WO2022107840A1 - 中空パッケージの製造方法及び感光性組成物の提供方法 - Google Patents
中空パッケージの製造方法及び感光性組成物の提供方法 Download PDFInfo
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- WO2022107840A1 WO2022107840A1 PCT/JP2021/042389 JP2021042389W WO2022107840A1 WO 2022107840 A1 WO2022107840 A1 WO 2022107840A1 JP 2021042389 W JP2021042389 W JP 2021042389W WO 2022107840 A1 WO2022107840 A1 WO 2022107840A1
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- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- JCMFJIHDWDKYIL-UHFFFAOYSA-N propyl 3-methoxypropanoate Chemical compound CCCOC(=O)CCOC JCMFJIHDWDKYIL-UHFFFAOYSA-N 0.000 description 1
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- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002345 steroid group Chemical group 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
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- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/02—Containers; Seals
- H01L23/06—Containers; Seals characterised by the material of the container or its electrical properties
- H01L23/08—Containers; Seals characterised by the material of the container or its electrical properties the material being an electrical insulator, e.g. glass
-
- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
- H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
- H03H3/00—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators
- H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
- H03H3/08—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of resonators or networks using surface acoustic waves
-
- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
- H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
- H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
- H03H9/25—Constructional features of resonators using surface acoustic waves
Definitions
- the present invention relates to a method for producing a hollow package and a method for providing a photosensitive composition.
- a hollow package encapsulating an electronic device using a surface acoustic wave (SAW) filter has a hollow structure for ensuring the propagation of surface acoustic waves and the mobility of movable members of the electronic device (patented). See Document 1).
- SAW surface acoustic wave
- the hollow package is formed by molding a hollow structure in which the wiring board on which the electrodes are formed is kept hollow with a photosensitive material.
- Patent Document 2 describes that an aluminum alloy is used as a SAW filter in a hollow structure.
- an object of the present invention is to provide a method for producing a hollow package and a method for providing a photosensitive composition capable of suppressing corrosion of aluminum wiring constituting the hollow package. And.
- a first aspect of the present invention is a method for manufacturing a hollow package including a hollow structure for accommodating the aluminum wiring on a substrate having the aluminum wiring, wherein the aluminum is placed on the substrate having the aluminum wiring. It has a step of forming a side wall surrounding the wiring and a step of forming a top plate portion on the side wall to form the hollow structure for accommodating the aluminum wiring, and has the side wall and / or the sky.
- the plate portion is characterized by being formed of a photosensitive composition, wherein the photosensitive composition contains a cationic polymerization initiator composed of a cationic portion and an anionic portion, and the anionic portion has the following general formula (I1-). It is a method for producing a hollow structure containing an anion represented by 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 of 1 to 6. However, when k is 2 or more, R may be a divalent or higher organic group coordinated to A by concatenating a plurality of existing Rs.
- m is an integer from 0 to 5.
- n is an integer of 1 to 3.
- m / (k + m) is 0 or more and less than 0.7.
- a second aspect of the present invention is a method for providing a photosensitive composition, which provides the photosensitive composition to a process line for executing the method for producing a hollow package according to the first aspect.
- aliphatic is a relative concept to aromatics and means a group having no aromaticity, a compound having no aromaticity, or the like.
- the "alkyl group” shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
- the "alkylene group” includes linear, branched and cyclic divalent saturated hydrocarbon groups.
- alkyl halide group is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- “Fluorinated alkyl group” refers to a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a fluorine atom.
- the “constituent unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
- the method for manufacturing a hollow package according to the present embodiment is a method for manufacturing a hollow package having a hollow structure for accommodating the aluminum wiring on a substrate having the aluminum wiring, and is on the substrate having the aluminum wiring.
- the side wall and / Alternatively, the top plate portion is characterized in that it is formed of a specific photosensitive composition.
- the method for manufacturing a hollow package of the embodiment includes a step of forming a side wall surrounding the aluminum wiring on a substrate having aluminum wiring (first step (S1)), and a top plate portion on the side wall.
- a step (second step (S2)) of forming the hollow structure for accommodating the aluminum wiring will be described with reference to FIGS. 1 and 2.
- FIG. 1 is a flow chart of a method for manufacturing a hollow package according to an embodiment of the present invention.
- FIG. 2 is a schematic diagram illustrating a second step (S2) described later in the method for manufacturing a hollow package of the embodiment.
- the first step S1 in the present embodiment includes a film forming step S11, an exposure step S12, and a developing step S13, and can be performed as follows.
- a photosensitive composition described later is applied onto a support (substrate 10) by a known method such as a spin coating method, a roll coating method, or a screen printing method, and a bake (post-apply bake (PAB)) treatment is performed. For example, it is applied for 2 to 60 minutes under a temperature condition of 50 to 150 ° C. to form a photosensitive resin film.
- a bake post-apply bake (PAB)
- the support (board 10) is not particularly limited, and conventionally known ones can be used. Examples thereof include a board for electronic components and a support having a predetermined wiring pattern formed therein. More specifically, it is made of metal such as silicon, silicon nitride, titanium, tantalate, lithium tantalate (LiTaO 3 ), niobium, lithium niobate (LiNbO 3 ), palladium, titanium tungsten, copper, chromium, iron and aluminum. Examples include a substrate and a glass substrate. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold and the like can be used.
- aluminum wiring is used for the wiring pattern.
- “Aluminum wiring” includes not only wiring made of aluminum alloy but also wiring made of alloy of aluminum and other metals. As the alloy constituting the wiring that can be used as the aluminum wiring, it is preferable to use an aluminum alloy, an aluminum copper alloy, or the like.
- the film thickness of the photosensitive resin film formed by the photosensitive composition is not particularly limited, but is preferably about 10 to 100 ⁇ m.
- PEB post-exposure baking
- the wavelength used for exposure is not particularly limited, and radiation, for example, ultraviolet rays having a wavelength of 300 to 500 nm, i-line (wavelength 365 nm), or visible light is selectively irradiated (exposed).
- a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser and the like can be used as the radiation source of these radiations.
- radiation means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, and the like.
- the irradiation amount varies depending on the type of each component in the composition, the blending amount, the film thickness of the coating film, and the like, but is 100 to 2000 mJ / cm 2 when, for example, an ultrahigh pressure mercury lamp is used.
- the exposure method of the photosensitive resin film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or immersion exposure (Liquid Immersion Lithography).
- the photosensitive resin film after the exposure step has high transparency, and for example, the haze value when irradiated with i-line (wavelength 365 nm) is preferably 3% or less, more preferably 1.0 to 2.7%. ..
- the photosensitive resin film formed by using the photosensitive composition of the above-described embodiment has high transparency. Therefore, during exposure in pattern formation, light transmission is increased, and a negative pattern having good lithography characteristics can be easily obtained.
- the haze value of the photosensitive resin film after such an exposure step is measured by using a method according to JIS K 7136 (2000).
- the organic solvent contained in the organic developer may be any one that can dissolve the component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specific examples thereof include ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, polar solvents such as ether solvents, hydrocarbon solvents and the like.
- ketone solvent examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone and methylethylketone.
- methylamylketone (2-heptanone) is preferable as the ketone solvent.
- ester solvent examples include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy acetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, and the like.
- nitrile-based solvent examples include acetonitrile, propionitril, valeronitrile, butyronitril and the like.
- a known additive can be added to the organic developer, if necessary.
- the additive include a surfactant.
- the surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used.
- a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
- the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.% With respect to the total amount of the organic developer. 5% by mass is more preferable.
- the developing process can be carried out by a known developing method.
- a method of immersing a support in a developing solution for a certain period of time dip method
- a method of raising the developing solution on the surface of the support by surface tension for a certain period of time A method of standing still (paddle method), a method of spraying the developer on the surface of the support (spray method), a method of applying the developer on the support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed.
- Examples include a method of continuously producing (dynamic dispense method).
- the rinsing treatment (cleaning treatment) using the rinsing liquid can be carried out by a known rinsing method.
- the rinsing treatment method include a method of continuously spraying the rinsing liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in the rinsing liquid for a certain period of time (dip method), and the like.
- Examples thereof include a method of spraying a rinse liquid on the surface of the support (spray method).
- a rinsing liquid containing an organic solvent it is preferable to use a rinsing liquid containing an organic solvent.
- the side wall 20 surrounding the aluminum wiring can be formed on the substrate 10 having the aluminum wiring.
- the substrate 10 on which the side wall 20 is formed, which is obtained in the first step, corresponds to the one shown in [Step (0)] of FIG.
- the recess 15 is formed by the side wall 20 surrounding the aluminum wiring and the substrate 10.
- the exposed portion 30A to be the top plate portion is formed on the side wall 20 formed in the first step to produce the hollow structure for accommodating the aluminum wiring.
- the second step in the present embodiment includes the following step (0), step (i), step (ii), step (iii), step (iv), and step (v).
- Step (0) Step of preparing the substrate 10 on which the side wall 20 obtained in the first step is formed and the photosensitive resist film 30F having the photosensitive resin film 30
- the photosensitive resist film 30F is arranged so as to close the opening surface of the recess 15 formed by the side wall 20 surrounding the aluminum wiring and the substrate 10, and the photosensitive resin film 30 constituting the photosensitive resist film 30F is arranged.
- the step of obtaining the hollow structure 100 in which the exposed portion 30A serving as the top plate portion is made of the cured body 40 of the photosensitive resin film.
- Step (0) S20
- the substrate 10 on which the side wall 20 obtained in the first step is formed and the photosensitive resist film 30F having a photosensitive resin film are prepared.
- the substrate 10 and the side wall 20 formed on the substrate 10 form a substrate having a recess 15 on the surface thereof.
- the photosensitive resist film 30F in the present embodiment has, for example, a negative type photosensitive resin film 30 containing an epoxy group-containing resin (component (A)) and a cationic polymerization initiator (component (I)).
- the photosensitive resin film 30 can be formed by a negative photosensitive composition described later.
- the photosensitive resin film 30 constituting the exposed portion 30A serving as the top plate portion may be the same material as the photosensitive resin material forming the side wall 20, or may be a different material.
- the exposed portion 30A of the photosensitive resin film 30 is (I).
- An acid is generated from the component, and the action of the acid causes ring-opening polymerization of the epoxy group in the component (A), thereby reducing the solubility of the component (A) in a developing solution containing an organic solvent, while reducing the solubility of the component (A).
- the solubility of the component (A) in the developing solution containing an organic solvent does not change, so that the exposed portion 30A and the unexposed portion 30B of the photosensitive resin film 30 are combined.
- the photosensitive resin film 30 is a negative type. Therefore, when the photosensitive resin film 30 is developed with a developing solution containing an organic solvent, the unexposed portion 30B is dissolved and removed, and a negative pattern is formed.
- the negative type photosensitive resin film 30 included in the photosensitive resist film 30F is typically composed of a B-stage (semi-cured) resin material.
- the photosensitive resist film 30F include a laminated film in which the photosensitive resin film 30 is laminated on a base film.
- a negative photosensitive composition in which the components (A) and (I) are dissolved in a solvent is applied onto a base film and dried to form a photosensitive resin film 30.
- the negative photosensitive composition may be applied onto the base film by an appropriate method using an applicator, a blade coater, a lip coater, a comma coater, a film coater, or the like.
- the thickness of the photosensitive resin film 30 is preferably 100 ⁇ m or less, more preferably 5 to 50 ⁇ m.
- the base film a known one can be used, for example, a thermoplastic resin film or the like is used.
- the thermoplastic resin include polyesters such as polyethylene terephthalate.
- the thickness of the base film is preferably 2 to 150 ⁇ m.
- steps (i) to (v) are performed using the substrate having a side wall on the surface prepared in the first step and the photosensitive resist film prepared in the step (0).
- the photosensitive resist film 30F is formed so that the surface of the photosensitive resin film 30 constituting the photosensitive resist film 30F closes the opening surface of the recess 15 formed by the side wall 20 and the substrate 10. Deploy. Then, the base film is peeled off from the photosensitive resin film 30 constituting the photosensitive resist film 30F. In FIG. 2, the photosensitive resin film 30 constituting the photosensitive resist film 30F is arranged so as to face the substrate 10 via the side wall 20. Then, a hollow closed space (cavity) surrounded by the substrate 10, the side wall 20, and the photosensitive resin film 30 is formed.
- Step (ii)] S22
- the photosensitive resin film 30 is exposed.
- the photosensitive resin film 30 is selectively exposed via a photomask 60 on which a predetermined pattern is formed by using a known exposure device.
- the wavelength used for exposure is not particularly limited, and radiation, for example, ultraviolet rays having a wavelength of 300 to 500 nm, i-line (wavelength 365 nm), or visible light is selectively irradiated (exposed).
- radiation for example, ultraviolet rays having a wavelength of 300 to 500 nm, i-line (wavelength 365 nm), or visible light is selectively irradiated (exposed).
- a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser and the like can be used.
- Step (iii)] S23
- the photosensitive resin film 30 after exposure is subjected to heat treatment, so-called post-exposure baking (PEB) treatment.
- the PEB treatment is performed, for example, under a temperature condition of 80 to 150 ° C. for 40 to 600 seconds, preferably 60 to 300 seconds.
- the heat treatment in the step (iii) the photosensitive resin film 30 after exposure becomes an exposed portion 30A in which the epoxy group in the component (A) is ring-opened and polymerized, and an unexposed portion 30B in which there is no change.
- the photosensitive resin film 30 (exposed portion 30A, unexposed portion 30B) after the PEB treatment is developed to form a negative pattern (exposed portion 30A).
- the development here can be performed in the same manner as in the above-mentioned [development step].
- a rinsing treatment is preferably performed.
- the unexposed portion 30B is dissolved and removed, and an exposed portion 30A which becomes a top plate portion (roof that closes the opening surface of the wall portion) remains as a negative pattern.
- Step (v)] S25
- the negative pattern (exposed portion 30A) after development is further cured by heat treatment (cure operation), and the top plate portion is made of a cured body 40 of the photosensitive resin film 30.
- a hollow structure 100 is obtained.
- the photosensitive resin material forming the side wall 20 and the photosensitive resin film 30 are cured and integrated.
- the hollow structure 100 according to the present embodiment has a substrate 10 having aluminum wiring and a cured body 40.
- the negative-type photosensitive composition (hereinafter, may be simply referred to as “photosensitive composition”) used in the method for producing a hollow package of the present embodiment contains a cationic polymerization initiator (I) composed of a cationic moiety and an anionic moiety. do.
- the negative photosensitive composition used in the method for producing a hollow package of the present embodiment contains a cationic polymerization initiator (I) and an epoxy group-containing compound (A) as a resin.
- the component of the cationic polymerization initiator (I) is also referred to as “(I) component”
- the epoxy group-containing compound (A) is also referred to as “(A) component”.
- the cation portion of the component (I) is formed in the exposed portion of the photosensitive resin film.
- Decomposition produces an acid, and the action of the acid causes ring-opening polymerization of the epoxy group in the component (A), reducing the solubility of the component (A) in the developing solution containing the organic solvent.
- the solubility of the component (A) in the developing solution containing the organic solvent does not change, so that the organic solvent is used between the exposed portion and the unexposed portion of the photosensitive resin film.
- There is a difference in solubility in the developing solution containing Therefore, when the photosensitive resin film is developed with a developing solution containing an organic solvent, the unexposed portion is dissolved and removed, and a negative pattern is formed.
- ⁇ Cationic polymerization initiator (I)> The cationic polymerization initiator (component (I)) is irradiated with ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF and ArF, and active energy rays such as X-rays and electron beams to generate cations, and the cations are polymerized. It is a compound that can be an initiator.
- the anion portion of the cationic polymerization initiator (I) contains an anion represented by the following general 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 of 1 to 6. However, when k is 2 or more, R may be a divalent or higher organic group coordinated to A by concatenating a plurality of existing Rs.
- m is an integer from 0 to 5.
- n is an integer of 1 to 3.
- m / (k + m) is 0 or more and less than 0.7.
- A is a heteroatom selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic, antimony and bismuth. These heteroatoms are composed of Group 13 and Group 15 metals. Among these heteroatoms, as the heteroatom selected as A, boron, aluminum, gallium, phosphorus and antimony are preferable, boron and phosphorus are more preferable, and boron is further preferable. For these heteroatoms, one heteroatom may be selected, or two or more heteroatoms may be selected.
- R is a monovalent organic group.
- a plurality of existing Rs may be linked to form an organic group having a divalent value or more coordinated to A.
- An "organic group” is a group containing a carbon atom and has an atom other than the carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, etc.)). You may.
- 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 a halogen atom may be linear, branched or cyclic, and has preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. , 1 to 8 carbon atoms are particularly preferable.
- R may not contain a halogen atom (fluorine atom, chlorine atom, etc.).
- R is a monovalent organic group
- R is a fluorinated alkyl group, a fluorinated aryl group, a pentafluorophenyl group, a 3,5-ditrifluoromethylphenyl group, an alkoxylate, and a nonafluoro-tert-butyl alkoxy.
- Rate ((CF 3 ) 3CO- ) and the like can be mentioned.
- R is a divalent organic group
- examples of the case where R is a divalent organic group include catechol, a compound having a 2,2-prime dihydroxyphenyl group, succinic acid, oxalic acid and the like.
- m / (k + m) is 0 or more and less than 0.7.
- the upper limit of m / (k + m) is preferably less than 0.6, more preferably 0.5 or less, and particularly preferably less than 0.5.
- the numerical value of m / (k + m) is an index regarding the fact that the halogen atom is directly bonded to the hetero atom. The lower the value of m / (k + m), the better. Therefore, the numerical value of m / (k + m) is most preferably 0.
- the component (I) in the photosensitive composition used in the method for producing a hollow package of the present embodiment includes a compound represented by the following general formula (I1) (hereinafter referred to as “component (I1)”) and the following general formula (I2). ) (Hereinafter referred to as “component (I2)”), it is preferable that the compound contains at least one selected from the group.
- component (I) in the photosensitive composition used in the method for producing a hollow package of the present embodiment is further a compound represented by the following general formula (I3-1) or (I3-2) (hereinafter, “(I3)). Ingredients ”) may be included.
- both the component (I1) and the component (I2) generate a relatively strong acid by exposure, when a pattern is formed by using a photosensitive composition containing the component (I). , Sufficient sensitivity is obtained and a good pattern is formed.
- component (I1) is a compound represented by the following general formula (I1).
- R b01 to R b04 are aryl groups or fluorine atoms which may independently have a substituent. However, a relationship of m / (k + m) of 0 or more and less than 0.7 is established between the number of fluorine atoms (m) and the number of aryl groups (k) which may have substituents.
- q is an integer of 1 or more, and Q q + is an independently q-valent organic cation.
- R b01 to R b04 are aryl groups or fluorine atoms which may independently have a substituent.
- the aryl group in R b01 to R b04 preferably has 5 to 30 carbon atoms, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples thereof include a naphthyl group, a phenyl group, an anthrasenyl group and the like, and a phenyl group is preferable because it is easily available.
- the aryl group in R b01 to R b04 may have a substituent.
- the substituent is not particularly limited, but is a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably 1 to 5 carbon atoms), and an alkyl halide group.
- a halogen atom or an alkyl halide group having 1 to 5 carbon atoms is more preferable, and a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is particularly preferable.
- the aryl group has a fluorine atom because the polarity of the anion portion is increased.
- R b01 to R b04 of the formula (I1) a fluorinated phenyl group is preferable, and a perfluorophenyl group is particularly preferable.
- Tetrakis (pentafluorophenyl) borate [B (C 6 F 5 ) 4 ] - ); Tetrakis [(trifluoromethyl) phenyl] borate ([B (C 6 H 4 CF 3 ) 4 ] - ); Difluorobis (pentafluorophenyl) borate ([(C 6 F 5 ) 2 BF 2 ] - ); tetrakis (difluorophenyl) borate ([B (C 6 H 3 F 2 ) 4 ] - ) and the like can be mentioned.
- tetrakis (pentafluorophenyl) borate [B (C 6 F 5 ) 4 ] -
- anions having a number of fluorine atoms directly bonded to borane of "0" (([B (C 6 F 5 ) 4 ] - ), ([B (C 6 H 4 CF 3 ) 4 ] - ) , ([B (C 6 H 3 F 2 ) 4 ] - ), ([B (C 6 F 5 ) 4 ] - )), even if it has the number of fluorine atoms (m) and a substituent.
- q is an integer of 1 or more
- Q q + is an organic cation having a q valence independently.
- Sulfonium cations and iodonium cations are preferably mentioned as the Q q +
- organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferable.
- R 201 to R 207 and R 211 to R 212 each independently represent an aryl group, a heteroaryl group, an alkyl group or an alkenyl group which may have a substituent.
- R 201 to R 203 , R 206 to R 207 , and R 211 to R 212 may be bonded to each other to form a ring together with the sulfur atom in the formula.
- R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- R 210 may have an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
- Y 201 independently represents an arylene group, an alkylene group or an alkenylene group.
- x is 1 or 2.
- W 201 represents a linking group of (x + 1) valence. ]
- Examples of the aryl group in R 201 to R 207 and R 211 to R 212 include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
- Examples of the heteroaryl group in R 201 to R 207 and R 211 to R 212 include those in which a part of the carbon atom constituting the aryl group is replaced with a hetero atom.
- Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
- heteroaryl group examples include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and examples of the substituted heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthene-9-one.
- the alkyl group in R 201 to R 207 and R 211 to R 212 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
- the alkenyl group in R 201 to R 207 and R 211 to R 212 preferably has 2 to 10 carbon atoms.
- Examples thereof include O), an aryl group, and a group represented by the following formulas (ca-r-1) to (ca-r-10), respectively.
- R'201 independently has a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group that may be present.
- R'201 independently has a hydrogen atom and a cyclic group and a substituent which may have a substituent. It is a chain-like alkyl group which may be present, or a chain-like alkenyl group which may have a substituent.
- Cyclic group which may have a substituent The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
- the aromatic hydrocarbon group in R'201 is a hydrocarbon group having an aromatic ring.
- the number of carbon atoms of the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the carbon number does not include the carbon number in the substituent.
- benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings is substituted with a hetero atom.
- Examples thereof include aromatic heterocycles, or rings in which a part of hydrogen atoms constituting these aromatic rings or aromatic heterocycles is substituted with an oxo group or the like.
- Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
- the aromatic hydrocarbon group in R'201 a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, anthracenyl group, etc.), a hydrogen atom of the aromatic ring.
- a group in which one of the groups is substituted with an alkylene group for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.
- an alkylene group for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.
- a group obtained by removing one hydrogen atom from a ring in which a part of the hydrogen atom constituting the aromatic ring is substituted with an oxo group or the like for example, anthr
- the carbon number of the alkylene group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
- Examples of the cyclic aliphatic hydrocarbon group in R'201 include an aliphatic hydrocarbon group containing a ring in the structure.
- an aliphatic hydrocarbon group (a group obtained by removing one hydrogen atom from the alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
- As the monocyclic alicyclic hydrocarbon group a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms.
- the polycycloalkane is a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecan; a fused ring system such as a cyclic group having a steroid skeleton.
- Polycycloalkanes having a polycyclic skeleton of are more preferred.
- cyclic aliphatic hydrocarbon group in R'201 a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane is preferable, and a group obtained by removing one hydrogen atom from a polycycloalkane is preferable. More preferably, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.
- the linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 4 carbon atoms. Is more preferable, and 1 to 3 are most preferable.
- a linear alkylene group is preferable, and specifically, a methylene group [-CH 2- ], an ethylene group [-(CH 2 ) 2- ], a trimethylene group [ -(CH 2 ) 3- ], tetramethylene group [-(CH 2 ) 4- ], pentamethylene group [-(CH 2 ) 5- ] and the like can be mentioned.
- branched alkylene group As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH 3 )-, -CH (CH 2 CH 3 )-, and -C (CH 3 ). 2- , -C (CH 3 ) (CH 2 CH 3 )-, -C (CH 3 ) (CH 2 CH 2 CH 3 )-, -C (CH 2 CH 3 ) 2 -etc.
- Alkyl methylene groups ;- CH (CH 3 ) CH 2- , -CH (CH 3 ) CH (CH 3 )-, -C (CH 3 ) 2 CH 2- , -CH (CH 2 CH 3 ) CH 2- , -C (CH 2 ) CH 3 ) 2 -CH 2 -etc.
- Alkylethylene groups -CH (CH 3 ) CH 2 CH 2- , -CH 2 CH (CH 3 ) CH 2 -etc.
- alkyl group in the alkylalkylene group a linear alkyl group having 1 to 5 carbon atoms is preferable.
- Chain-like alkyl group which may have a substituent may be either linear or branched.
- the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
- Examples thereof include a group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group and a docosyl group.
- the branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms.
- 1-methylethyl group 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples thereof include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.
- Chain alkenyl group which may have a substituent may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5, and even more preferably 2 to 4. 3 is particularly preferable.
- Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like.
- Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.
- a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.
- Examples of the substituent in the cyclic group, chain-like alkyl group or alkenyl group of R'201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group and an oxo group. Examples thereof include a cyclic group, an alkylcarbonyl group and a thienylcarbonyl group in R'201 .
- R'201 is preferably a cyclic group which may have a substituent and a chain alkyl group which may have a substituent.
- R 201 to R 203 , R 206 to R 207 , and R 211 to R 212 are bonded to each other to form a ring together with the sulfur atom in the formula, heteroatoms such as sulfur atom, oxygen atom, and nitrogen atom, or heteroatoms such as nitrogen atom and nitrogen atom are formed.
- one ring containing a sulfur atom in its ring skeleton, including the sulfur atom is preferably a 3- to 10-membered ring, and particularly preferably a 5- to 7-membered ring.
- the formed ring include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxatiin ring, tetrahydro.
- Examples thereof include a thiophenium ring and a tetrahydrothiopyranium ring.
- R 208 to R 209 independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. In the case of, they may be bonded to each other to form a ring.
- R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an alkenyl group which may have a substituent. It is a —SO2 -containing cyclic group which may have a substituent.
- the aryl group in R 210 include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
- the alkyl group in R 210 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
- the alkenyl group in R 210 preferably has 2 to 10 carbon atoms.
- Y 201 independently represents an arylene group, an alkylene group or an alkenylene group, respectively.
- the arylene group in Y 201 include a group obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group in R'201 .
- the alkylene group and the alkenylene group in Y 201 include a chain alkyl group in R'201 and a group in which one hydrogen atom is removed from the group exemplified as the chain alkenyl group.
- W 201 is a (x + 1) valence, i.e., a divalent or trivalent linking group.
- a divalent hydrocarbon group which may have a substituent is preferable, and a substituent exemplified by REP in the above formula ( abp1 ) may be possessed. Groups similar to divalent hydrocarbon groups are preferred.
- the divalent linking group in W 201 may be linear, branched or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group or a group consisting of only an arylene group is preferable.
- Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
- Examples of the trivalent linking group in W 201 include a group obtained by removing one hydrogen atom from the divalent linking group in W 201 , a group in which the divalent linking group is further bonded to the divalent linking group, and the like. Can be mentioned.
- As the trivalent linking group in W 201 a group in which two carbonyl groups are bonded to an arylene group is preferable.
- Suitable cations represented by the above formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-24).
- R " 201 is a hydrogen atom or a substituent.
- substituents those listed as the substituents that the R 201 to R 207 and the R 210 to R 212 may have. The same is true.
- R'211 is an alkyl group.
- R hal is a hydrogen atom or a halogen atom.
- Suitable cation represented by the above formula (ca-2) include diphenyliodonium cation, bis (4-tert-butylphenyl) iodonium cation and the like.
- Suitable cations represented by the above formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).
- Suitable cations represented by the above formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).
- R'212 is an alkyl group or a hydrogen atom.
- R'211 is an alkyl group.
- the cation portion [(Q q + ) 1 / q ] is preferably a cation represented by the general formula (ca-1), and is represented by the formulas (ca-1-1) to (ca-1-48), respectively.
- the cations represented are more preferable, and the cations represented by the formulas (ca-1-25), the formula (ca-1-35), and the formula (ca-1-48) are more preferable, and the cations represented by the formula (ca-1-48) are more preferable. 25) and the cations represented by the formulas (ca-1-48) are particularly preferable.
- m / (k + m) which is a relational expression between the number of fluorine atoms (m) and the number of aryl groups (k) which may have a substituent, is Both are 0.
- component (I2) is a compound represented by the following general formula (I2).
- R b05 is a fluorinated alkyl group or a fluorine atom which may have a substituent.
- the plurality of R b05s may be the same as or different from each other. However, a relationship of m / (k + m) of 0 or more and less than 0.7 is established between the number of fluorine atoms (m) and the number of fluorinated alkyl groups (k) which may have substituents. .. q is an integer of 1 or more, and Q q + is an independently q-valent organic cation. ]
- R b05 is a fluorinated alkyl group or a fluorine atom which may have a substituent.
- the plurality of R b05s may be the same as or different from each other.
- the fluorinated alkyl group in R b05 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
- a group in which a part or all of a hydrogen atom is replaced with a fluorine atom can be mentioned.
- R b05 a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a fluorine atom, a trifluoromethyl group or a pentafluoro is preferable. Ethyl groups are more preferred.
- the anion portion of the compound represented by the formula (I2) is preferably an anion represented by the following general formula (b0-2a).
- R bf05 is a fluorinated alkyl group which may have a substituent.
- nb 1 is an integer of 2 to 6.
- the fluorinated alkyl group which may have a substituent in R bf05 is the same as the fluorinated alkyl group which may have a substituent described in R b05 . be.
- R bf05 a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, a perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a trifluoromethyl group or a pentafluoroethyl group is further preferable.
- nb 1 is preferably an integer of 2 to 4, and most preferably 3.
- Preferred specific examples of the anion portion of the compound represented by the formula (I2) are (CF 3 CF 2 ) 2 PF 4- , (CF 3 CF 2 ) 3 PF 3- , ((CF 3 ) 2 CF) 2 PF. 4- , ((CF 3 ) 2 CF) 3 PF 3- , (CF 3 CF 2 CF 2 ) 2 PF 4- , (CF 3 CF 2 CF 2 ) 3 PF 3- , ((CF 3 ) 2 CFCF 2 ) ) 2 PF 4- , ((CF 3 ) 2 CFCF 2 ) 3 PF 3- , (CF 3 CF 2 CF 2 CF 2 ) 2 PF 4 - and (CF 3 CF 2 CF 2 CF 2 ) 3 PF 3- Examples thereof include represented anions.
- ((CF 3 ) 2 CF ) 3 PF 3- is preferable.
- the number of fluorine atoms (m) and the number of fluorinated alkyl groups which may have a substituent may be present.
- M / (k + m) which is a relational expression between (k) and (k), is 0.667.
- nb 1 in the general formula (b0-2a) is "3”
- m / (k + m) is 0.5.
- q is an integer of 1 or more
- Q q + is an organic cation having a q valence independently.
- the Q q + the same as the above formula (I1) can be mentioned, and among them, the cation represented by the general formula (ca-1) is preferable, and the formulas (ca-1-1) to (ca-1) are preferable.
- the cations represented by ⁇ 47) are more preferable, and the cations represented by the formulas (ca-1-35) and (ca-1-47) are further preferable.
- m / (k + m) is a relational expression between the number of fluorine atoms (m) and the number of fluorinated alkyl groups (k) which may have a substituent. ) Is 0.5.
- the content of the component (I) is preferably 0.5 to 5 parts by mass, more preferably 0.8 to 4.5 parts by mass with respect to 100 parts by mass of the component (A). It is particularly preferable that the amount is up to 4 parts by mass.
- the content of the component (I) is at least the lower limit of the above-mentioned preferable range, corrosion of the aluminum wiring constituting the hollow package can be sufficiently suppressed.
- sufficient sensitivity is obtained, and the lithography characteristics of the pattern are further improved.
- the strength of the cured film is further increased.
- the sensitivity is appropriately controlled, and it becomes easy to obtain a pattern having a good shape.
- component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).
- R b11 to R b12 are a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a halogen atom. It is a chain alkenyl group which may have a substituent other than the above.
- m is an integer of 1 or more, and M m + is an independently m-valent organic cation.
- R b12 is a cyclic group which may have a substituent other than a halogen atom, and a chain alkyl group which may have a substituent other than a halogen atom.
- a chain alkenyl group that may have a substituent other than a halogen atom among the cyclic group, chain alkyl group, and chain alkenyl group described above in R'201 .
- the R b12 is preferably a chain alkyl group which may have a substituent other than a halogen atom, or an aliphatic cyclic group which may have a substituent other than a halogen atom.
- the chain-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms.
- the aliphatic cyclic group a group obtained by removing one or more hydrogen atoms from adamantan, norbornan, isobornan, tricyclodecane, tetracyclododecane and the like (may have a substituent other than a halogen atom); camphor.
- the hydrocarbon group of R b12 may have a substituent other than the halogen atom, and the substituent may be a hydrocarbon group (aromatic hydrocarbon group, aliphatic group) in R b11 of the above formula (I3-2).
- the term "may have a substituent other than a halogen atom" as used herein means not only excluding the case of having a substituent consisting of only a halogen atom but also the case of having a substituent containing at least one halogen atom. (For example, when the substituent is a fluorinated alkyl group, etc.) is excluded.
- M m + is an m-valent organic cation.
- the same cations as those represented by the above general formulas (ca-1) to (ca-5) are preferably mentioned, and among these, the above general formula (ca-1) is used.
- the cation represented by is more preferable.
- at least one of R 201 , R 202 , and R 203 in the above general formula (ca-1) may have a substituent and may have an organic group having 16 or more carbon atoms (aryl group, heteroaryl).
- a sulfonium cation (group, alkyl group or alkenyl group) is particularly preferable because it improves resolution and roughness characteristics.
- Groups and groups represented by the above formulas (ca-r-1) to (ca-r-10) can be mentioned.
- the number of carbon atoms in the organic group is preferably 16 to 25, more preferably 16 to 20, particularly preferably 16 to 18, and such M m +.
- the cations represented by (ca-1-46) and (ca-1-47) are preferably mentioned, and among them, the cation represented by the above formula (ca-1-29) is particularly preferable.
- R b11 is a cyclic group which may have a substituent other than a halogen atom, and a chain alkyl group which may have a substituent other than a halogen atom.
- R b11 is a chain alkenyl group that may have a substituent other than a halogen atom, among the cyclic group, chain alkyl group, and chain alkenyl group described above in R'201 .
- R b11 an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a halogen.
- a chain alkyl group which may have a substituent other than an atom is preferable.
- the substituent that these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof.
- an alkylene group may be used as a substituent.
- the substituents are shown in the following general formulas (y-al-1) to (y-al-7), respectively. Linking groups are preferred.
- V'101 is a single bond or an alkylene group having 1 to 5 carbon atoms
- V'102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.
- the divalent saturated hydrocarbon group in V'102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 5 carbon atoms. Is more preferable.
- the alkylene group in V'101 and V'102 may be a linear alkylene group or a branched chain alkylene group, and a linear alkylene group is preferable.
- Specific examples of the alkylene group in V'101 and V'102 are methylene groups [-CH 2 -];-CH (CH 3 )-, -CH (CH 2 CH 3 )-, -C (CH 3 ). 2- , -C (CH 3 ) (CH 2 CH 3 )-, -C (CH 3 ) (CH 2 CH 2 CH 3 )-, -C (CH 2 CH 3 ) 2 -etc.
- Alkyl methylene group ethylene Group [-CH 2 CH 2- ]; -CH (CH 3 ) CH 2- , -CH (CH 3 ) CH (CH 3 )-, -C (CH 3 ) 2 CH 2- , -CH (CH 2 CH) 3 ) Alkylethylene group such as CH 2- ; trimethylene group (n-propylene group) [-CH 2 CH 2 CH 2- ]; -CH (CH 3 ) CH 2 CH 2- , -CH 2 CH (CH 3 ) Alkyltrimethylene groups such as CH 2- ; Tetramethylene groups [-CH 2 CH 2 CH 2 CH 2- ]; -CH (CH 3 ) CH 2 CH 2 CH 2- , -CH 2 CH (CH 3 ) CH 2 Alkyltetramethylene groups such as CH 2- ; pentamethylene groups [-CH 2 CH 2 CH 2 CH 2- ] and the like can be mentioned.
- a part of the methylene group in the alkylene group in V'101 or V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms.
- the aliphatic ring-type group is obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group of R'201 (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group).
- a divalent group is preferable, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferable.
- the aromatic hydrocarbon group a phenyl group or a naphthyl group is more preferable.
- the aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
- the chain-like alkyl group preferably has 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like.
- Linear alkyl groups such as nonyl group and decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl
- Examples thereof include branched alkyl groups such as a group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
- R b11 a cyclic group which may have a substituent other than a halogen atom is preferable.
- a preferable specific example of the anion portion of the component (I3-2) is shown below.
- M m + is an organic cation having an m valence, which is the same as M m + in the formula (I3-1).
- the component (I) one type may be used alone, or two or more types may be used in combination.
- the component (I) contains one or more selected from the group consisting of the component (I1) and the component (I2), and may further contain the component (I3).
- the component (I) is a cationic polymerization initiator that generates an acid having a pKa (acid dissociation constant) of -5 or less by exposure because of the high elasticity of the resin film and the tendency to form a fine structure without residue. It is preferable to have.
- High sensitivity to exposure can be obtained by using a cationic polymerization initiator that generates an acid having a pKa of -6 or less, more preferably -8 or less.
- the lower limit of pKa of the acid generated by the component is preferably -15 or more.
- pKa acid dissociation constant
- pKa in this specification is a value under the temperature condition of 25 degreeC.
- the pKa value can be measured and obtained by a known method.
- calculated values using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development) can also be used.
- the epoxy group-containing compound (component (A)) used in the photosensitive composition of the present embodiment includes a compound represented by the following general formula (A1) (hereinafter referred to as “component (A1)”) and the following general formula (hereinafter referred to as “component (A1)”).
- component (A1) a compound represented by the following general formula (hereinafter referred to as “component (A1)”
- component (A1) the following general formula (hereinafter referred to as “component (A1)”.
- a compound represented by A2) hereinafter referred to as "(A2) component
- component (A1) component ⁇
- Examples of the component (A1) include an epoxy resin having a structure represented by the following general formula (abp1).
- R EP is an epoxy group-containing group
- Ra 31 and Ra 32 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms
- na 31 is an integer of 1 to 50.
- R EP is an epoxy group-containing group.
- the epoxy group-containing group of REP is not particularly limited, and is a group consisting only of an epoxy group; a group consisting only of an alicyclic epoxy group; an epoxy group or an alicyclic epoxy group and a divalent linking group. A group having and can be mentioned.
- the alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a 3-membered ring ether, and specifically, a group having an alicyclic group and an oxacyclopropane structure.
- the alicyclic group which is the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic.
- Examples of the monocyclic alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.
- Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like.
- the hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group or the like.
- the epoxy group or the alicyclic epoxy group is via a divalent linking group bonded to an oxygen atom (—O—) in the formula. It is preferable that the groups are bonded.
- the divalent linking group is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like are preferable.
- the divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.
- the linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
- a linear alkylene group is preferable, and specifically, a methylene group [-CH 2- ], an ethylene group [-(CH 2 ) 2- ], a trimethylene group [ -(CH 2 ) 3- ], tetramethylene group [-(CH 2 ) 4- ], pentamethylene group [-(CH 2 ) 5- ] and the like can be mentioned.
- the branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms.
- a branched alkylene group is preferable, and specifically, -CH (CH 3 )-, -CH (CH 2 CH 3 )-, and -C (CH 3 ).
- Alkyl methylene groups ;- CH (CH 3 ) CH 2- , -CH (CH 3 ) CH (CH 3 )-, -C (CH 3 ) 2 CH 2- , -CH (CH 2 CH 3 ) CH 2- , -C (CH 2 ) CH 3 ) 2 -CH 2 -etc.
- Alkylethylene groups -CH (CH 3 ) CH 2 CH 2- , -CH 2 CH (CH 3 ) CH 2 -etc.
- alkyl group in the alkylalkylene group a linear alkyl group having 1 to 5 carbon atoms is preferable.
- an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from the alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples thereof include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
- the aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n + 2) ⁇ electrons, and may be a monocyclic type or a polycyclic type.
- the number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12.
- Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned.
- the hetero atom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
- Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
- the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings.
- a group from which two hydrogen atoms have been removed from for example, biphenyl, fluorene, etc.
- one of the hydrogen atoms of the group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring examples of the hetero atom in the aromatic heterocycle.
- Hydrogen from an aryl group in an arylalkyl group such as a group substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group).
- an alkylene group for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group.
- a group from which one atom is further removed) and the like can be mentioned.
- the carbon number of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
- the divalent hydrocarbon group may have a substituent.
- the linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent.
- the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group and the like.
- the alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in the structure as the divalent hydrocarbon group may or may not have a substituent.
- substituents include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
- alkyl group as the substituent an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
- an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are preferable, and methoxy is preferable.
- Groups and ethoxy groups are most preferred.
- the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- halogenated alkyl group examples include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
- a part of the carbon atom constituting the ring structure may be substituted with a substituent containing a heteroatom.
- the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent.
- a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent.
- the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group and the like.
- the alkyl group as the substituent an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
- the alkoxy group, the halogen atom and the alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the alicyclic hydrocarbon group.
- the hetero atom in the divalent linking group including the hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
- the H may be substituted with a substituent such as an alkyl group or an acyl.
- the substituent alkyl group, acyl group, etc.
- the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
- the divalent hydrocarbon group is the "divalent hydrocarbon group which may have a substituent" mentioned in the above description as the divalent linking group. Similar things can be mentioned.
- a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable.
- a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable.
- the alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
- b' is an integer of 1 to 10 and 1 to 8. Is preferred, an integer of 1 to 5 is more preferred, 1 or 2 is even more preferred, and 1 is most preferred.
- the glycidyl group is preferable as the epoxy group-containing group in REP .
- Ra31 and Ra32 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
- the alkyl group having 1 to 5 carbon atoms of R a31 and Ra 32 is, for example, a linear, branched chain, or cyclic alkyl group having 1 to 5 carbon atoms.
- Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like.
- cyclic alkyl group examples include a cyclobutyl group and a cyclopentyl group.
- Ra 31 and Ra 32 a hydrogen atom or a linear or branched alkyl group is preferable, a hydrogen atom or a linear alkyl group is more preferable, and a hydrogen atom or a methyl group is further preferable.
- na 31 is an integer of 1 to 50, preferably an integer of 4 to 50, more preferably an integer of 4 to 15, and even more preferably 5 to 8.
- Examples of the preferable component (A1) include an epoxy resin having a structure represented by the following general formula (a1-01) or the following general formula (a1-02).
- R EP is an epoxy group-containing group
- na 31 is an integer of 4 to 50.
- R EP is an epoxy group-containing group
- na 31 is an integer of 4 to 50.
- the R EP is an epoxy group-containing group, and has the same description as the R EP in the formula (abp1). Of these, the glycidyl group is preferable as the epoxy group-containing group in REP .
- na 31 is an integer of 4 to 50, preferably an integer of 4 to 15, and more preferably an integer of 5 to 8. be.
- An epoxy resin having a structure represented by the above general formula (a1-01) is preferable because the stress inside the cured film can be easily suppressed to a lower level.
- An epoxy resin having a structure represented by the above general formula (a1-02) is preferable because the mold resistance can be easily enhanced.
- the component (A1) Commercially available products that can be used as the component (A1) include, for example, JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (all manufactured by Mitsubishi Chemical Corporation); , EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above, manufactured by DIC Corporation); LCE-21, RE-602S (above, manufactured by Nippon Kayaku Corporation) and the like.
- the component (A1) one type may be used alone, or two or more types may be used in combination.
- the content of the component (A1) is 60 to 100 parts by mass and 70 to 100 parts by mass with respect to the total mass (100% by mass) of the component (A). It is preferably 50 to 100 parts by mass, and more preferably 50 to 100 parts by mass.
- the component (A2) is an epoxy resin represented by the following general formula (A2-1) whose epoxy equivalent is smaller than that of the component (A1). That is, a novolak type epoxy resin (Anv) is used as the component (A2).
- the component (A2) may have an epoxy equivalent that is relatively smaller than the epoxy equivalent in the component (A1).
- R p1 and R p2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
- the plurality of R p1s may be the same as or different from each other.
- the plurality of R p2s may be the same as or different from each other.
- n 1 is an integer of 1 to 5.
- R EP is an epoxy group-containing group.
- the plurality of R EPs may be the same as or different from each other.
- the alkyl groups having 1 to 5 carbon atoms of R p1 and R p2 are, for example, linear, branched or cyclic alkyl groups having 1 to 5 carbon atoms.
- the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like.
- the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group.
- R p1 and R p2 a hydrogen atom or a linear or branched alkyl group is preferable, a hydrogen atom or a linear alkyl group is more preferable, and a hydrogen atom or a methyl group is further preferable.
- the plurality of R p1s may be the same or different from each other.
- the plurality of R p2s may be the same as or different from each other.
- n 1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.
- R EP is an epoxy group-containing group, and has the same description as R EP in the above formula (abp1). Of these, the glycidyl group is preferable as the epoxy group-containing group in REP .
- the component (A2) one type may be used alone, or two or more types may be used in combination.
- the content of the component (A2) is 15 to 60% by mass and 20 to 55% by mass with respect to the total mass (100% by mass) of the component (A). It is preferably 25 to 50% by mass, and more preferably 25 to 50% by mass.
- the component (A) is an epoxy group-containing compound other than the component (A1) and the component (A2) (hereinafter, this is also referred to as “component (A3)”). May include.
- Examples of the component (A3) include a novolak type epoxy resin (Anv) having a structural unit represented by the following general formula (anv1).
- R EP is an epoxy group-containing group
- Ra 22 and Ra 23 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or halogen atoms, respectively.
- the alkyl groups having 1 to 5 carbon atoms of R a22 and R a23 are the same as the alkyl groups having 1 to 5 carbon atoms of R p1 and R p2 in the formula (A2-1).
- the halogen atom of R a22 and R a23 is preferably a chlorine atom or a bromine atom.
- the R EP is the same as the R EP in the formula (abp1), and a glycidyl group is preferable.
- the novolak type epoxy resin (Av) may be a resin composed of only the constituent unit (anv1), or may be a resin having a constituent unit (anv1) and another constituent unit.
- Examples of other structural units include structural units represented by the following general formulas (anv2) to (anv3).
- Ra24 is a hydrocarbon group which may have a substituent.
- R a25 to Ra26 and R a28 to Ra30 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or halogen atoms, respectively.
- Ra27 is a hydrocarbon group which may have an epoxy group-containing group or a substituent.
- Ra24 is a hydrocarbon group which may have a substituent.
- the hydrocarbon group which may have a substituent include a linear or branched alkyl group or a cyclic hydrocarbon group.
- the linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the branched-chain alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
- the aliphatic hydrocarbon group which is a monocyclic group a group obtained by removing one hydrogen atom from a monocycloalkane is preferable.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
- the aromatic hydrocarbon group of Ra24 is an aromatic hydrocarbon group
- the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 ⁇ electrons, and may be a monocyclic type or a polycyclic type.
- the number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12.
- Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms.
- hetero atom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
- aromatic heterocycle examples include a pyridine ring and a thiophene ring.
- aromatic hydrocarbon group in Ra24 a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle; and containing two or more aromatic rings.
- a group obtained by removing one hydrogen atom from an aromatic compound for example, biphenyl, fluorene, etc.
- a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or the aromatic heterocycle is substituted with an alkylene group for example, a benzyl group, etc.
- alkylene group for example, a benzyl group, etc.
- examples thereof include an arylalkyl group such as a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group).
- the carbon number of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
- Ra25 to Ra26 and Ra28 to Ra30 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms or halogen atoms, and have 1 to 5 carbon atoms, respectively.
- the alkyl group and the halogen atom are the same as those of Ra 22 and Ra 23 , respectively.
- Ra27 is a hydrocarbon group which may have an epoxy group-containing group or a substituent.
- the epoxy group-containing group of Ra 27 is the same as R EP in the above formula ( A2-1 ), and the hydrocarbon group which may have a substituent of Ra 27 is the same as Ra 24.
- the ratio of each structural unit in the resin (Anv) is not particularly limited, but the resin (Anv). ),
- the total of the constituent units having an epoxy group is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%, based on the total of all the constituent units constituting the above.
- novolak type epoxy resin (Anv) are, for example, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, and 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 Nittetsu Chemical & Materials Co., Ltd.) and the like.
- a compound represented by the following chemical formula (A3-1) may be used in addition to the above-mentioned resin.
- Examples of commercially available products that can be used as the compound represented by the following chemical formula (A3-1) include TECHMORE VG-3101L (manufactured by Printec Co., Ltd.).
- a compound represented by the following chemical formula (A3-2) may be used in addition to the above-mentioned resin.
- Examples of commercially available products that can be used as the compound represented by the following chemical formula (A3-2) include Showfree (registered trademark) BATG (manufactured by Showa Denko KK) and the like.
- the component (A3) includes, for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylol propanetetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl.
- examples of the component (A3) include an aliphatic epoxy resin and an acrylic resin (Aac).
- examples of the aliphatic epoxy resin and acrylic resin (Aac) include resins having epoxy group-containing units represented by the following general formulas (a1-1) to (a1-2).
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms.
- Va 41 is a divalent hydrocarbon group which may have a substituent.
- na 41 is an integer of 0 to 2.
- R a41 and R a42 are epoxy group-containing groups.
- na 42 is 0 or 1.
- Wa 41 is a (na 43 +1) valent aliphatic hydrocarbon group.
- na 43 is an integer of 1 to 3.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
- the alkyl group having 1 to 5 carbon atoms of R is preferably linear or branched, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl. Examples include a group, a pentyl group, an isopentyl group, a neopentyl group and the like.
- the halogenated alkyl group having 1 to 5 carbon atoms of R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
- R a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.
- Va 41 is a divalent hydrocarbon group which may have a substituent and has a substituent described in REP in the formula ( abp1 ). Examples thereof include groups similar to divalent hydrocarbon groups which may be present.
- the hydrocarbon group of Va 41 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, and further preferably a linear aliphatic hydrocarbon group. Linear alkylene groups are particularly preferred.
- na 41 is an integer of 0 to 2, preferably 0 or 1.
- R a41 and R a42 are epoxy group-containing groups and are the same as R EP in the above formula (abp1).
- the (na 43 +1) valent aliphatic hydrocarbon group in Wa 41 means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated. It is also good, usually preferably saturated.
- the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a linear or branched aliphatic hydrocarbon group. And a group combining an aliphatic hydrocarbon group containing a ring in the structure can be mentioned.
- na 43 is an integer of 1 to 3, preferably 1 or 2.
- R ⁇ represents a hydrogen atom, a methyl group or a trifluoromethyl group.
- R a51 represents a divalent hydrocarbon group having 1 to 8 carbon atoms.
- R a52 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
- R a53 represents a hydrogen atom or a methyl group.
- na 51 is an integer of 0 to 10.
- R a51 , R a52 , and R a53 may be the same or different from each other.
- the acrylic resin (Aac) may have a structural unit derived from another polymerizable compound for the purpose of appropriately controlling physical and chemical properties.
- a polymerizable compound include known radically polymerizable compounds and anionic polymerizable compounds.
- polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy.
- Styrene derivatives having carboxyl groups and ester bonds such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth).
- the content ratio of the epoxy group-containing unit in the resin is preferably 5 to 40 mol%, preferably 10 to 30 mol%. Is more preferable, and most preferably 15 to 25 mol%.
- a compound containing a partial structure represented by the following general formula (m1) (hereinafter, also referred to as “(m1) component”) is preferably mentioned.
- n 2 is an integer of 1 to 4. * Indicates a bond. ]
- n 2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.
- Examples of the component (m1) include compounds in which a plurality of partial structures represented by the above general formula (m1) are bonded via a divalent linking group or a single bond. Among these, a compound in which a plurality of partial structures represented by the above general formula (m1) are bonded via a divalent linking group is preferable.
- the divalent linking group here is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like.
- the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom the substituent described in REP (epoxy group-containing group) in the above formula ( abp1 ) is used.
- Y21 a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
- aliphatic epoxy resin a compound represented by the following general formula (m2) (hereinafter, also referred to as “(m2) component”) is preferably mentioned.
- R EP is an epoxy group-containing group.
- the plurality of R EPs may be the same as or different from each other. ]
- the R EP is an epoxy group-containing group and is the same as the R EP in the above formula (abp1).
- ADEKA RESIN EP-4080S, EP-4085S, EP-4088S all manufactured by ADEKA Corporation
- Selokiside 8000, Selokiside 8010, EHPE-3150, EPOLEAD PB 3600, PB 4700 all manufactured by Daicel Co., Ltd.
- 850L all manufactured by Nagase ChemteX Corporation
- TEPIC-VL manufactured by Nissan Chemical Co., Ltd.
- the content of the (A3) component shall be 30% by mass or less with respect to the total mass (100% by mass) of the (A) component. It is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 5 to 20% by mass.
- the content of the component (A) in the photosensitive composition of the present embodiment may be adjusted according to the film thickness of the photosensitive resin film to be formed and the like.
- the content of the component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total mass (100% by mass) of the photosensitive composition. It is preferable, 95% by mass or more is more preferable, and 97% by mass or more is particularly preferable.
- the component (A1) and the component (A2) are mixed and used in the photosensitive composition of the present embodiment, it is preferably contained in a ratio of 25 parts by mass: 75 parts by mass to 75 parts by mass: 25 parts by mass.
- the photosensitive composition of the present embodiment contains 50 parts by mass: 50 parts by mass.
- the photosensitive composition used in the method for producing a hollow package of the present embodiment may contain other components, if necessary, in addition to the above-mentioned components (A) and (I).
- the photosensitive composition used in the method for producing a hollow package of the present embodiment contains, if desired, a miscible additive such as a metal oxide (M), a silane coupling agent, a sensitizer component, a solvent, and a film. Additional resins, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, antihalation agents and the like for improving the performance can be appropriately added and contained.
- M Metal oxide (M) ⁇
- a cured film having increased strength can be easily obtained.
- M) (hereinafter, also referred to as “(M) component”) may be contained. Further, by having the component (M) together, a high-resolution pattern can be formed with a good shape.
- the component (M) include oxides of metals such as silicon (metal silicon), titanium, zirconium, and hafnium. Among these, an oxide of silicon is preferable, and among these, silica is particularly preferable.
- the shape of the component (M) is preferably particulate.
- the particle-like (M) component those having a volume average particle diameter of 5 to 40 nm are preferable, those having a volume average particle diameter of 5 to 30 nm are more preferable, and those having a volume average particle diameter of 5 to 30 nm are more preferable.
- a particle group having a particle size of 10 to 20 nm is more preferable.
- the particle size of the component (M) may be appropriately selected according to the exposure light source. Generally, it is said that the influence of light scattering is almost negligible for particles having a particle diameter of 1/10 or less with respect to the wavelength of light.
- the (M) component is a particle group having a primary particle diameter (volume average value) of 10 to 20 nm (particularly preferably a silica particle group). ) Is preferably used.
- the component (M) one type may be used alone, or two or more types may be used in combination.
- the content is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the component (A).
- the content of the component (M) is at least the lower limit of the above-mentioned preferable range, the strength of the cured film is further increased.
- the transparency of the resin film is further enhanced.
- the photosensitive composition used in the method for producing a hollow package of the present embodiment may further contain an adhesive aid in order to improve the adhesiveness with the substrate.
- an adhesive aid a silane coupling agent is preferable.
- the silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, and an epoxy group.
- silane coupling agent may be used alone, or two or more types may be used in combination.
- the content is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 0.5 to 10 parts by mass.
- the strength of the cured film is further increased.
- the adhesiveness between the cured film and the substrate is further strengthened.
- the photosensitive composition used in the method for producing a hollow package of the present embodiment may further contain a sensitizer component.
- the sensitizer component is not particularly limited as long as it can absorb energy from exposure and transfer the energy to other substances.
- Specific examples of the sensitizer component include benzophenone-based photosensitizers such as benzophenone and p, p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetphen-based photosensitizers, and 1,5-dihydroxynaphthalene.
- Naphthalene-based photosensitizers such as, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, and known photosensitizers such as biacetyl, eosin, rosebengal, pyrene, phenothiazine, and antron. Can be used.
- the sensitizer component one type may be used alone, or two or more types may be used in combination.
- the content is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 0.5 to 5 parts by mass.
- the content of the sensitizer component is in the above-mentioned preferable range, the sensitivity and the resolvability are further enhanced.
- the photosensitive composition used in the method for producing a hollow package of the present embodiment may further contain a solvent (hereinafter, may be referred to as “(S) component”).
- a solvent hereinafter, may be referred to as “(S) component”.
- the component (S) include lactones such as ⁇ -butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; ethylene glycol and diethylene glycol.
- Polyvalent alcohols such as propylene glycol, dipropylene glycol; 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol.
- a compound having an ester bond such as monoacetate, a monomethyl ether such as the polyhydric alcohol or the compound having the ester bond, a monoalkyl ether such as monoethyl ether, monopropyl ether, or monobutyl ether, or an ether bond such as monophenyl ether.
- polyhydric alcohols such as compounds having [Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable]; cyclic ethers such as dioxane, methyl lactate, and lactic acid.
- PGMEA propylene glycol monomethyl ether acetate
- PGME propylene glycol monomethyl ether
- cyclic ethers such as dioxane, methyl lactate, and lactic acid.
- Esters such as ethyl (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, diphenyl ether, di Examples thereof include aromatic organic solvents such as benzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, simene and mesityrene, and dimethylsulfoxide (DMSO).
- component (S) one type may be used alone, or two or more types may be used as a mixed solvent.
- the amount to be used when the component (S) is contained is not particularly limited, and is appropriately set according to the coating film thickness at a concentration at which the photosensitive composition can be applied to a substrate or the like without dripping.
- the component (S) can be used so that the solid content concentration is 50% by mass or more, and the component (S) can be used so that the solid content concentration is 60% by mass or more.
- an embodiment in which the component (S) is substantially not contained that is, an embodiment in which the solid content concentration is 100% by mass
- the hollow package manufactured by the method for manufacturing the medium space package of the present embodiment described above includes aluminum wiring and a hollow structure.
- the hollow structure included in the hollow package manufactured by the manufacturing method of the present embodiment described above is formed of a photosensitive composition containing an anion represented by the general formula (I1-an).
- m / (k + m) is 0 or more and less than 0.7.
- the anion of the component (I) the halogen atom directly bonded to the hetero atom (A in the formula) is easily liberated.
- an anion having few or no halogen atoms directly bonded to such a hetero atom (A in the formula) is contained (I). By using the component), the amount of halogen atoms liberated can be reduced.
- the above-mentioned free halogen atoms contribute to the corrosion of the aluminum wiring provided in the hollow package.
- the component (I) that reduces the amount of halogen atoms released is adopted, it is possible to manufacture a hollow package in which corrosion of aluminum wiring is suppressed.
- a resin composition can be used as the sealing material.
- the resin used for the encapsulant is not particularly limited as long as the hollow structure can be sealed and insulated at least, and examples thereof include epoxy resins and silicone resins.
- the encapsulant may contain other components such as a filler in addition to the resin.
- the method of sealing the hollow structure with a sealing material is not particularly limited, and the heat-melted sealing material is supplied onto the hollow structure so as to cover the hollow structure and is compression-molded to form a hollow structure.
- a hollow package having a sealing material layer on the structure is produced.
- the encapsulant layer has a function of protecting the MEMS, wiring portion, etc. in the hollow structure from the external environment.
- the method for providing a photosensitive composition of the present embodiment provides a photosensitive composition for a process line for executing the above-mentioned method for producing a hollow package.
- the photosensitive composition here may be prepared by appropriately selecting from the above-mentioned materials, and the timing of preparing the photosensitive composition may be determined according to the size of the process line and the operating speed.
- the business entity that executes the hollow package manufacturing method and the business entity that executes the present provision method do not necessarily have to be the same.
- (A2) -1 A compound represented by the following chemical formula (A2-1).
- (I1) -1 Cationic polymerization initiator represented by the following chemical formula (I1-1). m / (k + m) is 0.5.
- (I1) -2 Cationic polymerization initiator represented by the following chemical formula (I1-2). m / (k + m) is 0.
- (I1) -3 Cationic polymerization initiator represented by the following chemical formula (I1-3). [2-tert-Butyl-5-methyl-4- (2-thioxanthonylthio) phenyl] (5-tert-butyl-2-methylphenyl) (2-thioxanthonyl) sulfonium tetrakis (pentafluorophenyl) borate. m / (k + m) is 0.
- (I1) -4 Cationic polymerization initiator represented by the following chemical formula (I1-4). m / (k + m) is 1.
- (I3) -1 Cationic polymerization initiator represented by the following chemical formula (I3-1-1).
- (SC) -1 A compound represented by the following chemical formula (SC-1).
- (D) -1 Sensitizer. ⁇ -Naphthol.
- Preparation of resist film The negative photosensitive composition of each of the above-mentioned preparation examples is applied onto the base film using an applicator, and the photosensitive resin is subjected to baking treatment (PAB) at 70 ° C. for 10 minutes in an oven. A film was formed to obtain a photosensitive resist film.
- PAB baking treatment
- Preparation of cured product The resist film was irradiated with ghi rays at an irradiation amount of 10000 mJ / cm 2 .
- the base film was peeled off and cured by heat treatment in an oven to obtain a cured product.
- Example 1 [First step]: S1 By the following film forming step, exposure step, and developing step, a side wall surrounding the aluminum wiring was formed on the substrate having the aluminum wiring.
- the negative photosensitive composition of Preparation Example 1 is applied onto the support using an applicator, applied onto the base film using an applicator, and baked in an oven at 70 ° C. for 10 minutes.
- PAB photosensitive resin film having a thickness of 20 ⁇ m was formed, and a photosensitive resist film was obtained.
- the photosensitive resin film formed from the negative photosensitive composition of Preparation Example 1 and the silicon wafer on which aluminum was vapor-deposited had a thickness of 20 ⁇ m under the conditions of 80 ° C., 0.3 MPa, and 0.5 m / min. Laminated to be.
- the negative pattern is further cured by heat treatment in an oven, and a substrate having a wall portion having a side wall made of a cured body of a photosensitive resin film made of the negative photosensitive composition of Preparation Example 1 is provided. Formed.
- Step (0)] S20 First, an aluminum-deposited aluminum substrate having a side wall obtained in the first step was prepared.
- the negative photosensitive composition of Preparation Example 1 is applied onto the base film using an applicator, applied onto the base film using an applicator, and baked in an oven at 70 ° C. for 10 minutes.
- PAB photosensitive resin film having a thickness of 45 ⁇ m was formed, and a photosensitive resist film was obtained.
- Example 2 A hollow structure was obtained in the same manner as in Example 1 except that the negative photosensitive composition of Preparation Example 1 was changed to the negative photosensitive composition of Preparation Example 2.
- Example 3 The negative photosensitive composition of Preparation Example 1 used for the side wall was changed to the negative photosensitive composition of Preparation Example 3, and the negative photosensitive composition of Preparation Example 1 used for the top plate was prepared. A hollow structure was obtained in the same manner as in Example 1 except that the composition was changed to the negative photosensitive composition of 4.
- Example 4 A hollow structure was obtained in the same manner as in Example 1 except that the aluminum layer formed on the silicon wafer was changed to a 1% aluminum copper alloy layer (AlCu layer).
- Example 5 Except that 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 the aluminum 1% copper alloy layer (AlCu layer). Obtained a hollow structure in the same manner as in Example 1.
- Example 6 The negative photosensitive composition of Preparation Example 1 used for the side wall was changed to the negative photosensitive composition of Preparation Example 3, and the negative photosensitive composition of Preparation Example 1 used for the top plate was prepared. A hollow structure was obtained in the same manner as in Example 1 except that the negative photosensitive composition of No. 4 was changed and the aluminum layer formed on the silicon wafer was changed to a 1% aluminum copper alloy layer.
- FIG. 3 shows the results of photographing the state of the hollow package before and after the HAST test with an optical microscope.
- Comparative Example 1 it was observed through the top plate portion 4 that the inside of the side wall 3 was blackened because the aluminum-deposited substrate inside surrounded by the side wall 3 was corroded.
- Example 3 the inside surrounded by the side wall 1 did not corrode, and the substrate could be observed through the top plate portion 2.
- the results of internal corrosion of Examples 1 and 2 were similar to those of Example 3.
- FIG. 4 shows the results of photographing the state of the hollow package before and after the PCT test with an optical microscope.
- Comparative Example 2 it was observed through the top plate portion 4 that the inside of the side wall 3 was blackened because the aluminum-1% copper alloy vapor-deposited substrate inside surrounded by the side wall 3 was corroded.
- Example 6 the inside surrounded by the side wall 1 did not corrode, and the substrate could be observed through the top plate portion 2.
- the results of internal corrosion of Examples 4-5 were similar to those of Example 6.
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Abstract
Description
本願は、2020年11月19日に日本に出願された、特願2020-192768号に基づき優先権主張し、その内容をここに援用する。
そこで本発明は、上記事情に鑑みてなされたものであり、中空パッケージを構成するアルミニウム配線の腐食を抑制することができる中空パッケージの製造方法及び感光性組成物の提供方法を提供することを目的とする。
本発明の第1の態様は、アルミニウム配線を有する基板上に、前記アルミニウム配線を収容する中空構造体を備えた中空パッケージの製造方法であって、前記のアルミニウム配線を有する基板上に、前記アルミニウム配線を囲む側壁を形成する工程と、前記側壁上に、天板部を形成して、前記アルミニウム配線を収容する前記中空構造体を作製する工程と、を有し、前記側壁及び/又は前記天板部は感光性組成物により形成されることを特徴とし、前記感光性組成物は、カチオン部とアニオン部とからなるカチオン重合開始剤を含有し、前記アニオン部が、下記一般式(I1-an)で表されるアニオンを含む、中空構造体の製造方法である。
「アルキル基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の1価の飽和炭化水素基を包含するものとする。アルコキシ基中のアルキル基も同様である。
「アルキレン基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の2価の飽和炭化水素基を包含するものとする。
「ハロゲン化アルキル基」は、アルキル基の水素原子の一部又は全部がハロゲン原子で置換された基であり、該ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
「フッ素化アルキル基」は、アルキル基の水素原子の一部又は全部がフッ素原子で置換された基をいう。
「構成単位」とは、高分子化合物(樹脂、重合体、共重合体)を構成するモノマー単位(単量体単位)を意味する。
「置換基を有していてもよい」と記載する場合、水素原子(-H)を1価の基で置換する場合と、メチレン基(-CH2-)を2価の基で置換する場合と、の両方を含む。
「露光」は、放射線の照射全般を含む概念とする。
本実施形態に係る中空パッケージの製造方法は、アルミニウム配線を有する基板上に、前記アルミニウム配線を収容する中空構造体を備えた中空パッケージの製造方法であって、前記のアルミニウム配線を有する基板上に、前記アルミニウム配線を囲む側壁を形成する工程と、前記側壁上に、天板部を形成して、前記アルミニウム配線を収容する前記中空構造体を作製する工程と、を有し、前記側壁及び/又は前記天板部は、特定の感光性組成物により形成されることを特徴とする。
以下、図1および図2を参照しながら、側壁及び天板部が感光性組成物により形成される中空パッケージの製造方法の実施形態について説明する。
図1は、本発明に係る実施形態の中空パッケージの製造方法のフロー図である。
図2は、実施形態の中空パッケージの製造方法のうち、後述する第2工程(S2)を説明する模式図である。
本実施形態における第1工程では、アルミニウム配線を有する基板10上に、アルミニウム配線を囲む側壁20を形成する。
本実施形態における第1工程S1は、膜形成工程S11と、露光工程S12と、現像工程S13とを含み、以下のように行うことができる。
まず、支持体(基板10)上に、後述する感光性組成物を、スピンコート法、ロールコート法、スクリーン印刷法等の公知の方法で塗布し、ベーク(ポストアプライベーク(PAB))処理を、例えば50~150℃の温度条件にて2~60分間施し、感光性樹脂膜を形成する。
次に、形成された感光性樹脂膜に対し、公知の露光装置を用いて、所定のパターンが形成されたマスク(マスクパターン)を介した露光、又はマスクパターンを介さない電子線の直接照射による描画等による選択的露光を行う。
前記選択的露光を行った後、必要に応じてベーク(ポストエクスポージャーベーク(PEB))処理を、たとえば80~150℃の温度条件にて40~1200秒間、好ましくは40~1000秒間、より好ましくは60~900秒間施す。
ここで放射線とは、紫外線、可視光線、遠紫外線、X線、電子線などを意味する。放射線照射量は、組成物中の各成分の種類、配合量、塗膜の膜厚などによって異なるが、例えば超高圧水銀灯使用の場合、100~2000mJ/cm2である。
このように、上述した実施形態の感光性組成物を用いて形成された感光性樹脂膜は、透明性が高い。このため、パターン形成における露光の際、光透過性が高まり、良好なリソグラフィー特性のネガ型パターンが得られやすい。
かかる露光工程後の感光性樹脂膜のヘーズ値は、JIS K 7136(2000)に準拠した方法を用いて測定される。
次に、前記露光後の感光性樹脂膜を、有機溶剤を含有する現像液(有機系現像液)で現像する。現像の後、好ましくはリンス処理を行う。必要に応じてベーク処理(ポストベーク)を行ってもよい。
界面活性剤としては、非イオン性の界面活性剤が好ましく、非イオン性のフッ素系界面活性剤、又は非イオン性のシリコン系界面活性剤がより好ましい。
界面活性剤を配合する場合、その配合量は、有機系現像液の全量に対して、通常0.001~5質量%であり、0.005~2質量%が好ましく、0.01~0.5質量%がより好ましい。
リンス処理は、有機溶剤を含有するリンス液を用いることが好ましい。
本実施形態における第2工程では、前記第1工程で形成した側壁20上に、天板部となる露光部30Aを形成して、前記アルミニウム配線を収容する前記中空構造体を作製する。
本実施形態における第2工程は、下記の工程(0)と、工程(i)と、工程(ii)と、工程(iii)と、工程(iv)と、工程(v)とを有する。
工程(i):前記感光性レジストフィルム30Fが、アルミニウム配線を囲む側壁20と、基板10とで形成される凹部15の開口面を塞ぐように、前記感光性レジストフィルム30Fを配置し、前記感光性レジストフィルム30Fを構成する感光性樹脂膜30から、前記基材フィルムを剥離する工程
工程(ii):前記工程(i)後、前記感光性樹脂膜30を露光する工程
工程(iii):前記工程(ii)後の前記感光性樹脂膜30に対して加熱処理を行う工程
工程(iv):前記工程(iii)後、前記感光性樹脂膜30を現像して、第1工程で形成した側壁20と、基板10とで形成される凹部15の開口面を塞ぐネガ型パターン(露光部30A)を形成する工程
工程(v):前記工程(iv)後の前記ネガ型パターン(露光部30A)に対し、さらに加熱処理を行うことにより硬化させて、前記天板部となる露光部30Aが前記感光性樹脂膜の硬化体40からなる中空構造体100を得る工程
本実施形態における工程(0)では、第1工程で得られた側壁20を形成した基板10と、感光性樹脂膜を有する感光性レジストフィルム30Fと、を用意する。
図2においては、基板10と、基板10上に形成された側壁20とによって、表面に凹部15を有する基板が構成されている。
本実施形態における感光性レジストフィルム30Fは、例えば、エポキシ基含有樹脂((A)成分)及びカチオン重合開始剤((I)成分)を含有するネガ型の感光性樹脂膜30を有する。感光性樹脂膜30は、後述するネガ型感光性組成物により形成することができる。
天板部となる露光部30Aを構成する感光性樹脂膜30は、側壁20を形成する感光性樹脂材料と同一の材料でもよいし、異なる材料でもよい。
感光性レジストフィルム30Fとしては、感光性樹脂膜30が基材フィルムに積層した積層フィルムからなるものが挙げられる。本実施形態に係る感光性レジストフィルム30Fは、感光性樹脂膜30が基材フィルムに積層した積層フィルムを用いることが好ましい。
基材フィルム上へのネガ型感光性組成物の塗布は、アプリケーター、ブレードコーター、リップコーター、コンマコーター、フィルムコーター等による適宜の方法を用いて行えばよい。
感光性樹脂膜30の厚さは、100μm以下が好ましく、より好ましくは5~50μmである。
工程(i)では、感光性レジストフィルム30Fを構成する感光性樹脂膜30の表面が、側壁20と、基板10とで形成される凹部15の開口面を塞ぐように、感光性レジストフィルム30Fを配置する。その後、前記感光性レジストフィルム30Fを構成する感光性樹脂膜30から、前記基材フィルムを剥離する。
図2において、感光性レジストフィルム30Fを構成する感光性樹脂膜30は、側壁20を介して基板10と対向するように配置される。そして、基板10と、側壁20と、感光性樹脂膜30とで囲まれた中空の密閉空間(キャビティ)が形成される。
工程(ii)では、感光性樹脂膜30を露光する。
例えば、感光性樹脂膜30に対し、公知の露光装置を用いて、所定のパターンが形成されたフォトマスク60を介した選択的露光を行う。
工程(iii)では、露光後の感光性樹脂膜30に対して加熱処理、いわゆるポストエクスポージャーベーク(PEB)処理を行う。
PEB処理は、例えば、80~150℃の温度条件にて40~600秒間、好ましくは60~300秒間で行う。
工程(iii)における加熱処理により、露光後の感光性樹脂膜30は、(A)成分中のエポキシ基が開環重合した露光部30Aと、変化のない未露光部30Bとなる。
工程(iv)では、PEB処理後の感光性樹脂膜30(露光部30A、未露光部30B)を現像してネガ型パターン(露光部30A)を形成する。
ここでの現像は、上述した[現像工程]と同様にして行うことができる。現像の後、好ましくはリンス処理を行う。
工程(iv)における現像により、未露光部30Bが溶解除去されて、ネガ型パターンとして天板部(壁部の開口面を塞ぐ屋根(Roof))となる露光部30Aが残像する。
工程(v)では、現像後のネガ型パターン(露光部30A)に対し、さらに加熱処理(キュア操作)を行うことにより硬化させて、天板部が感光性樹脂膜30の硬化体40からなる中空構造体100を得る。
図2において、硬化体40は、側壁20を形成する感光性樹脂材料と感光性樹脂膜30とがそれぞれ硬化して一体化している。
また、図2において、本実施形態に係る中空構造体100は、アルミニウム配線を有する基板10と、硬化体40とを有する。
本実施形態の中空パッケージの製造方法に用いるネガ型感光性組成物(以下単に「感光性組成物」ということがある)は、カチオン部とアニオン部とからなるカチオン重合開始剤(I)を含有する。
具体的に、本実施形態の中空パッケージの製造方法に用いるネガ型感光性組成物は、カチオン重合開始剤(I)と、樹脂としてエポキシ基含有化合物(A)とを含有している。 以下、カチオン重合開始剤(I)の成分を「(I)成分」、エポキシ基含有化合物(A)を「(A)成分」ともいう。
カチオン重合開始剤((I)成分)は、紫外線、遠紫外線、KrF、ArF等のエキシマレーザー光、X線、電子線等といった活性エネルギー線の照射を受けてカチオンを発生し、そのカチオンが重合開始剤となり得る化合物である。
「有機基」とは、炭素原子を含む基であり、炭素原子以外の原子(たとえば水素原子、酸素原子、窒素原子、硫黄原子、ハロゲン原子(フッ素原子、塩素原子等)等)を有していてもよい。
Rは、ハロゲン原子を含む1価の炭化水素基であることが好ましく、フッ素原子を含む1価の炭化水素基であることが特に好ましい。ハロゲン原子を含む炭化水素基としては、直鎖状、分岐鎖状または環状のいずれであってもよく、炭素数は1~15であることが好ましく、炭素数1~10であることがより好ましく、炭素数1~8が特に好ましい。
Rは、ハロゲン原子(フッ素原子、塩素原子等)を含まないものでもよい。
上記の中でも、(I1)成分及び(I2)成分は、いずれも、露光により比較的に強い酸を発生するため、(I)成分を含有する感光性組成物を用いてパターンを形成する場合に、充分な感度が得られて良好なパターンが形成される。
(I1)成分は、下記一般式(I1)で表される化合物である。
前記式(I1)中、Rb01~Rb04は、それぞれ独立に、置換基を有していてもよいアリール基、又はフッ素原子である。
Rb01~Rb04におけるアリール基は、炭素数が5~30であることが好ましく、5~20がより好ましく、6~15がさらに好ましく、6~12が特に好ましい。具体的には、ナフチル基、フェニル基、アントラセニル基などが挙げられ、入手が容易であることからフェニル基が好ましい。
Rb01~Rb04におけるアリール基は、置換基を有していてもよい。この置換基としては、特に限定されるものではないが、ハロゲン原子、水酸基、アルキル基(直鎖状又は分岐鎖状のアルキル基が好ましく、炭素数は1~5が好ましい)、ハロゲン化アルキル基が好ましく、ハロゲン原子又は炭素数1~5のハロゲン化アルキル基がより好ましく、フッ素原子又は炭素数1~5のフッ素化アルキル基が特に好ましい。アリール基がフッ素原子を有することにより、アニオン部の極性が高まり好ましい。
中でも、式(I1)のRb01~Rb04としては、それぞれ、フッ素化されたフェニル基が好ましく、パーフルオロフェニル基が特に好ましい。
テトラキス(ペンタフルオロフェニル)ボレート([B(C6F5)4]-);
テトラキス[(トリフルオロメチル)フェニル]ボレート([B(C6H4CF3)4]-);
ジフルオロビス(ペンタフルオロフェニル)ボレート([(C6F5)2BF2]-);テトラキス(ジフルオロフェニル)ボレート([B(C6H3F2)4]-)等が挙げられる。
中でも、テトラキス(ペンタフルオロフェニル)ボレート([B(C6F5)4]-)が特に好ましい。
上記アニオンのうち、ボランに直接結合するフッ素原子の個数が「0」のアニオン(([B(C6F5)4]-)、([B(C6H4CF3)4]-)、([B(C6H3F2)4]-)、([B(C6F5)4]-))において、フッ素原子の個数(m)と、置換基を有していてもよいフッ素化アルキル基の個数(k)と、の間の関係式である、m/(k+m)は0である。
上記アニオンのうち、ボランに直接結合するフッ素原子の個数が「2」のアニオン(([(C6F5)2BF2]-))において、式m/(k+m)は0.5である。
なお、ボランに直接結合するフッ素原子の個数が「3」のアニオン(([(C6F5)BF3]-))のような化合物の場合、式m/(k+m)は0.75となる。
式(I1)中、qは1以上の整数であって、Qq+は、それぞれ独立に、q価の有機カチオンである。
このQq+としては、スルホニウムカチオン、ヨードニウムカチオンが好適に挙げられ、下記の一般式(ca-1)~(ca-5)でそれぞれ表される有機カチオンが特に好ましい。
R201~R207、及びR211~R212におけるヘテロアリール基としては、前記アリール基を構成する炭素原子の一部がヘテロ原子で置換されたものが挙げられる。ヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。このヘテロアリール基として、9H-チオキサンテンから水素原子を1つ除いた基;置換ヘテロアリール基として、9H-チオキサンテン-9-オンから水素原子を1つ除いた基などが挙げられる。 R201~R207、及びR211~R212におけるアルキル基としては、鎖状又は環状のアルキル基であって、炭素数1~30のものが好ましい。
R201~R207、及びR211~R212におけるアルケニル基としては、炭素数が2~10であることが好ましい。
R201~R207、及びR210~R212が有していてもよい置換基としては、例えば、アルキル基、ハロゲン原子、ハロゲン化アルキル基、カルボニル基、シアノ基、アミノ基、オキソ基(=O)、アリール基、下記式(ca-r-1)~(ca-r-10)でそれぞれ表される基が挙げられる。
該環式基は、環状の炭化水素基であることが好ましく、該環状の炭化水素基は、芳香族炭化水素基であってもよく、環状の脂肪族炭化水素基であってもよい。脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。また、脂肪族炭化水素基は、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。
R’201における芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、フルオレン、ナフタレン、アントラセン、フェナントレン、ビフェニル、もしくはこれらの芳香環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環、又は、これらの芳香環もしくは芳香族複素環を構成する水素原子の一部がオキソ基などで置換された環が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
R’201における芳香族炭化水素基として具体的には、前記芳香環から水素原子を1つ除いた基(アリール基:例えば、フェニル基、ナフチル基、アントラセニル基など)、前記芳香環の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基など)、前記芳香環を構成する水素原子の一部がオキソ基などで置換された環(例えばアントラキノン等)から水素原子を1つ除いた基、芳香族複素環(例えば9H-チオキサンテン、9H-チオキサンテン-9-オンなど)から水素原子を1つ除いた基等が挙げられる。前記アルキレン基(アリールアルキル基中のアルキル鎖)の炭素数は、1~4であることが好ましく、1~2であることがより好ましく、1であることが特に好ましい。
この構造中に環を含む脂肪族炭化水素基としては、脂環式炭化水素基(脂肪族炭化水素環から水素原子を1個除いた基)、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。
前記脂環式炭化水素基は、炭素数が3~20であることが好ましく、3~12であることがより好ましい。
前記脂環式炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから1個以上の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから1個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素数7~30のものが好ましい。中でも、該ポリシクロアルカンとしては、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等の架橋環系の多環式骨格を有するポリシクロアルカン;ステロイド骨格を有する環式基等の縮合環系の多環式骨格を有するポリシクロアルカンがより好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基[-CH2-]、エチレン基[-(CH2)2-]、トリメチレン基[-(CH2)3-]、テトラメチレン基[-(CH2)4-]、ペンタメチレン基[-(CH2)5-]等が挙げられる。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等のアルキルエチレン基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素数1~5の直鎖状のアルキル基が好ましい。
R’201の鎖状のアルキル基としては、直鎖状又は分岐鎖状のいずれでもよい。
直鎖状のアルキル基としては、炭素数が1~20であることが好ましく、1~15であることがより好ましく、1~10が最も好ましい。具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デカニル基、ウンデシル基、ドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、イソヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基等が挙げられる。
分岐鎖状のアルキル基としては、炭素数が3~20であることが好ましく、3~15であることがより好ましく、3~10が最も好ましい。具体的には、例えば、1-メチルエチル基、1-メチルプロピル基、2-メチルプロピル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルブチル基、2-エチルブチル基、1-メチルペンチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基などが挙げられる。
R’201の鎖状のアルケニル基としては、直鎖状又は分岐鎖状のいずれでもよく、炭素数が2~10であることが好ましく、2~5がより好ましく、2~4がさらに好ましく、3が特に好ましい。直鎖状のアルケニル基としては、例えば、ビニル基、プロペニル基(アリル基)、ブチニル基などが挙げられる。分岐鎖状のアルケニル基としては、例えば、1-メチルビニル基、2-メチルビニル基、1-メチルプロペニル基、2-メチルプロペニル基などが挙げられる。
鎖状のアルケニル基としては、上記の中でも、直鎖状のアルケニル基が好ましく、ビニル基、プロペニル基がより好ましく、ビニル基が特に好ましい。
R210におけるアリール基としては、炭素数6~20の無置換のアリール基が挙げられ、フェニル基、ナフチル基が好ましい。
R210におけるアルキル基としては、鎖状又は環状のアルキル基であって、炭素数1~30のものが好ましい。
R210におけるアルケニル基としては、炭素数が2~10であることが好ましい。
Y201におけるアリーレン基は、R’201における芳香族炭化水素基として例示したアリール基から水素原子を1つ除いた基が挙げられる。
Y201におけるアルキレン基、アルケニレン基は、R’201における鎖状のアルキル基、鎖状のアルケニル基として例示した基から水素原子を1つ除いた基が挙げられる。
W201は、(x+1)価、すなわち2価または3価の連結基である。
W201における2価の連結基としては、置換基を有していてもよい2価の炭化水素基が好ましく、上記式(abp1)中のREPで例示した置換基を有していてもよい2価の炭化水素基と同様の基が好ましい。W201における2価の連結基は、直鎖状、分岐鎖状、環状のいずれであってもよく、環状であることが好ましい。なかでも、アリーレン基の両端に2個のカルボニル基が組み合わされた基、又はアリーレン基のみからなる基が好ましい。アリーレン基としては、フェニレン基、ナフチレン基等が挙げられ、フェニレン基が特に好ましい。
W201における3価の連結基としては、前記W201における2価の連結基から水素原子を1個除いた基、前記2価の連結基にさらに前記2価の連結基が結合した基などが挙げられる。W201における3価の連結基としては、アリーレン基に2個のカルボニル基が結合した基が好ましい。
具体例で示す化合物のアニオンにおいて、フッ素原子の個数(m)と、置換基を有していてもよいアリール基の個数(k)と、の間の関係式である、m/(k+m)はいずれも0である。
(I2)成分は、下記一般式(I2)で表される化合物である。
前記式(I2)中、Rb05は、置換基を有していてもよいフッ素化アルキル基、又はフッ素原子である。複数のRb05は、互いに同一であってもよく異なっていてもよい。 Rb05におけるフッ素化アルキル基は、炭素数が1~10であることが好ましく、1~8がより好ましく、1~5がさらに好ましい。具体的には、炭素数1~5のアルキル基において、水素原子の一部又は全部がフッ素原子で置換された基が挙げられる。
中でも、Rb05としては、フッ素原子又は炭素数1~5のフッ素化アルキル基が好ましく、フッ素原子又は炭素数1~5のパーフルオロアルキル基がより好ましく、フッ素原子、トリフルオロメチル基又はペンタフルオロエチル基がさらに好ましい。
中でも、Rbf05としては、炭素数1~5のフッ素化アルキル基が好ましく、炭素数1~5のパーフルオロアルキル基がより好ましく、トリフルオロメチル基又はペンタフルオロエチル基がさらに好ましい。
式(b0-2a)中、nb1は、2~4の整数が好ましく、3が最も好ましい。
(CF3CF2)2PF4 -、(CF3CF2)3PF3 -、((CF3)2CF)2PF4 -、((CF3)2CF)3PF3 -、(CF3CF2CF2)2PF4 -、(CF3CF2CF2)3PF3 -、((CF3)2CFCF2)2PF4 -、((CF3)2CFCF2)3PF3 -、(CF3CF2CF2CF2)2PF4 -及び(CF3CF2CF2CF2)3PF3 -で表されるアニオン等が挙げられる。
中でも、((CF3)2CF)3PF3 -が好ましい。
上記アニオンのうち、上記一般式(b0-2a)中のnb1が「2」であるアニオンにおいて、フッ素原子の個数(m)と、置換基を有していてもよいフッ素化アルキル基の個数(k)と、の間の関係式である、m/(k+m)は0.667である。
上記アニオンのうち、上記一般式(b0-2a)中のnb1が「3」であるアニオンにおいて、m/(k+m)は0.5である。
式(I2)中、qは1以上の整数であって、Qq+は、それぞれ独立に、q価の有機カチオンである。
このQq+としては、上記式(I1)と同様のものが挙げられ、その中でも、一般式(ca-1)で表されるカチオンが好ましく、式(ca-1-1)~(ca-1-47)でそれぞれ表されるカチオンがより好ましく、式(ca-1-35)、式(ca-1-47)でそれぞれ表されるカチオンがさらに好ましい。
具体例で示す化合物のアニオンにおいて、フッ素原子の個数(m)と、置換基を有していてもよいフッ素化アルキル基の個数(k)と、の間の関係式である、m/(k+m)は0.5である。
(I)成分の含有量が、前記の好ましい範囲の下限値以上であると、中空パッケージを構成するアルミニウム配線の腐食を充分に抑制することができる。また、充分な感度が得られて、パターンのリソグラフィー特性がより向上する。加えて、硬化膜の強度がより高められる。一方、前記の好ましい範囲の上限値以下であると、感度が適度に制御され、良好な形状のパターンが得られやすくなる。
(I3)成分は、下記一般式(I3-1)又は(I3-2)で表される化合物である。
・アニオン部
式(I3-1)中、Rb12は、ハロゲン原子以外の置換基を有していてもよい環式基、ハロゲン原子以外の置換基を有していてもよい鎖状のアルキル基、又はハロゲン原子以外の置換基を有していてもよい鎖状のアルケニル基であって、上述したR’201の説明中の環式基、鎖状のアルキル基、鎖状のアルケニル基のうち、置換基を有しないもの又はハロゲン原子以外の置換基を有するものが挙げられる。
Rb12としては、ハロゲン原子以外の置換基を有していてもよい鎖状のアルキル基、又はハロゲン原子以外の置換基を有していてもよい脂肪族環式基であることが好ましい。鎖状のアルキル基としては、炭素数1~10であることが好ましく、3~10であることがより好ましい。脂肪族環式基としては、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等から1個以上の水素原子を除いた基(ハロゲン原子以外の置換基を有していてもよい);カンファー等から1個以上の水素原子を除いた基であることがより好ましい。
Rb12の炭化水素基はハロゲン原子以外の置換基を有していてもよく、該置換基としては、前記式(I3-2)のRb11における炭化水素基(芳香族炭化水素基、脂肪族環式基、鎖状のアルキル基)が有していてもよいハロゲン原子以外の置換基と同様のものが挙げられる。
ここでいう「ハロゲン原子以外の置換基を有していてもよい」とは、ハロゲン原子のみからなる置換基を有する場合を排除するのみではなく、ハロゲン原子を1つでも含む置換基を有する場合(例えば、置換基がフッ素化アルキル基である場合等)を排除するものである。
式(I3-1)中、Mm+は、m価の有機カチオンである。
Mm+の有機カチオンとしては、上記一般式(ca-1)~(ca-5)でそれぞれ表されるカチオンと同様のものが好適に挙げられ、これらの中でも、上記一般式(ca-1)で表されるカチオンがより好ましい。この中でも、上記一般式(ca-1)中のR201、R202、R203のうちの少なくとも1つが、置換基を有していてもよい炭素数16以上の有機基(アリール基、ヘテロアリール基、アルキル基またはアルケニル基)であるスルホニウムカチオンが、解像性やラフネス特性が向上することから特に好ましい。 前記の有機基が有していてもよい置換基としては、上記と同様であり、アルキル基、ハロゲン原子、ハロゲン化アルキル基、カルボニル基、シアノ基、アミノ基、オキソ基(=O)、アリール基、上記式(ca-r-1)~(ca-r-10)でそれぞれ表される基が挙げられる。
前記の有機基(アリール基、ヘテロアリール基、アルキル基またはアルケニル基)における炭素数は、好ましくは16~25、より好ましくは16~20であり、特に好ましくは16~18であり、かかるMm+の有機カチオンとしては、例えば、上記式(ca-1-25)、(ca-1-26)、(ca-1-28)~(ca-1-36)、(ca-1-38)、(ca-1-46)、(ca-1-47)でそれぞれ表されるカチオンが好適に挙げられ、その中でも、上記式(ca-1-29)で表されるカチオンが特に好ましい。
・アニオン部
式(I3-2)中、Rb11は、ハロゲン原子以外の置換基を有していてもよい環式基、ハロゲン原子以外の置換基を有していてもよい鎖状のアルキル基、又はハロゲン原子以外の置換基を有していてもよい鎖状のアルケニル基であって、上述したR’201の説明中の環式基、鎖状のアルキル基、鎖状のアルケニル基のうち、置換基を有しないもの又はハロゲン原子以外の置換基を有するものが挙げられる。
エーテル結合やエステル結合を置換基として含む場合、アルキレン基を介していてもよく、この場合の置換基としては、下記一般式(y-al-1)~(y-al-7)でそれぞれ表される連結基が好ましい。
V’101及びV’102におけるアルキレン基として、具体的には、メチレン基[-CH2-];-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;エチレン基[-CH2CH2-];-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-等のアルキルエチレン基;トリメチレン基(n-プロピレン基)[-CH2CH2CH2-];-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;テトラメチレン基[-CH2CH2CH2CH2-];-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基;ペンタメチレン基[-CH2CH2CH2CH2CH2-]等が挙げられる。
また、V’101又はV’102における前記アルキレン基における一部のメチレン基が、炭素数5~10の2価の脂肪族環式基で置換されていてもよい。当該脂肪族環式基は、R’201の環状の脂肪族炭化水素基(単環式の脂環式炭化水素基、多環式の脂環式炭化水素基)から水素原子をさらに1つ除いた2価の基が好ましく、シクロへキシレン基、1,5-アダマンチレン基又は2,6-アダマンチレン基がより好ましい。
前記脂肪族環式基としては、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等のポリシクロアルカンから1個以上の水素原子を除いた基であることがより好ましい。
前記鎖状のアルキル基としては、炭素数が1~10であることが好ましく、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の直鎖状のアルキル基;1-メチルエチル基、1-メチルプロピル基、2-メチルプロピル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルブチル基、2-エチルブチル基、1-メチルペンチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基等の分岐鎖状のアルキル基が挙げられる。
式(I3-2)中、Mm+は、m価の有機カチオンであり、前記式(I3-1)中のMm+と同様である。
ここで「pKa(酸解離定数)」とは、対象物質の酸強度を示す指標として一般的に用いられているものをいう。なお、本明細書におけるpKaは、25℃の温度条件における値である。また、pKa値は、公知の手法により測定して求めることができる。また、「ACD/Labs」(商品名、Advanced Chemistry Development社製)等の公知のソフトウェアを用いた計算値を用いることもできる。
本実施形態の感光性組成物で用いられるエポキシ基含有化合物((A)成分)は、下記一般式(A1)で表される化合物(以下「(A1)成分」という)と、下記一般式(A2)で表される化合物(以下「(A2)成分」という)を含んでもよい。
(A1)成分としては、例えば、下記一般式(abp1)で表される構造のエポキシ樹脂が挙げられる。
REPのエポキシ基含有基としては、特に限定されるものではなく、エポキシ基のみからなる基;脂環式エポキシ基のみからなる基;エポキシ基又は脂環式エポキシ基と、2価の連結基とを有する基が挙げられる。
脂環式エポキシ基とは、3員環エーテルであるオキサシクロプロパン構造を有する脂環式基であって、具体的には、脂環式基とオキサシクロプロパン構造とを有する基である。 脂環式エポキシ基の基本骨格となる脂環式基としては、単環でも多環でもよい。単環の脂環式基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。また、多環の脂環式基としては、ノルボルニル基、イソボルニル基、トリシクロノニル基、トリシクロデシル基、テトラシクロドデシル基等が挙げられる。また、これら脂環式基の水素原子は、アルキル基、アルコキシ基、水酸基等で置換されてもよい。
エポキシ基又は脂環式エポキシ基と、2価の連結基とを有する基の場合、式中の酸素原子(-O-)に結合した2価の連結基を介してエポキシ基又は脂環式エポキシ基が結合することが好ましい。
かかる2価の炭化水素基は、脂肪族炭化水素基でもよく、芳香族炭化水素基でもよい。 2価の炭化水素基における脂肪族炭化水素基は、飽和でもよく、不飽和でもよく、通常は飽和であることが好ましい。
該脂肪族炭化水素基として、より具体的には、直鎖状若しくは分岐鎖状の脂肪族炭化水素基、又は構造中に環を含む脂肪族炭化水素基等が挙げられる。
前記分岐鎖状の脂肪族炭化水素基は、炭素数が2~10であることが好ましく、2~6がより好ましく、2~4がさらに好ましく、2又は3が最も好ましい。分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等のアルキルエチレン基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素数1~5の直鎖状のアルキル基が好ましい。
前記脂環式炭化水素基は、炭素数が3~20であることが好ましく、3~12であることがより好ましい。
前記脂環式炭化水素基は、多環式基でもよく、単環式基でもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから2個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式の脂環式炭化水素基としては、ポリシクロアルカンから2個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素数7~12のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等が挙げられる。
芳香族炭化水素基として具体的には、前記芳香族炭化水素環または芳香族複素環から水素原子を2つ除いた基(アリーレン基またはヘテロアリーレン基);2以上の芳香環を含む芳香族化合物(例えばビフェニル、フルオレン等)から水素原子を2つ除いた基;前記芳香族炭化水素環または芳香族複素環から水素原子を1つ除いた基(アリール基またはヘテロアリール基)の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基におけるアリール基から水素原子をさらに1つ除いた基)等が挙げられる。前記アリール基またはヘテロアリール基に結合するアルキレン基の炭素数は、1~4であることが好ましく、1~2であることがより好ましく、1であることが特に好ましい。
2価の炭化水素基としての、直鎖状または分岐鎖状の脂肪族炭化水素基は、置換基を有してもよく、有していなくてもよい。該置換基としては、フッ素原子、フッ素原子で置換された炭素数1~5のフッ素化アルキル基、カルボニル基等が挙げられる。
前記置換基としてのアルキル基としては、炭素数1~5のアルキル基が好ましく、メチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基であることが最も好ましい。
前記置換基としてのアルコキシ基としては、炭素数1~5のアルコキシ基が好ましく、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基、tert-ブトキシ基が好ましく、メトキシ基、エトキシ基が最も好ましい。
前記置換基としてのハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。
前記置換基としてのハロゲン化アルキル基としては、前記アルキル基の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。
脂環式炭化水素基は、その環構造を構成する炭素原子の一部がヘテロ原子を含む置換基で置換されてもよい。該ヘテロ原子を含む置換基としては、-O-、-C(=O)-O-、-S-、-S(=O)2-、-S(=O)2-O-が好ましい。
前記置換基としてのアルキル基としては、炭素数1~5のアルキル基が好ましく、メチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基であることが最も好ましい。
前記置換基としてのアルコキシ基、ハロゲン原子及びハロゲン化アルキル基としては、前記脂環式炭化水素基が有する水素原子を置換する置換基として例示したものが挙げられる。
ヘテロ原子を含む2価の連結基におけるヘテロ原子とは、炭素原子及び水素原子以外の原子であり、例えば酸素原子、窒素原子、硫黄原子、ハロゲン原子等が挙げられる。
前記へテロ原子を含む2価の連結基が-C(=O)-NH-、-NH-、-NH-C(=O)-O-、-NH-C(=NH)-の場合、そのHはアルキル基、アシル等の置換基で置換されてもよい。該置換基(アルキル基、アシル基等)は、炭素数が1~10であることが好ましく、1~8であることがさらに好ましく、1~5であることが特に好ましい。
式-Y21-O-Y22-、-Y21-O-、-Y21-C(=O)-O-、-C(=O)-O-Y21-、-[Y21-C(=O)-O]m”-Y22-または-Y21-O-C(=O)-Y22-中、Y21及びY22は、それぞれ独立して、置換基を有してもよい2価の炭化水素基である。該2価の炭化水素基としては、上述した2価の連結基としての説明で挙げた「置換基を有してもよい2価の炭化水素基」と同様のものが挙げられる。
Y21としては、直鎖状の脂肪族炭化水素基が好ましく、直鎖状のアルキレン基がより好ましく、炭素数1~5の直鎖状のアルキレン基がさらに好ましく、メチレン基またはエチレン基が特に好ましい。
Y22としては、直鎖状または分岐鎖状の脂肪族炭化水素基が好ましく、メチレン基、エチレン基またはアルキルメチレン基がより好ましい。該アルキルメチレン基におけるアルキル基は、炭素数1~5の直鎖状のアルキル基が好ましく、炭素数1~3の直鎖状のアルキル基がより好ましく、メチル基が最も好ましい。
式-[Y21-C(=O)-O]m”-Y22-で表される基において、m”は0~3の整数であり、0~2の整数であることが好ましく、0または1がより好ましく、1が特に好ましい。つまり、式-[Y21-C(=O)-O]m”-Y22-で表される基としては、式-Y21-C(=O)-O-Y22-で表される基が特に好ましい。なかでも、式-(CH2)a’-C(=O)-O-(CH2)b’-で表される基が好ましい。該式中、a’は、1~10の整数であり、1~8の整数が好ましく、1~5の整数がより好ましく、1または2がさらに好ましく、1が最も好ましい。b’は、1~10の整数であり、1~8の整数が好ましく、1~5の整数がより好ましく、1または2がさらに好ましく、1が最も好ましい。
Ra31、Ra32の炭素数1~5のアルキル基は、例えば炭素数1~5の直鎖状、分岐鎖状、又は環状のアルキル基である。直鎖状又は分岐鎖状のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられ、環状のアルキル基としては、シクロブチル基、シクロペンチル基等が挙げられる。
なかでもRa31、Ra32としては、水素原子又は直鎖状もしくは分岐鎖状のアルキル基が好ましく、水素原子又は直鎖状のアルキル基がより好ましく、水素原子又はメチル基がさらに好ましい。
前記式(a1-01)中及び前記式(a1-02)中、na31はそれぞれ、4~50の整数であり、好ましくは4~15の整数であり、より好ましくは5~8の整数である。
モールド耐性をより高められやすい点から、上記一般式(a1-02)で表される構造のエポキシ樹脂が好ましい。
本実施形態の感光性組成物中、(A1)成分の含有量は、(A)成分の総質量(100質量%)に対して、60~100質量部であり、70~100質量部であることが好ましく、50~100質量部であることがより好ましい。
(A2)成分は、エポキシ当量が前記(A1)成分より小さい下記一般式(A2-1)で表されるエポキシ樹脂である。すなわち、(A2)成分には、ノボラック型エポキシ樹脂(Anv)を用いる。
(A2)成分は、前記(A1)成分におけるエポキシ当量より相対的にエポキシ当量が小さいものであればよい。
式(A2-1)中、複数のRp1は、互いに同一でもよく異なってもよい。複数のRp2は、互いに同一でもよく異なってもよい。
本実施形態の感光性組成物中、(A2)成分の含有量は、(A)成分の総質量(100質量%)に対して、15~60質量%であり、20~55質量%であることが好ましく、25~50質量%であることがより好ましい。
本実施形態の感光性組成物において、(A)成分は、(A1)成分及び(A2)成分に加えて、これら以外のエポキシ基含有化合物(以下これを「(A3)成分」ともいう。)を含んでもよい。
式(anv1)中、REPは、前記式(abp1)中のREPと同様であって、グリシジル基が好ましい。
該直鎖状のアルキル基は、炭素数が1~5であることが好ましく、1~4がより好ましく、1または2がさらに好ましい。具体的には、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基等が挙げられる。これらの中でも、メチル基、エチル基またはn-ブチル基が好ましく、メチル基またはエチル基がより好ましい。
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから1個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから1個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素数7~12のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等が挙げられる。
この芳香環は、4n+2個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素数は5~30であることが好ましく、5~20がより好ましく、6~15がさらに好ましく、6~12が特に好ましい。芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環;前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
Ra24における芳香族炭化水素基として具体的には、前記芳香族炭化水素環または芳香族複素環から水素原子を1つ除いた基(アリール基またはヘテロアリール基);2以上の芳香環を含む芳香族化合物(例えばビフェニル、フルオレン等)から水素原子を1つ除いた基;前記芳香族炭化水素環または芳香族複素環の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基など)等が挙げられる。前記芳香族炭化水素環または芳香族複素環に結合するアルキレン基の炭素数は、1~4であることが好ましく、1~2であることがより好ましく、1であることが特に好ましい。
かかる脂肪族エポキシ樹脂、アクリル樹脂(Aac)としては、例えば、下記一般式(a1-1)~(a1-2)でそれぞれ表されるエポキシ基含有単位を有する樹脂が挙げられる。
Rの炭素数1~5のアルキル基は、直鎖状または分岐鎖状が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。
Rの炭素数1~5のハロゲン化アルキル基は、前記炭素数1~5のアルキル基の水素原子の一部または全部がハロゲン原子で置換された基である。該ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、特にフッ素原子が好ましい。 Rとしては、水素原子、炭素数1~5のアルキル基又は炭素数1~5のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子又はメチル基が最も好ましい。
上記の中でも、Va41の炭化水素基は、脂肪族炭化水素基が好ましく、直鎖状または分岐鎖状の脂肪族炭化水素基がより好ましく、直鎖状の脂肪族炭化水素基がさらに好ましく、直鎖状のアルキレン基が特に好ましい。
Ra51は、炭素数1~8の2価の炭化水素基を示す。Ra52は、炭素数1~20の2価の炭化水素基を示す。Ra53は、水素原子又はメチル基を示す。na51は、0~10の整数である。
Ra51、Ra52、Ra53は、それぞれ同一であっても異なっていてもよい。
このような重合性化合物としては、公知のラジカル重合性化合物や、アニオン重合性化合物が挙げられる。このような重合性化合物としては、例えば、アクリル酸、メタクリル酸、クロトン酸等のモノカルボン酸類;マレイン酸、フマル酸、イタコン酸等のジカルボン酸類;2-メタクリロイルオキシエチルコハク酸、2-メタクリロイルオキシエチルマレイン酸、2-メタクリロイルオキシエチルフタル酸、2-メタクリロイルオキシエチルヘキサヒドロフタル酸等のカルボキシル基及びエステル結合を有するメタクリル酸誘導体類;メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート等の(メタ)アクリル酸アルキルエステル類;2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキルエステル類;フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート等の(メタ)アクリル酸アリールエステル類;マレイン酸ジエチル、フマル酸ジブチル等のジカルボン酸ジエステル類;スチレン、α-メチルスチレン、クロロスチレン、クロロメチルスチレン、ビニルトルエン、ヒドロキシスチレン、α-メチルヒドロキシスチレン、α-エチルヒドロキシスチレン等のビニル基含有芳香族化合物類;酢酸ビニル等のビニル基含有脂肪族化合物類;ブタジエン、イソプレン等の共役ジオレフィン類;アクリロニトリル、メタクリロニトリル等のニトリル基含有重合性化合物類;塩化ビニル、塩化ビニリデン等の塩素含有重合性化合物;アクリルアミド、メタクリルアミド等のアミド結合含有重合性化合物類;等が挙げられる。
ここでの2価の連結基としては、特に限定されないが、置換基を有していてもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基等が好適なものとして挙げられる。置換基を有していてもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基については、上記式(abp1)中のREP(エポキシ基含有基)において説明した、置換基を有していてもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基と同様であり、この中でもヘテロ原子を含む2価の連結基が好ましく、-Y21-C(=O)-O-で表される基、-C(=O)-O-Y21-で表される基がより好ましい。Y21としては、直鎖状の脂肪族炭化水素基が好ましく、直鎖状のアルキレン基がより好ましく、炭素数1~5の直鎖状のアルキレン基がさらに好ましく、メチレン基またはエチレン基が特に好ましい。
例えば、本実施形態の感光性組成物中、(A)成分の含有量は、感光性組成物の総質量(100質量%)に対して、80質量%以上が好ましく、90質量%以上がより好ましく、95質量%以上がさらに好ましく、97質量%以上が特に好ましい。
本実施形態の感光性組成物中、(A1)成分及び(A2)成分を混合して用いる場合、25質量部:75質量部~75質量部:25質量部の割合で含むことが好ましい。または、(A1)成分を2種用いる場合、本実施形態の感光性組成物中、50質量部:50質量部で含むことが好ましい。
本実施形態の中空パッケージの製造方法に用いる感光性組成物は、上述した(A)成分及び(I)成分以外に、必要に応じてその他成分を含有してもよい。
本実施形態の中空パッケージの製造方法に用いる感光性組成物には、所望により、混和性のある添加剤、例えば金属酸化物(M)、シランカップリング剤、増感剤成分、溶剤、膜の性能を改良するための付加的樹脂、溶解抑制剤、塩基性化合物、可塑剤、安定剤、着色剤、ハレーション防止剤などを適宜、添加含有させることができる。
本実施形態の中空パッケージの製造方法に用いる感光性組成物は、(A)成分及び(I)成分に加えて、強度が高められた硬化膜が得られやすいことから、さらに、金属酸化物(M)(以下「(M)成分」ともいう)を含有してもよい。また、(M)成分を併有することで、良好な形状で高解像のパターンを形成し得る。
(M)成分としては、例えば、ケイ素(金属ケイ素)、チタン、ジルコニウム、ハフニウム等の金属の酸化物が挙げられる。これらの中でも、ケイ素の酸化物が好ましく、この中でもシリカを用いることが特に好ましい。
かかる粒子状の(M)成分としては、体積平均粒子径が5~40nmの粒子群からなるものが好ましく、体積平均粒子径が5~30nmの粒子群からなるものがより好ましく、体積平均粒子径が10~20nmの粒子群からなるものがさらに好ましい。
(M)成分の体積平均粒子径が、前記の好ましい範囲の下限値以上であると、硬化膜の強度が高められやすくなる。一方、前記の好ましい範囲の上限値以下であると、パターンの形成において、残渣が生じにくくなり、より高解像のパターンが形成されやすくなる。加えて、樹脂膜の透明性が高められる。
(M)成分の粒子径は、露光光源に応じて適宜選択すればよい。一般的に、光の波長に対して、1/10以下の粒子径を持つ粒子は、光散乱の影響はほぼ考えなくてよいとされている。このため、例えばi線(365nm)でのフォトリソグラフィーにより微細構造を形成する場合、(M)成分としては、1次粒子径(体積平均値)10~20nmの粒子群(特に好ましくはシリカ粒子群)を用いることが好ましい。
(M)成分を含む場合の含有量は、(A)成分100質量部に対して、5~50質量部であることが好ましく、10~40質量部であることがより好ましい。
(M)成分の含有量が、前記の好ましい範囲の下限値以上であると、硬化膜の強度がより高められる。一方、前記の好ましい範囲の上限値以下であると、樹脂膜の透明性がより高められる。
本実施形態の中空パッケージの製造方法に用いる感光性組成物は、基板との接着性を向上させるため、さらに接着助剤を含有していてもよい。この接着助剤としては、シランカップリング剤が好ましい。
シランカップリング剤としては、例えばカルボキシ基、メタクリロイル基、イソシアナート基、エポキシ基等の反応性置換基を有するシランカップリング剤が挙げられる。具体例としては、トリメトキシシリル安息香酸、γ-メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等が挙げられる。
シランカップリング剤は、1種を単独で用いてもよく、2種以上を併用してもよい。 シランカップリング剤を含む場合の含有量は、(A)成分100質量部に対して、0.1~20質量部であることが好ましく、0.3~15質量部であることがより好ましく、0.5~10質量部であることがさらに好ましい。
シランカップリング剤の含有量が、前記の好ましい範囲であると、硬化膜の強度がより高められる。加えて、硬化膜と基板との接着性がより強められる。
本実施形態の中空パッケージの製造方法に用いる感光性組成物は、さらに、増感剤成分を含有してもよい。
増感剤成分としては、露光によるエネルギーを吸収して、そのエネルギーを他の物質に伝達し得るものであれば特に限定されるものではない。
増感剤成分として具体的には、ベンゾフェノン、p,p’-テトラメチルジアミノベンゾフェノン等のベンゾフェノン系光増感剤、カルバゾール系光増感剤、アセトフェン系光増感剤、1,5-ジヒドロキシナフタレン等のナフタレン系光増感剤、フェノール系光増感剤、9-エトキシアントラセン等のアントラセン系光増感剤、ビアセチル、エオシン、ローズベンガル、ピレン、フェノチアジン、アントロン等の公知の光増感剤を用いることができる。
増感剤成分は、1種を単独で用いてもよく、2種以上を併用してもよい。
増感剤成分を含む場合の含有量は、(A)成分100質量部に対して、0.1~15質量部であることが好ましく、0.3~10質量部であることがより好ましく、0.5~5質量部であることがさらに好ましい。
増感剤成分の含有量が前記の好ましい範囲であると、感度及び解像性がより高められる。
本実施形態の中空パッケージの製造方法に用いる感光性組成物は、さらに、溶剤(以下「(S)成分」ということがある)を含有してもよい。
(S)成分としては、例えば、γ-ブチロラクトン等のラクトン類;アセトン、メチルエチルケトン(MEK)、シクロヘキサノン、メチル-n-ペンチルケトン、メチルイソペンチルケトン、2-ヘプタノンなどのケトン類;エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコールなどの多価アルコール類;2-メトキシブチルアセテート、3-メトキシブチルアセテート、4-メトキシブチルアセテート、エチレングリコールモノアセテート、ジエチレングリコールモノアセテート、プロピレングリコールモノアセテート、またはジプロピレングリコールモノアセテート等のエステル結合を有する化合物、前記多価アルコール類または前記エステル結合を有する化合物のモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテル等のモノアルキルエーテルまたはモノフェニルエーテル等のエーテル結合を有する化合物等の多価アルコール類の誘導体[これらの中では、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、プロピレングリコールモノメチルエーテル(PGME)が好ましい];ジオキサンのような環式エーテル類や、乳酸メチル、乳酸エチル(EL)、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチルなどのエステル類;アニソール、エチルベンジルエーテル、クレジルメチルエーテル、ジフェニルエーテル、ジベンジルエーテル、フェネトール、ブチルフェニルエーテル、エチルベンゼン、ジエチルベンゼン、ペンチルベンゼン、イソプロピルベンゼン、トルエン、キシレン、シメン、メシチレン等の芳香族系有機溶剤、ジメチルスルホキシド(DMSO)等が挙げられる。
(S)成分は、1種を単独で用いてもよく、2種以上の混合溶剤として用いてもよい。
たとえば、固形分濃度が50質量%以上となるように(S)成分を使用することができ、60質量%以上となるように(S)成分を使用することができる。
また、(S)成分を実質的に含まない態様(すなわち、固形分濃度が100質量%である態様)も採用できる。
上述した本実施形態の製造方法により製造される中空パッケージが備える中空構造体は、上記一般式(I1-an)で表されるアニオンを含む感光性組成物により形成されている。上記一般式(I1-an)中、m/(k+m)は、0以上0.7未満である。
(I)成分のアニオンにおいて、ヘテロ原子(式中のA)に直接結合しているハロゲン原子は、容易に遊離する。これに対して、本実施形態では、中空構造体を形成する際に、そのようなヘテロ原子(式中のA)に直接結合しているハロゲン原子が少ないか、又は無いアニオンを含有する(I)成分を用いることで、ハロゲン原子が遊離する量を低減することができる。
上述の実施形態において、第1工程と、第2工程と、を有する中空パッケージの製造方法について説明したが、任意工程として、封止材により封止して中空パッケージを得る工程(第3工程)をさらに有してもよい。
封止材は、樹脂に加えて、フィラー等の他の成分を含んでいてもよい。
前記封止材層は、外部環境から中空構造体内のMEMSや配線部位等を保護する機能を有する。
本実施形態の感光性組成物の提供方法は、上述した中空パッケージの製造方法を実行するプロセスラインに対し、感光性組成物を提供する。
ここでの感光性組成物は、上述した材料の中から適宜選択して調製したものであればよく、プロセスラインの大きさ、稼働スピードに応じて感光性組成物の調製タイミングを図ればよい。
また、中空パッケージの製造方法を実行する事業主体と、本提供方法を実行する事業主体は必ずしも同一である必要はない。
(調製例1~5)
表1に示す各成分を混合して溶解し、PTFEフィルター(孔径1μm、PALL社製)を用いて濾過を行い、各調製例のネガ型感光性組成物(固形分が約84質量%のMEK溶液)をそれぞれ調製した。
(A1)-1:下記一般式(A1-1)で表されるエポキシ基含有樹脂。商品名「EPICLON1055」、DIC製。
(I1)-2:下記化学式(I1-2)で表されるカチオン重合開始剤。m/(k+m)は、0である。
(I1)-3:下記化学式(I1-3)で表されるカチオン重合開始剤。[2-tert-ブチル-5-メチル-4-(2-チオキサントニルチオ)フェニル](5-tert-ブチル-2-メチルフェニル)(2-チオキサントニル)スルホニウムテトラキス(ペンタフルオロフェニル)ボレート。m/(k+m)は、0である。
(I1)-4:下記化学式(I1-4)で表されるカチオン重合開始剤。m/(k+m)は、1である。
(D)-1:増感剤。αナフトール。
(試験例1~5)
基材フィルムとして、シリコーン系表面離型処理PETフィルム(商品名「A53」、帝人株式会社製)を用いた。
上述した各調製例のネガ型感光性組成物を、前記基材フィルム上に、アプリケーターを用いて塗布し、オーブンにて70℃、10分間でベーク処理(PAB)を行うことにより、感光性樹脂膜を形成して、感光性レジストフィルムを得た。
上記レジストフィルムに、10000mJ/cm2の照射量でghi線を照射した。基材フィルムを剥離し、オーブンにて加熱処理を行うことにより硬化させ、硬化物を得た。
各例のネガ型感光性組成物を用いて、フッ素イオン流出量の評価を行った。
蓋つきのPTFE樹脂容器に、上述した調製例1~5のネガ型感光性組成物を用いて作製したそれぞれの硬化物4g、及び、抽出溶媒として純水40gを入れ、蓋をした。ステンレス製オートクレーブに、前記の蓋をしたPTFE樹脂容器を格納し、120℃のオーブン中で、20時間処理した。室温に冷却後、抽出液を採取し、イオンクロマトグラフィーにより、フッ素イオン流出量を定量した。測定結果を表2に示す。
かかる試験例1~4によれば、フッ素の流出を抑制するのに有効なネガ型感光性組成物を用いた硬化物を提供することができることが確認できた。
(実施例1~6、比較例1~2)
基材フィルムとして、シリコーン系表面離型処理PETフィルム(商品名「A53」、帝人株式会社製)を用いた。
[第1工程]:S1
下記の膜形成工程、露光工程、及び現像工程により、アルミニウム配線を有する基板上に、前記アルミニウム配線を囲む側壁を形成した。
まず、アルミニウム蒸着基板を作製するために、シリコンウェーハ上に、金属薄膜形成装置PMC800-2MS(シンクロン社製)を用いて、膜厚150nmのアルミニウム層(Al層)を形成し、支持体を得た。
調製例1のネガ型感光性組成物を、前記支持体上に、アプリケーターを用いて塗布し、前記基材フィルム上に、アプリケーターを用いて塗布し、オーブンにて70℃、10分間でベーク処理(PAB)を行うことにより、膜厚20μmの感光性樹脂膜を形成して、感光性レジストフィルムを得た。
該20μmの膜厚を有する感光性樹脂膜に接する基材フィルムを剥離し、Canon PLA-501 ghi線 アライナーを用い、該感光性樹脂膜に、300mJ/cm2の照射量でghi線を照射した。その後、90℃のホットプレート上で、5分間の加熱処理を行った。
加熱処理後の感光性樹脂膜を、現像液としてプロピレングリコールモノメチルエーテルアセテートを用いて23℃でパドル現像することにより、側壁となるネガ型パターンをシリコンウェーハ上に形成した。
下記の工程(0)~工程(v)により、側壁上に、天板部を形成して、アルミニウム配線を収容する中空構造体を作製した。
まず、上記第1工程で得られた、側壁を有するアルミニウム蒸着基板を用意した。
調製例1のネガ型感光性組成物を、前記基材フィルム上に、アプリケーターを用いて塗布し、前記基材フィルム上に、アプリケーターを用いて塗布し、オーブンにて70℃、10分間でベーク処理(PAB)を行うことにより、膜厚45μmの感光性樹脂膜を形成して、感光性レジストフィルムを得た。
感光性レジストフィルムの感光性樹脂膜表面が、側壁を有する基板における前記側壁の開口面を塞ぐように、45μmの膜厚を有する感光性レジストフィルムを配置した。
その後、前記感光性レジストフィルムの感光性樹脂膜から前記基材フィルムを剥離する操作を行った。
次いで、Canon PLA-501 ghi線 アライナーを用い、該感光性樹脂膜に、300mJ/cm2の照射量でghi線を照射した。
前記工程(ii)における露光後の感光性樹脂膜に対し、90℃のホットプレート上で、5分間の加熱処理を行った。
前記工程(iii)における加熱処理後の感光性樹脂膜を、現像液としてプロピレングリコールモノメチルエーテルアセテートを用いて23℃でパドル現像することにより、天板部となるネガ型パターンを形成した。
前記工程(iv)後の前記ネガ型パターンに対し、さらに、オーブンにて加熱処理を行うことにより硬化させて、天板部が調製例1のネガ型感光性組成物からなる感光性樹脂膜の硬化体からなる中空構造体を得た。
調製例1のネガ型感光性組成物を、調製例2のネガ型感光性組成物へ変更した以外は、実施例1と同様にして中空構造体を得た。
側壁に用いた調製例1のネガ型感光性組成物を、調製例3のネガ型感光性組成物へ変更し、天板部に用いた調製例1のネガ型感光性組成物を、調製例4のネガ型感光性組成物へ変更した以外は、実施例1と同様にして中空構造体を得た。
調製例1のネガ型感光性組成物を、調製例5のネガ型感光性組成物へ変更した以外は、実施例1と同様にして中空構造体を得た。
シリコンウェーハ上に形成したアルミニウム層を、アルミニウム1%銅合金層(AlCu層)へ変更した以外は、実施例1と同様にして中空構造体を得た。
調製例1のネガ型感光性組成物を、調製例2のネガ型感光性組成物へ変更し、シリコンウェーハ上に形成したアルミニウム層を、アルミニウム1%銅合金層(AlCu層)へ変更した以外は、実施例1と同様にして中空構造体を得た。
側壁に用いた調製例1のネガ型感光性組成物を、調製例3のネガ型感光性組成物へ変更し、天板部に用いた調製例1のネガ型感光性組成物を、調製例4のネガ型感光性組成物へ変更し、シリコンウェーハ上に形成したアルミニウム層を、アルミニウム1%銅合金層へ変更した以外は、実施例1と同様にして中空構造体を得た。
調製例1のネガ型感光性組成物を、調製例5のネガ型感光性組成物へ変更し、シリコンウェーハ上に形成したアルミニウム層を、アルミニウム1%銅合金層(AlCu層)へ変更した以外は、実施例1と同様にして中空構造体を得た。
得られた各例の中空構造体を、光学顕微鏡を用いて観測し、基板上のアルミニウム配線が腐食されていないことをHAST試験及びPCT試験で評価した。
実施例1~3及び比較例1の中空構造体は、中空構造が形成されたアルミニウム蒸着基板のHAST(85℃、湿度85%、100時間)処理を行ったのち、光学顕微鏡を用いて観測し、腐食の有無を観測した。結果を図3及び表3に示す。
実施例4~6及び比較例2の中空構造体は、中空構造が形成されたアルミニウム-銅1%合金蒸着基板のPCT(120℃、96時間)処理を行ったのち、光学顕微鏡を用いて観測し、腐食の有無を観測した。結果を図4及び表4に示す。
図3は、HAST試験の前後における中空パッケージの状態を光学顕微鏡で撮影した結果を示す。比較例1では、側壁3に囲まれている内部のアルミニウム蒸着基板が腐食しているため、側壁3の内部が黒くなっていることが、天板部4越しに観察できた。一方、実施例3では、側壁1に囲まれている内部が腐食せず、天板部2越しに基板が観察できた。実施例1~2の内部腐食の結果は、実施例3と同様であった。
2、4 天板部
10 基板
15 凹部
30 感光性樹脂膜
30A 露光部
30B 未露光部
30F 感光性レジストフィルム
40 硬化体
60 フォトマスク
Claims (8)
- アルミニウム配線を有する基板上に、前記アルミニウム配線を収容する中空構造体を備えた中空パッケージの製造方法であって、
前記のアルミニウム配線を有する基板上に、前記アルミニウム配線を囲む側壁を形成する工程と、
前記側壁上に、天板部を形成して、前記アルミニウム配線を収容する前記中空構造体を作製する工程と、
を有し、
前記側壁及び/又は前記天板部は感光性組成物により形成され、
前記感光性組成物は、カチオン部とアニオン部とからなるカチオン重合開始剤を含有し、
前記アニオン部が、下記一般式(I1-an)で表されるアニオンを含む、中空パッケージの製造方法。
- 前記一般式(I1-an)における、m/(k+m)が0.5未満である、請求項1に記載の中空パッケージの製造方法。
- 前記側壁及び前記天板部の双方が感光性組成物により形成される、請求項1又は2に記載の中空パッケージの製造方法。
- 前記側壁及び/又は前記天板部を形成する前記感光性組成物は、前記カチオン重合開始剤と、エポキシ基含有化合物と、を含有するネガ型感光性組成物である、請求項1ないし4のいずれか一項に記載の中空パッケージの製造方法。
- 前記ネガ型感光性組成物中の前記カチオン重合開始剤の含有量は、前記エポキシ基含有化合物100質量部に対して0.5~5質量部である、請求項5に記載の中空パッケージの製造方法。
- 前記の中空構造体を作製する工程の後に、前記中空構造体を封止材により封止する工程をさらに有する、請求項1ないし6のいずれか一項に記載の中空パッケージの製造方法。
- 請求項1ないし7のいずれか一項に記載の中空パッケージの製造方法を実行するプロセスラインに対し、前記感光性組成物を提供する、感光性組成物の提供方法。
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