26 R a28 ~R a30 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. R a27 It can be an epoxy group or a hydrocarbon group that may have substituents.

[0392] In equation (anv2), R a24 It is a hydrocarbon group that may have substituents. Examples of hydrocarbon groups that may have substituents include straight-chain or branched alkyl groups, or cyclic hydrocarbon groups.

[0393] The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, and methyl or ethyl are more preferred.

[0394] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0395] R a24 When the hydrocarbon group is cyclic, it can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, it can be a polycyclic group or a monocyclic group.

[0396] Regarding the aliphatic hydrocarbon group as a monocyclic group, it is preferably a group formed by removing one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. are examples.

[0397] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferred to be a group formed by removing one hydrogen atom from a polycyclic alkane. As for the polycyclic alkane, it is preferred to be a polycyclic alkane with 7 to 12 carbon atoms. Specifically, examples include adamantane, norbornene, isoboronane, tricyclodecane, tetracyclododecane, etc.

[0398] R a24 When a cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0399] The aromatic ring need only be a cyclic conjugated system with 4n+2 π electrons; there are no particular limitations. It can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specifically, examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by replacing a portion of the carbon atoms in the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0400] As R a24 The aromatic hydrocarbon group in the compound can specifically include groups (aryl or heteroaryl) formed by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups formed by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups formed by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups, etc.). The alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0401] In equations (anv2) and (anv3), R a25 ~R a26 R a28 ~R a30 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, wherein the alkyl group having 1 to 5 carbon atoms and the halogen atom having 1 to 5 carbon atoms are respectively associated with the aforementioned R. a22 R a23 same.

[0402] In equation (anv3), R a27 It is a group containing an epoxy group or a hydrocarbon group that may have substituents. R a27 The epoxy-containing group and R in the aforementioned formula (A2-1) EP Similarly, R a27 Hydrocarbon groups that may have substituents and Ra24 same.

[0403] The following are specific examples of the structural units represented by the aforementioned equations (anv2) to (anv3).

[0404] [Chemical Formula 30]

[0405]

[0406] When the Novolac type epoxy resin (Anv) has other structural units besides the structural unit (anv1), the proportion of each structural unit in the resin (Anv) is not particularly limited. The total number of structural units with epoxy groups is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol% relative to the total number of all structural units constituting the resin (Anv).

[0407] Commercially available products that can be used with the Novolac type epoxy resin (Anv) mentioned above include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON HP5000 (all manufactured by DIC Corporation); EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.); YDCN-704 (manufactured by Nippon Steel Chemical Materials Co., Ltd.), etc.

[0408] In addition to the resin mentioned above, components (A3) may also include compounds represented by the following chemical formula (A3-1). Commercially available products that can be used as compounds represented by the following chemical formula (A3-1) include, for example, TECHMORE VG-3101L (manufactured by Printech Co., Ltd.).

[0409] [Chemical Formula 31]

[0410]

[0411] In addition to the resin described above, compounds represented by the following chemical formula (A3-2) may also be used in component (A3). Commercially available products that can be used as compounds represented by the following chemical formula (A3-2) include, for example, SHOFREE (registered trademark) BATG (manufactured by Showa Denko Co., Ltd.).

[0412] [Chemical Formula 32]

[0413]

[0414] In addition, as components of (A3), examples include, for example, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether; pentaerythritol tetraglycidyl ether, bis(trimethylolpropane) tetraglycidyl ether, diglycerol tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, inositol hexaglycidyl ether, etc.

[0415] In addition, as components (A3), aliphatic epoxy resins and acrylic resins (Aac) can also be cited as examples.

[0416] As examples of the aforementioned aliphatic epoxy resins and acrylic resins (Aac), resins having epoxy-containing units represented by the following general formulas (a1-1) to (a1-2) can be cited.

[0417] [Chemical Formula 33]

[0418]

[0419] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Va] 41 It is a divalent hydrocarbon group that can have substituents. na 41 R is an integer between 0 and 2. a41 R a42 It is a group containing an epoxy group. na 42 It can be 0 or 1. Wa 41 for(na 43 +1) valence aliphatic hydrocarbon group. na 43 [Integers from 1 to 3.]

[0420] In the aforementioned formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms.

[0421] The alkyl group of R having 1 to 5 carbon atoms is preferably straight-chain or branched. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0422] The alkyl halogroup R with 1 to 5 carbon atoms is a group formed by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with 1 to 5 carbon atoms with halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0423] R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. From the perspective of industrial availability, a hydrogen atom or a methyl group is most preferred.

[0424] In the aforementioned equation (a1-1), Va 41 For divalent hydrocarbon groups that can have substituents, examples include R in the aforementioned formula (abp1). EP The same group as the divalent hydrocarbon group described herein, which may have substituents.

[0425] In the above, Va 41 The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a straight-chain or branched aliphatic hydrocarbon group, even more preferably a straight-chain aliphatic hydrocarbon group, and particularly preferably a straight-chain alkylene group.

[0426] In equation (a1-1), na 41 It is an integer from 0 to 2, preferably 0 or 1.

[0427] In equations (a1-1) and (a1-2), R a41 R a42 It is an epoxy group, which is related to R in the aforementioned formula (abp1). EP same.

[0428] In formula (a1-2), Wa 41 (na) 43 +1) An aliphatic hydrocarbon group with a valence of 1) refers to a hydrocarbon group that does not possess aromaticity. It can be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aforementioned aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing rings in their structure, or groups formed by combining straight-chain or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing rings in their structure.

[0429] In equation (a1-2), na 43 It is an integer from 1 to 3, preferably 1 or 2.

[0430] The following are specific examples of the structural units represented by the aforementioned formulas (a1-1) or (a1-2).

[0431] [Chemical Formula 34]

[0432]

[0433] [Chemical Formula 35]

[0434]

[0435] [Chemical Formula 36]

[0436]

[0437] [Chemical Formula 37]

[0438]

[0439] In the above formula, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0440] R a51 R represents a divalent hydrocarbon group with 1 to 8 carbon atoms. a52 R represents a divalent hydrocarbon group with 1 to 20 carbon atoms. a53 This indicates a hydrogen atom or a methyl group. (na) 51 Integers from 0 to 10.

[0441] R a51 R a52 R a53 They can be the same or different.

[0442] In addition, for the purpose of moderately controlling physical and chemical properties, acrylic resins (Aac) may also have structural units derived from other polymeric compounds.

[0443] Examples of such polymerizable compounds include known free radical polymers and anionic polymers. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives with carboxyl and ester bonds such as 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate, and 2-methacryloyloxyethyl hexahydrophthalate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; and so on. (Meth)acrylate aryl esters such as phenyl acrylate and benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymeric compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymeric compounds such as vinyl chloride and vinylidene chloride; polymeric compounds containing amide bonds such as acrylamide and methacrylamide; and so on.

[0444] When aliphatic epoxy resins and acrylic resins (Aac) have other structural units, the content ratio of epoxy-containing units in the resin is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and most preferably 15 to 25 mol%.

[0445] In addition, as an aliphatic epoxy resin, a compound comprising a partial structure represented by the following general formula (m1) is also preferred (hereinafter referred to as "(m1) component").

[0446] [Chemical Formula 38]

[0447]

[0448] [In the formula, n² is an integer from 1 to 4. * indicates a linking key.]

[0449] In formula (m1), n2 is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 2.

[0450] As component (m1), examples include compounds in which multiple partial structures represented by the above general formula (m1) are bonded by divalent linking groups or single bonds. Among these, compounds in which multiple partial structures represented by the above general formula (m1) are preferably bonded by divalent linking groups.

[0451] The divalent linking group here is not particularly limited, but preferred examples include divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms. Regarding divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms, the R in the above formula (abp1) is... EP The divalent hydrocarbon group with substituents described in (groups containing epoxy groups) and the divalent linking group containing heteroatoms are also preferred, wherein the divalent linking group containing heteroatoms is more preferably -Y. 21 -C(=O)-O- represents the group, -C(=O)-OY 21 - indicates a group. As Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0452] In addition, compounds represented by the following general formula (m2) (hereinafter also referred to as "(m2) component") are preferably used as aliphatic epoxy resins.

[0453] [Chemical Formula 39]

[0454]

[0455] [In the formula, R] EP It is a group containing an epoxy group. Multiple R EP They can be the same or different.

[0456] In formula (m2), R EP It is an epoxy group, which is related to R in the aforementioned formula (abp1).EP same.

[0457] Commercially available products that can be used as the aforementioned aliphatic epoxy resins include, for example, ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, and ADEKA RESIN EP-4088S (all manufactured by ADEKA Corporation); CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (all manufactured by Daicel Corporation); DENACOL EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (all manufactured by Nagase-Chemtex Corporation); TEPIC-VL (manufactured by Nissan Chemical Corporation), etc.

[0458] When component (A3) is used in the photosensitive composition of this embodiment, the content of component (A3) is preferably 30% by mass or less, more preferably 1 to 30% by mass, further preferably 5 to 25% by mass, and particularly preferably 5 to 20% by mass, relative to the total mass (100% by mass) of component (A).

[0459] The content of component (A) in the photosensitive composition of this embodiment can be prepared according to the film thickness of the photosensitive resin film to be formed.

[0460] For example, in the photosensitive composition of this embodiment, the content of component (A) is preferably 80% or more by mass, more preferably 90% or more by mass, further preferably 95% or more by mass, and particularly preferably 97% or more by mass, relative to the total mass (100% by mass) of the photosensitive composition.

[0461] In the photosensitive composition of this embodiment, when components (A1) and (A2) are used in combination, they are preferably contained in a ratio of 25 parts by weight: 75 parts by weight to 75 parts by weight: 25 parts by weight. Alternatively, when two components (A1) are used, the photosensitive composition of this embodiment is preferably contained in a ratio of 50 parts by weight: 50 parts by weight.

[0462] <Optional Ingredients>

[0463] In addition to components (A) and (I) mentioned above, the photosensitive composition used in the manufacturing method of the hollow package of this embodiment may also contain other components as needed.

[0464] The photosensitive composition used in the method for manufacturing the hollow encapsulation body of this embodiment may contain additives with mixed properties, such as metal oxides (M), silane coupling agents, sensitizer components, solvents, additional resins for improving the performance of the film, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, anti-halo agents, etc., as desired.

[0465] Metal Oxides (M)

[0466] Considering the ease of obtaining a cured film with improved strength, the photosensitive composition used in the manufacturing method of the hollow package in this embodiment may contain a metal oxide (M) (hereinafter also referred to as "(M) component") in addition to components (A) and (I). Furthermore, by using component (M) in combination, high-resolution patterns can be formed with good shape.

[0467] As a component (M), examples include oxides of metals such as silicon (metallic silicon), titanium, zirconium, and hafnium. Among these, oxides of silicon are preferred, and silicon dioxide is particularly preferred.

[0468] In addition, the shape of component (M) is preferably particulate.

[0469] As the particulate (M) component, it is preferable to be a material formed from a group of particles with a volume average particle size of 5 to 40 nm, more preferably a material formed from a group of particles with a volume average particle size of 5 to 30 nm, and even more preferably a material formed from a group of particles with a volume average particle size of 10 to 20 nm.

[0470] If the volume average particle size of component (M) is above the lower limit of the aforementioned preferred range, the strength of the cured film can be easily improved. On the other hand, if it is below the upper limit of the aforementioned preferred range, residues are less likely to be generated during pattern formation, and higher resolution patterns can be easily formed. In addition, the transparency of the resin film is improved.

[0471] The particle size of the (M) component can be appropriately selected based on the exposure light source. It is generally considered that the effect of light scattering is negligible for particles with a particle size of less than 1 / 10 of the wavelength of light. Therefore, for example, when forming a fine structure by photolithography using an i-line (365 nm), a particle group (particularly preferably a silicon dioxide particle group) with a primary particle size (volume average) of 10 to 20 nm is preferably used as the (M) component.

[0472] As component (M), one type can be used alone, or two or more types can be used together.

[0473] When the component (M) is included, its content relative to 100 parts by mass of component (A) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass.

[0474] If the content of component (M) is above the lower limit of the aforementioned preferred range, the strength of the cured film is further improved. On the other hand, if it is below the upper limit of the aforementioned preferred range, the transparency of the resin film is further improved.

[0475] Silane coupling agents

[0476] To improve adhesion to the substrate, the photosensitive composition used in the manufacturing method of the hollow package of this embodiment may further contain an adhesive aid. A silane coupling agent is preferably used as this adhesive aid.

[0477] Examples of silane coupling agents include those with reactive substituents such as carboxyl, methacryloyl, isocyanate, and epoxy groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0478] The silane coupling agent can be used alone or in combination with two or more. When the silane coupling agent is included, its content relative to 100 parts by weight of component (A) is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight.

[0479] If the content of the silane coupling agent is within the aforementioned preferred range, the strength of the cured film is further improved. Furthermore, the adhesion between the cured film and the substrate is further enhanced.

[0480] Sensitizer Ingredients

[0481] The photosensitive composition used in the manufacturing method of the hollow package in this embodiment may also contain a sensitizer component.

[0482] As a sensitizer component, it is only required to absorb the energy generated by exposure and transfer that energy to other substances; there are no particular limitations.

[0483] Specifically, as sensitizing agents, known photosensitizers such as benzophenone, p,p'-tetramethyldiaminobenzophenone, carbazole, acetophenone, naphthalene, phenol, anthracene, 9-ethoxyanthracene, and diacetyl, eosin, rose red, pyrene, phenothiazine, and anthrone can be used.

[0484] Sensitizers can be used alone or in combination with two or more.

[0485] When the sensitizer component is included, its content relative to 100 parts by weight of component (A) is preferably 0.1 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight.

[0486] When the content of the sensitizer component is within the aforementioned preferred range, the sensitivity and resolution are further improved.

[0487] Solvent

[0488] The photosensitive composition used in the method for manufacturing the hollow package in this embodiment may also contain a solvent (hereinafter, sometimes referred to as "(S) component").

[0489] Examples of (S) components 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; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds with ester bonds such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; and compounds with ether bonds such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc., of the aforementioned polyols or compounds with ester bonds, or monoalkyl ethers or monophenyl ethers, etc. Derivatives of polyols [preferably propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME)]; cyclic ethers such as dioxane-1, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.; aromatic organic solvents such as anisole, ethyl benzyl ether, toluene, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, isopropyltoluene, mesitylene, etc.; dimethyl sulfoxide (DMSO); etc.

[0490] (S) Component can be used alone or as a mixed solvent of two or more components.

[0491] The amount of component (S) is not particularly limited, and the concentration that allows the photosensitive composition to be coated onto a substrate or the like without dripping can be appropriately set according to the coating film thickness.

[0492] For example, component (S) can be used in a manner where the concentration of solid component is 50% by mass or more, or component (S) can be used in a manner where the concentration is 60% by mass or more.

[0493] Alternatively, a method that substantially does not contain (S) components can be adopted (i.e., a solid component concentration of 100% by mass).

[0494] The hollow package manufactured by the hollow package manufacturing method of this embodiment described above has aluminum wiring and a hollow structure.

[0495] The hollow structure of the hollow package manufactured by the manufacturing method of this embodiment is formed from a photosensitive composition containing anion represented by the above general formula (I1-an). In the above general formula (I1-an), m / (k+m) is 0 or more and less than 0.7.

[0496] In the anion of component (I), halogen atoms that are directly bonded to heteroatoms (A in the formula) are prone to ionization. In contrast, in this embodiment, when forming a hollow structure, by using component (I) containing anions with few or no halogen atoms that are directly bonded to heteroatoms (A in the formula), the amount of halogen atoms ionized can be reduced.

[0497] One reason for the corrosion of aluminum wiring in hollow packages is believed to be the aforementioned free halogen atoms. In this embodiment, component (I) with reduced free halogen atoms is used, thus enabling the manufacture of hollow packages in which corrosion of aluminum wiring is suppressed.

[0498] (Modified Example)

[0499] In the above embodiments, a method for manufacturing a hollow package having a first step and a second step has been described, but a step (a third step) of obtaining a hollow package by sealing with a sealing material may also be included as an optional step.

[0500] As a sealing material, a resin composition can be used, for example. The resin used in the sealing material is not particularly limited as long as it can achieve at least one of sealing and insulating the hollow structure; examples include epoxy resins and silicone resins.

[0501] In addition to resin, sealing materials may also contain other components such as fillers.

[0502] There are no particular limitations on the method of sealing a hollow structure with a sealing material. The heated and molten sealing material is supplied to the hollow structure in a manner that covers the hollow structure and is then compressed and molded, thereby creating a hollow encapsulated body with a sealing material layer on the hollow structure.

[0503] The aforementioned sealing material layer has the function of protecting the MEMS, wiring parts and other components inside the hollow structure from the influence of the external environment.

[0504] The above embodiments describe a method for manufacturing a hollow package with sidewalls and top plate formed from a photosensitive composition, but are not limited thereto. Either the sidewalls or the top plate can be formed from a photosensitive composition.

[0505] (Method for providing the photosensitizing composition)

[0506] In the method for providing the photosensitive composition of this embodiment, the photosensitive composition is provided to a production line that performs the above-described method for manufacturing a hollow package.

[0507] The photosensitive composition here can be prepared by appropriately selecting from the above-mentioned materials, and the timing of preparation of the photosensitive composition can be determined according to the size and operating speed of the production line.

[0508] Furthermore, the business entity performing the manufacturing method of the hollow package does not necessarily have to be the same as the business entity performing the method provided herein.

[0509] Example

[0510] The present invention will be described in more detail below through embodiments, but the present invention is not limited to the following embodiments.

[0511] <Preparation of Photosensitive Compositions>

[0512] (Preparation Examples 1-5)

[0513] The components shown in Table 1 were mixed and dissolved, and filtered using a PTFE filter (1 μm pore size, manufactured by PALL Corporation) to prepare negative photosensitive compositions (solid components of approximately 84% by mass MEK solution) for each preparation example.

[0514] [Table 1]

[0515]

[0516] In Table 1, each abbreviation has the following meaning. The values ​​in [] are the proportions of each component (parts by mass; converted according to solid components).

[0517] (A1)-1: Resin containing epoxy groups, represented by the following general formula (A1-1). Trade name "EPICLON1055", manufactured by DIC.

[0518] [Chemical Formula 40]

[0519]

[0520] (A2)-1: The compound represented by the following chemical formula (A2-1). Trade name "jER-157S70", manufactured by Mitsubishi Chemical Corporation.

[0521] [Chemical Formula 41]

[0522]

[0523] (I1)-1: The cationic polymerization initiator represented by the following chemical formula (I1-1). m / (k+m) is 0.5.

[0524] (I1)-2: The cationic polymerization initiator represented by the following chemical formula (I1-2). m / (k+m) is 0.

[0525] (I1)-3: The cationic polymerization initiator represented by the following chemical formula (I1-3): [2-tert-butyl-5-methyl-4-(2-thioxanthonethio)phenyl](5-tert-butyl-2-methylphenyl)(2-thioxanthone)sulfonium tetra(pentafluorophenyl)borate. m / (k+m) is 0.

[0526] (I1)-4: The cationic polymerization initiator represented by the following chemical formula (I1-4). m / (k+m) is 1.

[0527] [Chemical Formula 42]

[0528]

[0529] (I3)-1: The cationic polymerization initiator represented by the following chemical formula (I3-1-1).

[0530] [Chemical Formula 43]

[0531]

[0532] (SC)-1: The compound represented by the following chemical formula (SC-1).

[0533] (D)-1: Sensitizer. α-Naphthol.

[0534] [Chemical Formula 44]

[0535]

[0536] <Test of fluoride ion effluent>

[0537] (Experimental Examples 1-5)

[0538] As the substrate film, a silicone-based surface-release PET film (trade name "A53", manufactured by Teijin Corporation) is used.

[0539] Preparation of resist film:

[0540] The negative photosensitive compositions of each of the above preparation examples were coated onto the aforementioned substrate film using a coating applicator, and then baked in an oven at 70°C for 10 minutes (PAB) to form a photosensitive resin film, thereby obtaining a photosensitive resist film.

[0541] Preparation of cured materials:

[0542] At 10000mJ / cm 2 The resist film was irradiated with ghi rays at a certain irradiation level. The substrate film was then peeled off and heated in an oven to cure it, resulting in a cured product.

[0543] [Evaluation of fluoride ion efflux]

[0544] The amount of fluoride ion efflux was evaluated using the negative photosensitive compositions of each example.

[0545] Add 4g of each cured product prepared using the negative photosensitive compositions of Preparation Examples 1-5 described above, and 40g of pure water as the extraction solvent to a PTFE resin container with a lid, and then cover the container. Place the lidded PTFE resin container in a stainless steel autoclave and treat it in an oven at 120°C for 20 hours. After cooling to room temperature, collect the extract and quantify the fluoride ion elution using ion chromatography. The results are shown in Table 2.

[0546] [Table 2]

[0547]

[0548] The results shown in Table 2 confirm that in Test Examples 1 to 4, which utilize the negative photosensitive composition used in the manufacturing method of the hollow encapsulation of the present invention, the effluent of fluoride ions can be suppressed. Among these, Test Examples 2 to 4 yielded excellent results regarding the effluent of fluoride ions in the extract. In particular, no fluoride ions were detected in the extract in Test Examples 3 and 4.

[0549] It can be confirmed that, based on the above-mentioned test examples 1 to 4, cured products using a negative photosensitive composition that is effective in suppressing the efflux of fluorine can be provided.

[0550] <Manufacturing Method of Hollow Encapsulated Body>

[0551] (Examples 1-6, Comparative Examples 1-2)

[0552] As the substrate film, a silicone-based surface-release PET film (trade name "A53", manufactured by Teijin Corporation) is used.

[0553] (Example 1)

[0554] [First Process]: S1

[0555] Through the following film formation process, exposure process and development process, sidewalls surrounding the aforementioned aluminum wiring are formed on a substrate having aluminum wiring.

[0556] [[Membrane Formation Process]]: S11

[0557] First, in order to fabricate the aluminum vapor-deposited substrate, a metal thin film forming apparatus PMC800-2MS (manufactured by Shincron) is used to form an aluminum layer (Al layer) with a thickness of 150nm on a silicon wafer to obtain the support.

[0558] The negative photosensitive composition of Preparation Example 1 was applied to the aforementioned support using a coating applicator, and then applied to the aforementioned substrate film using a coating applicator. The film was then baked in an oven at 70°C for 10 minutes (PAB) to form a photosensitive resin film with a film thickness of 20 μm, thereby obtaining a photosensitive resist film.

[0559] Under conditions of 80°C, 0.3 MPa, and 0.5 m / min, a photosensitive resin film formed from the negative photosensitive composition of Preparation Example 1 was laminated with an aluminum-deposited silicon wafer with a film thickness of 20 μm.

[0560] [Exposure Process]: S12

[0561] The substrate film in contact with the photosensitive resin film, which has a thickness of 20 μm, was peeled off, and a Canon PLA-501ghi line calibrator was used at 300 mJ / cm. 2 The photosensitive resin film was irradiated with ghi rays. Then, it was heat-treated on a heating plate at 90°C for 5 minutes.

[0562] [Developing Process]: S13

[0563] Using propylene glycol monomethyl ether acetate as the developer, the heat-treated photosensitive resin film was subjected to spin-dip development at 23°C, thereby forming a negative pattern that forms the sidewalls on the silicon wafer.

[0564] The aforementioned negative pattern is further heated in an oven to cure it, forming a substrate with a wall portion formed by a cured body of a photosensitive resin film, wherein the photosensitive resin film is formed from the negative photosensitive composition of Preparation Example 1.

[0565] [Second Process]: S2

[0566] Through the following processes (0) to (v), a top plate is formed on the side wall, and a hollow structure for housing aluminum wiring is produced.

[0567] [[Process (0)]]: S20

[0568] First, prepare the aluminum vapor-deposited substrate with sidewalls obtained in the first step above.

[0569] Using a coating applicator, the negative photosensitive composition of Preparation Example 1 was coated onto the aforementioned substrate film, and baked in an oven at 70°C for 10 minutes (PAB) to form a photosensitive resin film with a film thickness of 45 μm, thereby obtaining a photosensitive resist film.

[0570] [[Process(i)]]: S21

[0571] A photosensitive resist film with a thickness of 45 μm is prepared by blocking the opening of the aforementioned sidewall in a substrate having sidewalls with the surface of the photosensitive resin film of the photosensitive resist film.

[0572] Then, the aforementioned substrate film is peeled off from the photosensitive resin film of the aforementioned photosensitive resist film.

[0573] [[Process (ii)]]: S22

[0574] Next, using a Canon PLA-501ghi line calibrator at 300 mJ / cm 2 The irradiation dose was ghi rays irradiating the photosensitive resin film.

[0575] [[Process (iii)]]: S23

[0576] The exposed photosensitive resin film from step (ii) is subjected to a 5-minute heat treatment on a heating plate at 90°C.

[0577] [[Process (iv)]]: S24

[0578] Using propylene glycol monomethyl ether acetate as the developer, the photosensitive resin film after the heat treatment in step (iii) above is subjected to spin-dip development at 23°C, thereby forming a negative pattern for the top plate.

[0579] [[Process (v)]]: S25

[0580] The aforementioned negative pattern after step (iv) is further heated in an oven to cure it, thereby obtaining a hollow structure formed by the cured body of a photosensitive resin film in the top plate portion, wherein the photosensitive resin film is formed by the negative photosensitive composition of Preparation Example 1.

[0581] (Example 2)

[0582] The negative photosensitive composition of Preparation Example 1 was changed to the negative photosensitive composition of Preparation Example 2. Otherwise, the same procedure as in Example 1 was followed to obtain a hollow structure.

[0583] (Example 3)

[0584] The negative photosensitive composition used for the sidewall in Preparation Example 1 was changed to the negative photosensitive composition in Preparation Example 3, and the negative photosensitive composition used for the top plate in Preparation Example 1 was changed to the negative photosensitive composition in Preparation Example 4. Otherwise, the same procedure as in Example 1 was followed to obtain a hollow structure.

[0585] (Comparative Example 1)

[0586] The negative photosensitive composition of Preparation Example 1 was changed to the negative photosensitive composition of Preparation Example 5. Otherwise, the same procedure as in Example 1 was followed to obtain a hollow structure.

[0587] (Example 4)

[0588] The aluminum layer formed on the silicon wafer was replaced with an aluminum-1% copper alloy layer (AlCu layer), and otherwise the same procedure was followed as in Example 1 to obtain a hollow structure.

[0589] (Example 5)

[0590] The negative photosensitive composition of Preparation Example 1 was changed to the negative photosensitive composition of Preparation Example 2, and the aluminum layer formed on the silicon wafer was changed to an aluminum 1% copper alloy layer (AlCu layer). Otherwise, the same procedure as in Example 1 was followed to obtain a hollow structure.

[0591] (Example 6)

[0592] The negative photosensitive composition used for the sidewall in Preparation Example 1 was changed to the negative photosensitive composition of Preparation Example 3, the negative photosensitive composition used for the top plate in Preparation Example 1 was changed to the negative photosensitive composition of Preparation Example 4, and the aluminum layer formed on the silicon wafer was changed to an aluminum 1% copper alloy layer. Otherwise, the same procedure as in Example 1 was followed to obtain a hollow structure.

[0593] (Comparative Example 2)

[0594] The negative photosensitive composition of Preparation Example 1 was changed to the negative photosensitive composition of Preparation Example 5, and the aluminum layer formed on the silicon wafer was changed to an aluminum 1% copper alloy layer (AlCu layer). Otherwise, the same procedure as in Example 1 was followed to obtain a hollow structure.

[0595] <Corrosion Evaluation of Aluminum Wiring on Substrate>

[0596] The hollow structures obtained were observed using an optical microscope, and the fact that the aluminum wiring on the substrate was not corroded was evaluated by HAST and PCT tests.

[0597] <HAST Experiment>

[0598] Regarding the hollow structures of Examples 1-3 and Comparative Example 1, the aluminum vapor-deposited substrates with the hollow structures were subjected to HAST (85°C, 85% humidity, 100 hours) treatment, and then observed using an optical microscope to detect the presence or absence of corrosion. The results are shown below. Figure 3 And Table 3.

[0599] <PCT Trial>

[0600] Regarding the hollow structures in Examples 4-6 and Comparative Example 2, after PCT (120°C, 96 hours) was performed on the aluminum-copper 1% alloy vapor-deposited substrates with the hollow structures, the presence or absence of corrosion was observed using an optical microscope. The results are shown below. Figure 4 And Table 4.

[0601] [Table 3]

[0602] sidewall Top plate Types of metal layers corrosion Example 1 Preparation Example 1 Preparation Example 1 Al layer none Example 2 Preparation Example 2 Preparation Example 2 Al layer none Example 3 Preparation Example 3 Preparation Example 4 Al layer none Comparative Example 1 Preparation Example 5 Preparation Example 5 Al layer have

[0603] [Table 4]

[0604] sidewall Top plate Types of metal layers corrosion Example 4 Preparation Example 1 Preparation Example 1 AlCu layer none Example 5 Preparation Example 2 Preparation Example 2 AlCu layer none Example 6 Preparation Example 3 Preparation Example 4 AlCu layer none Comparative Example 2 Preparation Example 5 Preparation Example 5 AlCu layer have

[0605] In the hollow structures of Examples 1 to 6 constructed using the present invention, no corrosion of the metal layer was detected.

[0606] Figure 3 The results are shown by photographing the hollow package before and after the HAST test using an optical microscope. In Comparative Example 1, the aluminum vapor-deposited substrate inside, surrounded by sidewall 3, was corroded, so the blackening of the interior of sidewall 3 could be observed through the top plate 4. On the other hand, in Example 3, the interior surrounded by sidewall 1 was not corroded, and the substrate could be observed through the top plate 2. The results of internal corrosion in Examples 1 and 2 were the same as in Example 3.

[0607] Figure 4 The results are shown by photographing the hollow package before and after the PCT test using an optical microscope. In Comparative Example 2, the aluminum-copper 1% alloy vapor-deposited substrate inside, surrounded by sidewall 3, was corroded, so the blackening of the interior of sidewall 3 could be observed through top plate 4. On the other hand, in Example 6, the interior surrounded by sidewall 1 was not corroded, and the substrate could be observed through top plate 2. The results of internal corrosion in Examples 4 and 5 were the same as in Example 6.

[0608] As described above, it can be seen that, according to the embodiments constructed using the present invention, corrosion of the aluminum wiring in the hollow package is suppressed.

[0609] Explanation of reference numerals in the attached figures

[0610] 1, 3, 20 sidewalls

[0611] 2, 4 Top Plate Section

[0612] 10 substrate

[0613] 15 concavity

[0614] 30 Photosensitive resin film

[0615] 30A Exposure Department

[0616] 30B Unexposed Section

[0617] 30F photosensitive resist film

[0618] 40 solid body

[0619] 60 photomask

Claims

1. A method for manufacturing a hollow package, wherein the hollow package has a hollow structure for housing the aluminum wiring on a substrate having aluminum wiring, the manufacturing method comprising: The process of forming sidewalls surrounding the aluminum wiring on the substrate having aluminum wiring; and The process of forming a top plate portion on the side wall to fabricate the hollow structure for housing the aluminum wiring. The sidewalls and / or the top plate portion are formed by a process including developing a photosensitive resin film formed from a photosensitive composition using an organic developing solution. The photosensitive composition contains: an epoxy-containing compound; and a cationic polymerization initiator (I) formed from a cationic portion and an anionic portion. The epoxy-containing compound contains at least one epoxy resin selected from the group consisting of epoxy resins having a structure represented by the following general formula (abp1) and Novolac-type epoxy resins, and the cationic polymerization initiator (I) comprises: a cationic polymerization initiator (I10) whose anionic portion is an anion represented by the following general formula (I1-an); and a cationic polymerization initiator (I3) represented by the following general formula (I3-1) or the following general formula (I3-2). In equation (abp1), R EP R is a group containing an epoxy group. a31 R a32 Each is an alkyl group having 1 to 5 carbon atoms, na 31 Integers from 1 to 50 In formula (I1-an), A is a heteroatom selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic, antimony, and bismuth; X is a halogen atom; R is a monovalent organic group; k is an integer from 1 to 6; wherein, with regard to R, when k is 2 or more, multiple R can be linked to become a divalent or more organic group coordinated with A; m is an integer from 0 to 5; n is an integer from 1 to 3; m / (k+m) is 0 or more and less than 0.

7. In equations (I3-1) and (I3-2), R b11 ~R b12 It can be a cyclic group having substituents other than halogen atoms, a chain-like alkyl group having substituents other than halogen atoms, or a chain-like alkenyl group having substituents other than halogen atoms; m is an integer of 1 or more, M m+ Each is an organic cation with an independent valence of m.

2. The method for manufacturing a hollow package as described in claim 1, wherein, In the general formula (I1-an), m / (k+m) is less than 0.

5.

3. The method for manufacturing a hollow package as described in claim 1, wherein, Both the sidewall and the top plate are formed of a photosensitive composition.

4. The method for manufacturing a hollow package as described in claim 1, wherein, The cationic polymerization initiator (I10) is a compound represented by the following general formula (I1). In equation (I1), R b01 ~R b04 Each is independently an aryl or fluorine atom that can have substituents; wherein, the relationship between the number of fluorine atoms m and the number of aryl groups that can have substituents k, m / (k+m) is greater than or equal to 0 and less than 0.7; q is an integer greater than or equal to 1, Q q+ It is an organic cation with a valence of q.

5. The method for manufacturing a hollow package as described in claim 1, wherein, The photosensitive composition forming the sidewall and / or the top plate is a negative photosensitive composition.

6. The method for manufacturing a hollow package as described in claim 5, wherein, The content of the cationic polymerization initiator (I) in the negative photosensitive composition is 0.5 to 5 parts by mass relative to 100 parts by mass of the epoxy-containing compound.

7. The method for manufacturing a hollow package as described in any one of claims 1 to 6, further comprising a step of sealing the hollow structure with a sealing material after the step of manufacturing the hollow structure.

8. A method for providing a photosensitizing composition, wherein, The photosensitive composition is provided to a production line that performs the method for manufacturing a hollow package according to any one of claims 1 to 7.

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