WO2023120274A1 - 光硬化性組成物及びパターン形成方法 - Google Patents
光硬化性組成物及びパターン形成方法 Download PDFInfo
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- WO2023120274A1 WO2023120274A1 PCT/JP2022/045665 JP2022045665W WO2023120274A1 WO 2023120274 A1 WO2023120274 A1 WO 2023120274A1 JP 2022045665 W JP2022045665 W JP 2022045665W WO 2023120274 A1 WO2023120274 A1 WO 2023120274A1
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- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 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
- GJSGGHOYGKMUPT-UHFFFAOYSA-N phenoxathiine Chemical group C1=CC=C2OC3=CC=CC=C3SC2=C1 GJSGGHOYGKMUPT-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 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
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 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
- VDNLFJGJEQUWRB-UHFFFAOYSA-N rose bengal free acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C(O)=C(I)C=C21 VDNLFJGJEQUWRB-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000006168 tricyclic group Chemical group 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
- 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
- 239000008096 xylene Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 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
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
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
-
- 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
- G03F7/20—Exposure; Apparatus therefor
Definitions
- the present invention relates to a photocurable composition and a pattern forming method.
- This application claims priority based on Japanese Patent Application No. 2021-206080 filed in Japan on December 20, 2021, the content of which is incorporated herein.
- a package having a hollow structure in which a wiring board on which electrodes are formed is kept hollow is used.
- This hollow package can be manufactured as follows. After applying a photosensitive composition on the wiring board so as to surround the electrodes, exposure through a photomask, post-exposure baking (PEB), and development are performed in this order to form sidewalls that will serve as spacers. Next, a hollow structure is produced by bonding a top plate portion onto the side walls. A hollow package is then produced by molding.
- PEB post-exposure baking
- photosensitive composition for example, a photocurable adhesive material containing a photocationically polymerizable compound and a polymerization initiator that generates a cationic species upon irradiation with light or heating has been proposed (for example, Patent Document 1 reference).
- photosensitive compositions are required to have various properties.
- the photosensitive composition is used as a material for the sidewalls that serve as spacers.
- the side walls are required to have adhesiveness with the top plate.
- the manufacture of electronic parts often includes a chemical solution treatment process, and the side walls are required to have chemical resistance to the chemical solution.
- further improvement in properties is required in conventional photocurable adhesive materials.
- the present invention has been made in view of the above circumstances, a photocurable composition having improved adhesion to an object when formed into a cured film, and excellent chemical resistance, and a pattern using the same
- An object of the present invention is to provide a forming method.
- the present invention adopts the following configuration.
- the first aspect of the present invention comprises an acrylic resin (AC), an epoxy group-containing compound (A) (excluding those corresponding to the acrylic resin (AC)), and a cationic polymerization initiator (I) and wherein the acrylic resin (AC) has a glass transition point of 0° C. or lower and has a structural unit (ac1) derived from an epoxy group-containing acrylic monomer. and the content ratio of the structural unit (ac1) is more than 0% by mass and less than 50% by mass with respect to the total (100% by mass) of all the structural units constituting the acrylic resin (AC). It is a photocurable composition.
- a second aspect of the present invention is a step of forming a photocurable film on a support using the photocurable composition according to the first aspect, exposing the photocurable film, and developing the exposed photocurable film with a developer containing an organic solvent to form a negative pattern.
- the present invention it is possible to provide a photocurable composition that can improve adhesion to an object when formed into a cured film and has excellent chemical resistance, and a pattern forming method using the same.
- alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group. Unless otherwise specified, the “alkylene group” includes straight-chain, branched-chain and cyclic divalent saturated hydrocarbon groups.
- a "halogenated alkyl group” is a group in which some or all of the hydrogen atoms of an alkyl group are substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms.
- a “fluorinated alkyl group” refers to a group in which some or all of the hydrogen atoms in an alkyl group have been substituted with fluorine atoms.
- a “structural unit” means a monomer unit (monomeric unit) that constitutes a polymer compound (resin, polymer, copolymer). When describing "optionally having a substituent", when a hydrogen atom (-H) is substituted with a monovalent group, and when a methylene group (-CH 2 -) is substituted with a divalent group and both. “Exposure” is a concept that includes irradiation of radiation in general.
- the photocurable composition of the present embodiment comprises an acrylic resin (AC), an epoxy group-containing compound (A) (excluding those corresponding to the acrylic resin (AC)), and a cationic polymerization initiator (I) and
- acrylic resin (AC), epoxy group-containing compound (A), and cationic polymerization initiator (I) are also referred to as (AC) component, (A) component, and (I) component, respectively.
- the cationic portion of the component (I) is formed in the exposed portion of the photocurable film. is decomposed to generate an acid, and the action of the acid causes ring-opening polymerization of the epoxy groups in the components (A) and (AC), and the component (A) and the component (A) for the developer containing an organic solvent. While the solubility of the (AC) component decreases, the solubility of the (A) component and the (AC) component in the developer containing an organic solvent does not change in the unexposed area of the photocurable film.
- the acrylic resin (AC) contained in the photocurable composition of the present embodiment has a glass transition point of 0° C. or lower and has a structural unit (ac1) derived from an epoxy group-containing acrylic monomer.
- the content of the structural unit (ac1) is more than 0% by mass and less than 50% by mass with respect to the total (100% by mass) of all structural units constituting the component (AC). That is, the (AC) component has a structural unit (ac1) and other structural units (ac2).
- Acrylic resin (AC) refers to a polymer produced by polymerizing at least acrylic acid ester as a monomer.
- the term "epoxy group-containing acrylic monomer” refers to an acrylic acid ester containing an epoxy group in its side chain.
- the hydrogen atom bonded to the ⁇ -position carbon atom may be substituted with a substituent.
- the substituent (R ⁇ x ) substituting the hydrogen atom bonded to the ⁇ -position carbon atom is an atom or group other than a hydrogen atom.
- the ⁇ -position carbon atom of the acrylic acid ester means the carbon atom to which the carbonyl group of acrylic acid is bonded.
- Examples of the substituent (R ⁇ x ) include an alkyl group having 1 to 5 carbon atoms, a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms.
- the glass transition point Tg (° C.) of an acrylic resin that is a copolymer of a structural unit derived from 2-methoxyethyl acrylate and a structural unit derived from n-butyl acrylate is as follows. can be calculated as Monomer (1) is 2-methoxyethyl acrylate. A homopolymer consisting of a repeating structure of the structural unit (1) derived from the monomer (1) has a glass transition point of ⁇ 50° C., and the ratio of the structural unit (1) is 73% by mass. Monomer (2) is n-butyl acrylate.
- a homopolymer consisting of a repeating structure of the structural unit (2) derived from the monomer (2) has a glass transition point of ⁇ 56° C., and the proportion of the structural unit (2) is 27 mass %.
- the glass transition point Tg of the component (AC) is 0°C or lower, preferably -100°C or higher and 0°C or lower, more preferably -75°C or higher and -5°C or lower, and further preferably -65°C or higher and -10°C or lower. . If the glass transition point Tg of the component (AC) is equal to or lower than the upper limit of the above range, the cured film can have enhanced adhesiveness to an object and improved reliability. On the other hand, when it is at least the lower limit of the above range, the chemical resistance of the resin pattern can be further enhanced, and the lithography properties during pattern formation can be improved.
- the glass transition point Tg of the (AC) component can be controlled by selecting the type of structural unit constituting the (AC) component or by adjusting the content of the structural unit.
- the (AC) component has a structural unit (ac1) derived from an epoxy group-containing acrylic monomer.
- a “structural unit derived from an epoxy group-containing acrylic monomer” means a structural unit formed by cleavage of an ethylenic double bond of an epoxy group-containing acrylic monomer.
- Examples of the structural unit (ac1) include a structural unit containing an epoxy group-containing group in the side chain.
- the "epoxy group-containing group” as used herein is not particularly limited, and includes 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 group having a linking group.
- An alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically a group having an alicyclic group and an oxacyclopropane structure.
- the alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
- a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group etc. are mentioned as a polycyclic alicyclic group.
- the hydrogen atoms of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like.
- the epoxy group or alicyclic epoxy It is preferred that the groups are attached.
- the divalent linking group is not particularly limited, but preferably includes a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.
- Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its 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 straight-chain alkylene group is preferable, and specifically, a methylene group [ --CH.sub.2-- ], an ethylene group [--( CH.sub.2 ) .sub.2-- ], a trimethylene group [ -(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] and the like.
- the branched chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms.
- the branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2- , -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups;- CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 Alkylethylene groups such as CH 3 ) 2
- the aliphatic hydrocarbon group containing a ring in the structure includes an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group intervenes in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those mentioned above.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, 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 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 preferably has 7 to 12 carbon atoms. includes adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
- the aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) ⁇ electrons, and may be monocyclic or polycyclic.
- the number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, still more preferably 6-15, and particularly preferably 6-12.
- Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; mentioned.
- the heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like.
- Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.
- aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); aromatic compounds containing two or more aromatic rings A group obtained by removing two hydrogen atoms from (e.g., biphenyl, fluorene, etc.); One of the hydrogen atoms of the group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) A group in which one is 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 hydrogen from an arylalkyl group such as a 2-naphthylethyl group) group from which one atom has been further removed), and the like.
- the divalent hydrocarbon group may have a substituent.
- a linear or branched aliphatic hydrocarbon group as a divalent hydrocarbon group may or may not have a substituent.
- the substituent include a fluorine atom, a fluorine-substituted fluorinated alkyl group having 1 to 5 carbon atoms, and a carbonyl group.
- An alicyclic hydrocarbon group in an aliphatic hydrocarbon group containing a ring in its structure as a divalent hydrocarbon group may or may not have a substituent.
- substituents include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group and the like.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
- the alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group.
- a methoxy group and an ethoxy group are most preferred.
- the halogen atom as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- a 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, a halogenated alkyl group, and a hydroxyl group.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
- the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the alicyclic hydrocarbon group.
- the heteroatom in the heteroatom-containing bivalent linking group is an atom other than a carbon atom and a hydrogen atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom and the like.
- Y 21 and Y 22 are each independently a divalent hydrocarbon group optionally having a substituent; , O is an oxygen atom, and m′′ is an integer from 0 to 3. ] and the like.
- the H may be substituted with a substituent such as an alkyl group or 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.
- Y 21 is preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, more preferably a straight-chain alkylene group having 1 to 5 carbon atoms, and a methylene group or an ethylene group.
- Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group.
- the alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
- m′′ is an integer of 0 to 3, preferably an integer of 0 to 2, and 0 or 1 is more preferred, and 1 is particularly preferred.
- 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 more preferred, and 1 is most preferred.
- a glycidyl group is preferable as the epoxy group-containing group.
- Examples of the structural unit (ac1) include epoxy group-containing units represented by general formulas (a1-1) and (a1-2) below.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Va 41 is a divalent hydrocarbon group optionally having a substituent.
- na 41 is an integer of 0-2.
- R a41 and R a42 are each 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 1-3.
- the alkyl group having 1 to 5 carbon atoms in R is preferably linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like.
- the halogenated alkyl group having 1 to 5 carbon atoms in R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms.
- the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferred.
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group in view of industrial availability.
- Va 41 is a divalent hydrocarbon group which may have a substituent, and has a substituent as described in the above "epoxy group-containing group".
- the same groups as the divalent hydrocarbon groups which are good are mentioned.
- the hydrocarbon group of Va 41 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, still more preferably a linear aliphatic hydrocarbon group, A straight-chain alkylene group is 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, which are the same as the above-mentioned "epoxy group-containing groups", and glycidyl groups are particularly preferred.
- the (na 43 +1)-valent aliphatic hydrocarbon group in Wa 41 means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated. may be used, and is usually preferably saturated.
- 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 from 0-10.
- R a51 , R a52 and R a53 may be the same or different.
- the structural unit (ac1) of the component (AC) may be of one type or two or more types.
- an epoxy group-containing unit represented by general formula (a1-1) above is preferred.
- the content of the structural unit (ac1) is more than 0% by mass and less than 50% by mass, and is 0.05% by mass or more with respect to the total (100% by mass) of all the structural units constituting the component (AC). It is preferably 40% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, further preferably 0.10% by mass or more and 10% by mass or less, and 0.20% by mass or more. It is particularly preferred that it is 5% by mass or less.
- the content of the structural unit (ac1) is above the lower limit of the above range, the chemical resistance of the resin pattern is further enhanced, the strength of the cured film is increased, and the lithography properties during pattern formation are improved. .
- the chemical resistance of the resin pattern can be further enhanced, the adhesiveness to the object when made into a cured film can be enhanced, and reliability can be improved.
- the (AC) component has a structural unit (ac2) other than the structural unit (ac1) described above.
- the structural unit (ac2) the glass transition point of the (AC) component, which is a copolymer with the structural unit (ac1), may be 0° C. or lower, and an acrylic acid ester other than an epoxy group-containing acrylic monomer.
- the hydrogen atom bonded to the ⁇ -position carbon atom may be substituted with a substituent.
- substituent (R ⁇ x ) for substituting the hydrogen atom bonded to the ⁇ -position carbon atom include an alkyl group having 1 to 5 carbon atoms, a halogen atom, and a halogenated alkyl group having 1 to 5 carbon atoms. be done.
- Examples of monomers from which the structural unit (ac2) is derived include 2-ethylhexyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl acrylate, n-butyl methacrylate, isobutyl methacrylate, and methacrylic acid.
- (meth)acrylic acid alkyl esters such as ethyl and methyl methacrylate; hydroxy (meth)acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate Alkyl esters; (meth)acrylic acid alkoxyalkyl esters such as 2-methoxyethyl acrylate and 2-methoxyethyl methacrylate; monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, itaconic acid, etc.
- dicarboxylic acids 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, methacrylic acid derivatives having a carboxyl group or an ester bond such as 2-methacryloyloxyethyl hexahydrophthalic acid; (Meth)acrylic acid aryl esters such as phenyl acrylate, benzyl acrylate, phenyl methacrylate, and benzyl methacrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, ⁇ -methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene , hydroxystyrene, ⁇ -methylhydroxystyrene, ⁇ -ethylhydroxystyrene and other vinyl group-containing aromatic compounds
- (meth)acrylic acid means one or both of acrylic acid and methacrylic acid.
- the structural unit (ac2) contained in the component (AC) may be of one type or two or more types.
- alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, and alkoxyalkyl (meth)acrylates are preferable as the monomer from which the structural unit (ac2) is derived.
- the alkyl in the alkyl ester portion preferably has 1 to 5 carbon atoms.
- the alkyl in the hydroxyalkyl ester portion preferably has 1 to 5 carbon atoms.
- the alkoxy in the alkoxyalkyl ester portion preferably has 1 to 3 carbon atoms, and the alkyl preferably has 1 to 5 carbon atoms.
- the content of the structural unit (ac2) is 50% by mass or more and 60% by mass or more and 99.95% by mass or less with respect to the total (100% by mass) of all the structural units constituting the component (AC). is preferably 80% by mass or more and 99.95% by mass or less, more preferably 90% by mass or more and 99.90% by mass or less, and 95% by mass or more and 99.80% by mass or less is particularly preferred. If the content of the structural unit (ac2) is at least the lower limit of the above range, the chemical resistance of the resin pattern can be further enhanced. On the other hand, when the amount is equal to or less than the upper limit of the above range, the chemical resistance of the resin pattern can be further enhanced, and the lithography properties during pattern formation can be improved.
- the acrylic resin (AC) contained in the photocurable composition of the present embodiment has a glass transition point of 0° C. or lower, and the content of the structural unit (ac1) is more than 0% by mass and less than 50% by mass.
- the content of these copolymers may be used alone, or two or more thereof may be used in combination.
- the content of structural units derived from the "acrylic acid ester" is 50% by mass or more with respect to the total (100% by mass) of all structural units constituting the (AC) component. is preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.
- Preferred copolymers in which the content of the structural unit (ac1) is more than 0% by mass and less than 50% by mass include the structural unit (ac1) and a structural unit derived from a (meth)acrylic acid alkyl ester.
- a preferred copolymer in which the content of the structural unit (ac1) is more than 0% by mass and less than 50% by mass is a structural unit derived from the structural unit (ac1) and a (meth)acrylic acid alkoxyalkyl ester.
- the structural unit (ac1) The content ratio is more than 0% by mass and 5% by mass or less, the content ratio of the structural unit derived from the (meth)acrylic acid alkoxyalkyl ester is 30% by mass or more and 99% by mass or less, and (meth)acrylic acid
- the content of structural units derived from hydroxyalkyl esters is 0.5% by mass or more and 5% by mass or less, and the content of structural units derived from (meth)acrylic acid alkyl esters is 20% by mass or more and 70% by mass. % by mass or less.
- the component (AC) is obtained by dissolving a monomer from which the structural unit (ac1) is derived and a monomer from which the structural unit (ac2) is derived in a polymerization solvent, It can be produced by adding a radical polymerization initiator such as dimethyl butyrate (eg, V-601) and conducting polymerization.
- a radical polymerization initiator such as dimethyl butyrate (eg, V-601) and conducting polymerization.
- the weight average molecular weight (Mw) of the component (AC) (standard polystyrene conversion standard by gel permeation chromatography GPC measurement) is not particularly limited, but is preferably 50,000 to 400,000, more preferably 60,000 to 380,000, and 70,000 to 360,000 is more preferred.
- the dispersity (Mw/Mn) of the component (AC) is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0. . Mn indicates number average molecular weight.
- the content of the (AC) component is preferably 1 to 45 parts by mass with respect to 100 parts by mass of the epoxy group-containing compound (A) described later. It is more preferably 1 to 40 parts by mass, even more preferably 5 to 30 parts by mass, and particularly preferably 10 to 25 parts by mass.
- the content of the component (AC) is preferably 1 to 40% by mass with respect to the total solid content (100% by mass) of the photocurable composition, and 3 It is more preferably up to 30% by mass, and even more preferably 5 to 20% by mass.
- the epoxy group-containing compound (A) contained in the photocurable composition of the present embodiment includes a compound having sufficient epoxy groups in one molecule to form a negative pattern by exposure.
- Examples of such component (A) include novolak type epoxy resins (hereinafter also referred to as "(A1) component”), bisphenol type epoxy resins (hereinafter also referred to as "(A2) component”), aliphatic epoxy resins, and the like.
- the component (A) may be used alone or in combination of two or more. However, the component (A) excludes the acrylic resin (AC) described above.
- Novolac type epoxy resin As the novolac type epoxy resin (component (A1)), epoxy resins represented by the following general formula (anv0) are suitable.
- R p1 and R p2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- a plurality of R p1 may be the same or different from each other.
- a plurality of R p2 may be the same or different from each other.
- n 1 is an integer from 1 to 5;
- REP is an epoxy group-containing group. Multiple REPs may be the same or different.
- the alkyl group having 1 to 5 carbon atoms of R p1 and R p2 is, for example, a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.
- Linear or branched alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like.
- a cyclobutyl group, a cyclopentyl group, etc. are mentioned as a cyclic alkyl group.
- R p1 and R p2 are preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, and particularly preferably a hydrogen atom or a methyl group.
- a plurality of R p1 may be the same or different.
- a plurality of R p2 may be the same or different from each other.
- n1 is an integer of 1 to 5, preferably 2 or 3, more preferably 2.
- REP is an epoxy group-containing group.
- the epoxy group-containing group of R EP is not particularly limited, and includes 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. and a group having The explanation of the epoxy group-containing group of REP is the same as the explanation of the above-mentioned "epoxy group-containing group". Among them, a glycidyl group is preferable as the epoxy group-containing group in REP .
- a resin having a structural unit represented by the following general formula (anv1) is also suitable.
- REP is an epoxy group-containing group.
- R a22 and R a23 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.
- the alkyl groups having 1 to 5 carbon atoms for R a22 and R a23 are the same as the alkyl groups having 1 to 5 carbon atoms for R p1 and R p2 in the formula (anv0). .
- the halogen atoms of R a22 and R a23 are preferably chlorine atoms or bromine atoms.
- R EP is the same as R EP in formula (anv0), and is preferably a glycidyl group.
- the (A1) component may be a resin consisting only of the structural unit (anv1), or may be a resin having the structural unit (anv1) and other structural units.
- Other structural units include, for example, structural units represented by the following general formulas (anv2) to (anv3).
- R a24 is a hydrocarbon group which may have a substituent.
- R a25 to R a26 and R a28 to R a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.
- R a27 is an epoxy group-containing group or a hydrocarbon group optionally having a substituent.
- R a24 is a hydrocarbon group which may have a substituent.
- the hydrocarbon group which may have a substituent includes 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, and still more preferably 1 or 2 carbon atoms.
- Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, 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, more preferably 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group and a 2,2-dimethylbutyl group, with an isopropyl group being preferred.
- R a24 is a cyclic hydrocarbon group
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
- the monocyclic aliphatic hydrocarbon group 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 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 preferably has 7 to 12 carbon atoms. adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
- the aromatic hydrocarbon group for R a24 is an aromatic hydrocarbon group
- the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
- the number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, even more preferably 6-15, and particularly preferably 6-12.
- Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; mentioned.
- the heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like.
- aromatic heterocycles include pyridine rings and thiophene rings.
- aromatic hydrocarbon group for R a24 include groups obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); containing two or more aromatic rings A group obtained by removing one hydrogen atom from an aromatic compound (e.g., biphenyl, fluorene, etc.); A group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, arylalkyl group such as 2-naphthylethyl group, etc.).
- the number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1
- R a25 to R a26 and R a28 to R a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.
- the alkyl group having 1 to 5 carbon atoms and the halogen atom are the same as defined above for R a22 and R a23 respectively.
- R a27 is an epoxy group-containing group or a hydrocarbon group which may have a substituent.
- the epoxy group-containing group of R a27 is the same as R EP in the formula (anv0).
- the hydrocarbon group optionally having a substituent for R a27 is the same as R a24 in the formula (anv2).
- the ratio of each structural unit in the component (A1) is not particularly limited, but it constitutes the component (A1).
- the total amount of constituent units having an epoxy group is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%, based on the total amount of all constituent units.
- component (A1) Commercially available products of component (A1) include, for example, novolak type epoxy resins such as jER-152, jER-154, jER-157S70, jER-157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N -740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON HP5000 (above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), and the like.
- novolak type epoxy resins such as jER-152, jER-154, jER-157S70, jER-157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, E
- the component (A1) one type may be used alone, or two or more types may be used in combination.
- the content of component (A1) is preferably 25% by mass or more, and 40% by mass or more, relative to 100% by mass of the total amount of component (A). is more preferable, and may be 50% by mass or more, 75% by mass or more, 90% by mass or more, or 100% by mass.
- the bisphenol-type epoxy resin (hereinafter also referred to as "(A2) component”) may be any resin having a structural unit containing a bisphenol skeleton, and among these, a solid bisphenol-type epoxy resin is preferable.
- a solid bisphenol type epoxy resin refers to a resin having a structural unit containing a bisphenol skeleton that is solid at 25°C.
- the epoxy equivalent of component (A2) is, for example, 500 g/eq. 550 to 1200 g/eq. is more preferable, and 600 to 1000 g/eq. is more preferred.
- the (A2) component is preferably an epoxy resin represented by the following general formula (abp1).
- REP is an epoxy group-containing group. Multiple REPs may be the same or different.
- R a31 and R a32 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms.
- na 31 is an integer of 1-50.
- R EP is the same as R EP in formula (anv0), and is preferably a glycidyl group.
- the alkyl group having 1 to 5 carbon atoms in R a31 and R a32 is the same as the alkyl group having 1 to 5 carbon atoms in R p1 and R p2 in the formula (anv0).
- each of R a31 and R a32 is preferably a hydrogen atom or a methyl group.
- na 31 is an integer of 1-50, preferably an integer of 4-15, more preferably an integer of 5-8.
- (A2) component Commercially available products that can be used as (A2) component are, for example, jER-4005, jER-4007, jER-4010 (manufactured by Mitsubishi Chemical Corporation); jER-827, jER-828, jER-834, jER-1001 , jER-1002, jER-1003, jER-1055, jER-1007, jER-1009, jER-1010 (manufactured by Mitsubishi Chemical Corporation); EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc. are mentioned.
- the component (A2) one type may be used alone, or two or more types may be used in combination.
- the content of component (A2) is preferably 50% by mass or more, and 60% by mass or more, relative to 100% by mass of the total amount of component (A). is more preferable, and may be 70% by mass or more, 80% by mass or more, 90% by mass or more, or 100% by mass.
- the ratio of the (A1) component and the (A2) component is 1/9 or more as a mass ratio represented by the (A1) component/(A2) component. It is preferably 7/3 or less, more preferably 2/8 or more and 6/4 or less, and even more preferably 3/7 or more and 5/5 or less. If the mass ratio is within the preferred range, the chemical resistance is likely to be improved, and the resolution is further enhanced.
- aliphatic epoxy resins include compounds represented by the following general formula (ta1) (hereinafter, this compound is also referred to as "(A3) component").
- REP is an epoxy group-containing group. Multiple REPs may be the same or different. ]
- REP is an epoxy group-containing group and is the same as REP in formula (anv0).
- the component (A3) Commercially available products that can be used as the component (A3) include, for example, TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC- FL, TEPIC series such as TEPIC-UC (manufactured by Nissan Chemical Industries, Ltd.); MA-DGIC, DA-MGIC, TOIC (manufactured by Shikoku Kasei Kogyo Co., Ltd.); As the component (A3), one type may be used alone, or two or more types may be used in combination.
- aliphatic epoxy resins also include compounds containing a partial structure represented by the following general formula (m1) (hereinafter also referred to as “component (m1)”).
- n 2 is an integer of 1 to 4. * indicates a bond.
- n2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.
- Component (m1) includes a compound in which a plurality of partial structures represented by the general formula (m1) are bonded via a divalent linking group or a single bond.
- a compound in which a plurality of partial structures represented by the general formula (m1) are bonded via a divalent linking group is preferable.
- the divalent linking group here is not particularly limited, but preferably includes an optionally substituted divalent hydrocarbon group and a heteroatom-containing divalent linking group.
- the divalent hydrocarbon group optionally having a substituent and the divalent linking group containing a hetero atom have a substituent as described in the above "epoxy group-containing group”.
- Y 21 is preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, more preferably a straight-chain alkylene group having 1 to 5 carbon atoms, and a methylene group or an ethylene group. Especially preferred.
- ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S manufactured by ADEKA Corporation
- Celoxide 8000, Celoxide 8010, EHPE-3150, EPOLEAD PB 3600, EPOLEAD PB 4700 manufactured by Daicel Corporation
- Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L above, manufactured by Nagase ChemteX Corporation
- a compound represented by the following chemical formula (A4-1) and a compound represented by the following chemical formula (A4-2) may be used.
- Commercially available products that can be used as the compound represented by the following chemical formula (A4-1) include, for example, TECHMORE VG-3101L (manufactured by Printec Co., Ltd.).
- Commercially available products that can be used as the compound represented by the following chemical formula (A4-2) include, for example, Showfree (registered trademark) BATG (manufactured by Showa Denko KK).
- Examples of the epoxy group-containing compound (A) include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, inositol hexaglycidyl ether and the like.
- the component (A) preferably contains at least one type of epoxy resin selected from the group consisting of a bisphenol type epoxy resin (A2) and a novolac type epoxy resin (A1). .
- the component (A) one containing a solid bisphenol type epoxy resin and the component (A1) is more preferable, and the epoxy resin represented by the general formula (abp1) and the general formula (anv0) Further preferred are those containing an epoxy resin.
- the polystyrene equivalent weight average molecular weight of component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, still more preferably 300 to 200,000. With such a weight average molecular weight, the chemical resistance of the resin pattern can be easily enhanced, and the strength of the formed cured film can be sufficiently enhanced.
- the content of component (A) in the photocurable composition of the present embodiment may be adjusted according to the film thickness of the photocurable film to be formed.
- the content of component (A) is preferably 40 to 99% by mass with respect to the total solid content (100% by mass) of the photocurable composition, and 50 It is more preferably up to 95% by mass, and even more preferably 60 to 90% by mass.
- the mass ratio is at least the lower limit of the preferred range, the chemical resistance of the resin pattern is likely to be enhanced, and the strength of the formed cured film is sufficiently enhanced, while the upper limit of the preferred range is When it is less than the value, it becomes easier to improve the adhesiveness to the object when it is made into a cured film.
- the cationic polymerization initiator (I) contained in the photocurable composition of the present embodiment is irradiated with active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser beams such as KrF and ArF, X-rays, and electron beams. It is a compound that generates cations and the cations can serve as polymerization initiators.
- component (I) examples include onium borate salts (hereinafter also referred to as “component (I1)”), compounds represented by general formula (I2-1) or (I2-2) described later (hereinafter referred to as “component (I2) ”), and compounds represented by general formula (I3-1) or (I3-2) described below (hereinafter also referred to as “component (I3)”).
- component (I1) onium borate salts
- component (I2) compounds represented by general formula (I2-1) or (I2-2) described later
- component (I3) compounds represented by general formula (I3-1) or (I3-2) described below
- Onium borate salt (component (I1)) generates a relatively strong acid upon exposure. Therefore, by forming a pattern using the photocurable composition containing the component (I1), sufficient sensitivity can be obtained and a good pattern can be formed. In addition, the use of component (I1) has a low risk of toxicity and metal corrosion.
- component (I1) for example, compounds represented by the following general formula (I1) are suitable.
- R b01 to R b04 are each independently an optionally substituted aryl group or a fluorine atom.
- q is an integer of 1 or more, and Q q+ is a q-valent organic cation.
- the aryl group in R b01 to R b04 preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and 6 to 12 carbon atoms. is particularly preferred. Specific examples include a naphthyl group, a phenyl group, an anthracenyl group, and the like, and a phenyl group is preferable because it is easily available.
- the aryl groups in R b01 to R b04 may have a substituent.
- the substituents are not particularly limited, but are halogen atoms, hydroxyl groups, alkyl groups (preferably linear or branched alkyl groups, preferably having 1 to 5 carbon atoms), and halogenated alkyl groups. is preferred, a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms is more preferred, and a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is particularly preferred.
- the aryl group has a fluorine atom, the polarity of the anion moiety is increased, which is preferable.
- each of R b01 to R b04 in formula (I1) is preferably a fluorinated phenyl group, and particularly preferably a perfluorophenyl group.
- Preferred specific examples of the anion portion of the compound represented by the formula (I1) include tetrakis(pentafluorophenyl)borate ([B(C 6 F 5 ) 4 ] ⁇ ); tetrakis[(trifluoromethyl)phenyl] Borate ([B(C 6 H 4 CF 3 ) 4 ] ⁇ ); difluorobis(pentafluorophenyl)borate ([(C 6 F 5 ) 2 BF 2 ] ⁇ ); trifluoro(pentafluorophenyl)borate ([ (C 6 F 5 )BF 3 ] ⁇ ); tetrakis(difluorophenyl)borate ([B(C 6 H 3 F 2 ) 4 ] ⁇ ); Among them, tetrakis(pentafluorophenyl)borate ([B(C 6 F 5 ) 4 ] ⁇ ) is particularly preferred.
- Q q+ preferably includes a sulfonium cation and an iodonium cation, and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred. preferable.
- R 201 to R 207 and R 211 to R 212 each independently represent an optionally substituted aryl group, heteroaryl group, alkyl group or alkenyl group.
- R 201 to R 203 , R 206 to R 207 and R 211 to R 212 may combine with 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 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted —SO 2 —containing cyclic group.
- Each Y 201 independently represents an arylene group, an alkylene group or an alkenylene group.
- x is 1 or 2;
- W 201 represents a (x+1)-valent linking group.
- the aryl group for R 201 to R 207 and R 211 to R 212 includes unsubstituted aryl groups having 6 to 20 carbon atoms, preferably phenyl group and naphthyl group.
- heteroaryl groups for R 201 to R 207 and R 211 to R 212 include those in which part of the carbon atoms constituting the aryl group are substituted with heteroatoms. Heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and the like.
- Examples of the heteroaryl group include groups obtained by removing one hydrogen atom from 9H-thioxanthene; examples of substituted heteroaryl groups include groups obtained by removing one hydrogen atom from 9H-thioxanthene-9-one.
- the alkyl group for 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 groups for R 201 to R 207 and R 211 to R 212 preferably have 2 to 10 carbon atoms.
- each R′ 201 is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or a substituted is a chain alkenyl group that may be ]
- R' 201 is each independently a hydrogen atom, an optionally substituted cyclic group, a substituent a chain alkyl group which may be substituted or a chain alkenyl 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.
- An aliphatic hydrocarbon group means a hydrocarbon group without aromaticity.
- the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
- the aromatic hydrocarbon group for R' 201 is a hydrocarbon group having an aromatic ring.
- the number of carbon atoms in 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, most preferably 6 to 10. .
- the number of carbon atoms does not include the number of carbon atoms in the substituent.
- Specific examples of the aromatic ring of the aromatic hydrocarbon group for R′ 201 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or those in which some of the carbon atoms constituting the aromatic ring are substituted with heteroatoms.
- the heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like.
- Specific examples of the aromatic hydrocarbon group for R′ 201 include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, an anthracenyl group, etc.), and a hydrogen atom of the aromatic ring.
- alkylene group e.g., a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, an arylalkyl group such as a 2-naphthylethyl group, etc.
- a group obtained by removing one hydrogen atom from a ring in which a portion of the hydrogen atoms constituting the aromatic ring is substituted with an oxo group e.g., anthraquinone, etc.
- an aromatic heterocyclic ring e.g., 9H-thioxanthene, 9H-thioxanthene) -9-one, etc.
- the alkylene group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms,
- the cyclic aliphatic hydrocarbon group for R' 201 includes an aliphatic hydrocarbon group containing a ring in its structure.
- the aliphatic hydrocarbon group containing a ring in this structure includes an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group intervenes in the middle of a linear or branched aliphatic hydrocarbon group.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms.
- the polycycloalkanes include polycycloalkanes having a bridged ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; condensed ring systems such as cyclic groups having a steroid skeleton; Polycycloalkanes having a polycyclic skeleton of are more preferred.
- the cyclic aliphatic hydrocarbon group for R′ 201 is preferably a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane, and a group obtained by removing one hydrogen atom from polycycloalkane. More preferred are an adamantyl group and a norbornyl group, and most preferred is an adamantyl group.
- 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 is more preferred, and 1-3 are most preferred.
- a straight-chain aliphatic hydrocarbon group a straight-chain alkylene group is preferable, and specifically, a methylene group [ --CH.sub.2-- ], an ethylene group [--( CH.sub.2 ) .sub.2-- ], a trimethylene group [ -(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] and the like.
- the branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2- , -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups;- CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 Alkylethylene groups such as CH 3 ) 2 -CH 2 -; alkyltrimethylene groups such as -CH(CH 3 )CH 2 CH 2 - and -CH 2 CH(CH 3 )CH 2 -; -CH(CH 3 ) Examples include alkylalky
- a chain alkyl group optionally having a substituent may be 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.
- 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.
- a chain alkenyl group optionally having a substituent may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably 2 to 4 carbon atoms. , 3 are particularly preferred.
- Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups.
- Examples of branched alkenyl groups include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like.
- the chain alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.
- substituents on the cyclic group, chain 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, an oxo group, and the above
- a cyclic group, an alkylcarbonyl group, a thienylcarbonyl group and the like for R' 201 can be mentioned.
- R' 201 is preferably an optionally substituted cyclic group or an optionally substituted chain alkyl group.
- R 201 to R 203 , R 206 to R 207 and R 211 to R 212 are mutually bonded to form a ring together with the sulfur atom in the formula, heteroatoms such as a sulfur atom, an oxygen atom and a nitrogen atom, a carbonyl group, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )- (the R N is an alkyl group having 1 to 5 carbon atoms); You may couple
- one ring containing a sulfur atom in the formula in its ring skeleton is preferably a 3- to 10-membered ring including a sulfur atom, particularly a 5- to 7-membered ring. preferable.
- the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiine ring, and a tetrahydro A thiophenium ring, a tetrahydrothiopyranium ring, and the like are included.
- R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, When forming an alkyl group, they may be bonded to each other to form a ring.
- R 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or It is a —SO 2 —containing cyclic group optionally having a substituent.
- the aryl group for R 210 includes an unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group.
- the alkyl group for R 210 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
- the alkenyl group for R 210 preferably has 2 to 10 carbon atoms.
- each Y 201 independently represents an arylene group, an alkylene group or an alkenylene group.
- the arylene group for Y 201 include groups obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group for R′ 201 .
- the alkylene group and alkenylene group for Y 201 include groups obtained by removing one hydrogen atom from the groups exemplified as the chain alkyl group and chain alkenyl group for R′ 201 .
- W 201 is a (x+1)-valent, ie divalent or trivalent linking group.
- the divalent linking group in W 201 is preferably a divalent hydrocarbon group which may have a substituent, and may have a substituent exemplified in the above-mentioned "epoxy group-containing group". Groups similar to divalent hydrocarbon groups are preferred.
- the divalent linking group in W 201 may be linear, branched or cyclic, preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting only of an arylene group is preferable.
- the arylene group includes a phenylene group, a naphthylene group and the like, and a phenylene group is particularly preferred.
- the trivalent linking group for W 201 includes a group obtained by removing one hydrogen atom from the divalent linking group for W 201 , a group obtained by further bonding the divalent linking group to the divalent linking group, and the like. mentioned.
- the trivalent linking group for W 201 is preferably a group in which two carbonyl groups are bonded to an arylene group.
- Suitable cations represented by formula (ca-1) include cations represented by formulas (ca-1-1) to (ca-1-24) below.
- R ′′ 201 is a hydrogen atom or a substituent . is.
- R′ 211 is an alkyl group.
- R hal is a hydrogen atom or a halogen atom.
- Suitable cations represented by the formula (ca-2) include diphenyliodonium cations, bis(4-tert-butylphenyl)iodonium cations, and the like.
- Suitable cations represented by formula (ca-3) above specifically include cations represented by formulas (ca-3-1) to (ca-3-6) below.
- Suitable cations represented by formula (ca-4) above specifically include cations represented by formulas (ca-4-1) to (ca-4-2) below.
- R′ 212 is an alkyl group or a hydrogen atom.
- R' 211 is an alkyl group.
- the cation moiety [(Q q+ ) 1/q ] is preferably a cation represented by the general formula (ca-1), and each of the formulas (ca-1-1) to (ca-1-48)
- the cation represented by the formula (ca-1-25) is more preferable, the cation represented by the formula (ca-1-29), the cation represented by the formula (ca-1-35), A cation represented by formula (ca-1-47) and a cation represented by formula (ca-1-48) are more preferable.
- component (I2) is a compound represented by the following general formula (I2-1) or (I2-2). Since component (I2) generates a relatively strong acid upon exposure, when a photocurable composition containing component (I) is used to form a pattern, sufficient sensitivity can be obtained to form a good pattern. is formed.
- R b05 is an optionally substituted fluorinated alkyl group or a fluorine atom.
- a plurality of R b05 may be the same or different.
- q is an integer of 1 or more, and Q q+ is a q-valent organic cation.
- R b06 is an optionally substituted fluorinated alkyl group or a fluorine atom.
- a plurality of R b06 may be the same or different.
- q is an integer of 1 or more, and Q q+ is a q-valent organic cation.
- R b05 is an optionally substituted fluorinated alkyl group or a fluorine atom.
- a plurality of R b05 may be the same or different.
- the fluorinated alkyl group for 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. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms.
- R b05 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, a fluorine atom, a trifluoromethyl group or pentafluoro Ethyl groups are more preferred.
- the anion portion of the compound represented by formula (I2-1) is preferably represented by the following general formula (b0-2a).
- Rbf05 is a fluorinated alkyl group which may have a substituent.
- nb 1 is an integer from 1 to 5; ]
- nb 1 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.
- R b06 is an optionally substituted fluorinated alkyl group or a fluorine atom.
- a plurality of R b06 may be the same or different.
- the fluorinated alkyl group for R b06 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms.
- R b06 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and still more preferably a fluorine atom.
- q is an integer of 1 or more
- Q q+ is a q-valent organic cation.
- Examples of Q q+ include those similar to Q q+ in the above formula (I1).
- the cation represented by general formula (ca-1) is preferable, and the Cations represented by (ca-1-48) are more preferable, respectively, a cation represented by formula (ca-1-25), a cation represented by formula (ca-1-29), a cation represented by formula (ca-1 -35) and the cation represented by the formula (ca-1-47) are more preferred.
- the (I3) component is a compound represented by the following general formula (I3-1) or (I3-2).
- R b11 to R b12 are a cyclic group optionally having a substituent other than a halogen atom, a chain alkyl group optionally having a substituent other than a halogen atom, or a halogen atom It is a chain alkenyl group optionally having a substituent other than .
- m is an integer of 1 or more, and each M m+ is independently an m-valent organic cation.
- R b12 is a cyclic group optionally having a substituent other than a halogen atom, a chain alkyl group optionally having a substituent other than a halogen atom , or a chain alkenyl group which may have a substituent other than a halogen atom, and which is a cyclic group, a chain alkyl group, and a chain alkenyl group in the description of R' 201 described above. , those having no substituents or those having substituents other than halogen atoms.
- R b12 is preferably a chain alkyl group optionally having a substituent other than a halogen atom or an aliphatic cyclic group optionally having a substituent other than a halogen atom.
- the chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms.
- Aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents other than halogen atoms); camphor It is more preferable to be a group obtained by removing one or more hydrogen atoms from etc.
- the hydrocarbon group of R b12 may have a substituent other than a halogen atom , and examples of the substituent include the hydrocarbon group (aromatic hydrocarbon group, aliphatic tricyclic group, chain alkyl group) may have the same substituents other than the halogen atom.
- substituents include the hydrocarbon group (aromatic hydrocarbon group, aliphatic tricyclic group, chain alkyl group) may have the same substituents other than the halogen atom.
- “may have a substituent other than a halogen atom” not only excludes the case of having a substituent consisting only of 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.).
- M m+ is an m-valent organic cation.
- the same cations as the cations represented by the above general formulas (ca-1) to (ca-5) are preferably mentioned, and among these, the above general formula (ca-1) A cation represented by is more preferable.
- at least one of R 201 , R 202 and R 203 in the general formula (ca-1) is an optionally substituted organic group having 16 or more carbon atoms (aryl group, hetero A sulfonium cation (aryl group, alkyl group or alkenyl group) is particularly preferred because it improves resolution and roughness characteristics.
- the number of carbon atoms in the organic group is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18.
- Examples of m+ organic cations include the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38) , (ca-1-46), and (ca-1-47) are preferable, and among them, the cation represented by the above formula (ca-1-29) is particularly preferable.
- R b11 is a cyclic group optionally having a substituent other than a halogen atom, a chain alkyl group optionally having a substituent other than a halogen atom , or a chain alkenyl group which may have a substituent other than a halogen atom, and which is a cyclic group, a chain alkyl group, and a chain alkenyl group in the description of R' 201 described above. , those having no substituents or those having substituents other than halogen atoms.
- R b11 is an aromatic hydrocarbon group optionally having a substituent other than a halogen atom, an aliphatic cyclic group optionally having a substituent other than a halogen atom, or a halogen
- a chain alkyl group which may have substituents other than atoms is preferred. Substituents these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, lactone-containing cyclic groups, ether bonds, ester bonds, and combinations thereof.
- 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 for 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 1 to 5 carbon atoms. is more preferably an alkylene group of
- the alkylene group for V' 101 and V' 102 may be a straight-chain alkylene group or a branched alkylene group, and a straight-chain alkylene group is preferred.
- Specific examples of the alkylene group for V' 101 and V' 102 include a methylene group [-CH 2 -]; -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; ethylene groups [-CH 2 CH 2 -]; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 ) Alkylethylene groups such as CH 2 -; trim
- part of the methylene groups 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 cyclic group is obtained by removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group) of R′ 201 .
- a divalent group is preferred, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferred.
- a phenyl group or a naphthyl group is more preferable as the aromatic hydrocarbon group. More preferably, the aliphatic cyclic group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
- the chain alkyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group.
- nonyl group linear alkyl group such as decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1- Examples include branched chain alkyl groups such as ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.
- R b11 is preferably a cyclic group optionally having a substituent other than a halogen atom. Preferred specific examples of the anion portion of component (I3-2) are shown below.
- M m+ is an m-valent organic cation, which is the same as M m+ in formula (I3-1).
- the component (I) is a cationic polymerization initiator that generates an acid with a pKa (acid dissociation constant) of -5 or less by exposure, in order to increase the elasticity of the resin film and to easily form a fine structure without residue.
- a cationic polymerization initiator that generates an acid having a pKa of preferably ⁇ 6 or less, more preferably ⁇ 8 or less, high sensitivity to exposure can be obtained.
- the lower limit of the pKa of the acid generated by component (I) is preferably -15 or higher.
- pKa acid dissociation constant
- pKa in this specification is a value in 25 degreeC temperature conditions.
- the pKa value can be obtained by measuring by a known method.
- calculated values using known software such as "ACD/Labs" (trade name, manufactured by Advanced Chemistry Development) can be used.
- the component (I) one type may be used alone, or two or more types may be used in combination.
- the component (I) preferably contains at least one selected from the group consisting of the component (I1), the component (I2) and the component (I3), and the component (I1) and (I2) more preferably contains at least one selected from the group consisting of components.
- the content of component (I) is 0.05 to 10 parts by mass with respect to 100 parts by mass of the total content of component (AC) and component (A). preferably 0.1 to 5 parts by mass, even more preferably 0.2 to 3 parts by mass.
- the content of component (I) is at least the lower limit of the preferred range, sufficient sensitivity is obtained, and the lithography properties of the resist pattern are further improved. In addition, the strength of the cured resin film is further enhanced.
- the sensitivity is moderately controlled, and a resist pattern with a good shape can be easily obtained.
- the photocurable composition of the present embodiment may contain other components (optional components) in addition to the components (AC), (A) and (I) described above, if necessary.
- Photocurable compositions of embodiments optionally include compatible additives such as metal oxides (M), sensitizer components, solvents, additional resins to improve film performance, dissolution inhibitors, Agents, basic compounds, plasticizers, stabilizers, colorants, antihalation agents and the like can be added as appropriate.
- compatible additives such as metal oxides (M), sensitizer components, solvents, additional resins to improve film performance, dissolution inhibitors, Agents, basic compounds, plasticizers, stabilizers, colorants, antihalation agents and the like can be added as appropriate.
- Such particulate component (M) preferably comprises a particle group having a volume average particle diameter of 5 to 40 nm, more preferably comprising a particle group having a volume average particle diameter of 5 to 30 nm. More preferably, it consists of a group of particles with a diameter of 10 to 20 nm.
- the photocurable composition of this embodiment may further contain a sensitizer component.
- the sensitizer component is not particularly limited as long as it can absorb energy due to exposure and transmit the energy to other substances.
- Specific examples of sensitizer components include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetophene-based photosensitizers, and 1,5-dihydroxynaphthalene.
- naphthalene-based photosensitizers phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, biacetyl, eosin, rose bengal, pyrene, phenothiazine, and known photosensitizers such as anthrone. can be used.
- the photocurable composition of the present embodiment may further contain a solvent (hereinafter sometimes referred to as "(S) component").
- a solvent hereinafter sometimes 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.
- propylene glycol dipropylene glycol
- monoalkyl ethers such as monomethyl ethers, monoethyl ethers, monopropyl ethers and monobutyl ethers of the polyhydric alcohols or compounds having an ester bond, or ether bonds such as monophenyl ethers
- PGMEA propylene glycol monomethyl ether acetate
- PGME propylene glycol monomethyl ether
- PGME propylene glycol monomethyl ether
- PGME propylene glycol monomethyl ether
- PGME propylene glycol monomethyl ether
- PGME propylene glycol monomethyl ether
- PGME propylene glycol monomethyl ether
- PGME prop
- the (S) component may be used singly or as a mixed solvent of two or more.
- the amount used is not particularly limited, and is appropriately set according to the coating film thickness at a concentration at which the photocurable composition can be coated onto a substrate or the like without dripping.
- the (S) component can be used so that the solid content concentration is 50% by mass or more, or the (S) component can be used so that the solid content concentration is 60% by mass or more.
- the aspect (namely, the aspect whose solid content concentration is 100 mass %) which does not contain (S) component substantially can be employ
- the photocurable composition of the present embodiment has a viscosity at 23° C. of, for example, 10 to 5000 mPa ⁇ s, may be 30 to 3000 mPa ⁇ s, or may be 50 to 2000 mPa ⁇ s. There may be.
- the photocurable composition of this embodiment described above contains an acrylic resin (AC), an epoxy group-containing compound (A), and a cationic polymerization initiator (I).
- an acrylic resin AC
- an epoxy group-containing compound A
- a cationic polymerization initiator I
- the (AC) component one having a glass transition point of 0° C. or lower is employed. This improves the properties of the cured film and enhances the adhesiveness to the object.
- the (AC) component one having a specific content ratio (greater than 0% by mass and less than 50% by mass) of a structural unit (ac1) derived from an epoxy group-containing acrylic monomer is employed.
- ac1 structural unit derived from an epoxy group-containing acrylic monomer
- the photocurable composition of the present embodiment in pattern formation, a high-resolution pattern can be formed in a favorable shape, and lithography properties can be improved.
- the photocurable composition of the present embodiment is used as a photocurable adhesive material used in the production of electronic components (for example, MEMS, bio, etc.) that require various properties such as compatibility between adhesiveness and chemical resistance. Useful.
- the pattern forming method of the present embodiment includes a step of forming a photocurable film on a support using the photocurable composition of the above-described embodiment (hereinafter referred to as a “film forming step”); A step of exposing the film (hereinafter referred to as “exposure step”), and a step of developing the photocurable film after exposure with a developer containing an organic solvent to form a negative pattern (hereinafter referred to as "development step”). ) and
- the pattern forming method of this embodiment can be performed, for example, as follows.
- the photocurable composition of the embodiment described above is applied onto a support by a known method such as a spin coating method, a roll coating method, or a screen printing method, followed by baking (post-apply baking (PAB)). , for example, at a temperature of 50 to 150° C. for 2 to 60 minutes to form a photocurable film.
- a known method such as a spin coating method, a roll coating method, or a screen printing method
- baking post-apply baking (PAB)
- PAB post-apply baking
- the support is not particularly limited, and a conventionally known one can be used. Examples thereof include substrates for electronic parts, substrates having predetermined wiring patterns formed thereon, and the like. More specifically, metals such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO 3 ), niobium, lithium niobate (LiNbO 3 ), palladium, titanium tungsten, copper, chromium, iron, aluminum, etc. A substrate, a glass substrate, and the like can be mentioned. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
- the film thickness of the photocurable film formed from the photocurable composition is not particularly limited, it is preferably about 10 to 50 ⁇ m.
- the formed photocurable film is exposed through a mask having a predetermined pattern (mask pattern) using a known exposure apparatus, or is directly irradiated with an electron beam without a mask pattern. Selective exposure such as drawing is performed. After performing the selective exposure, baking (post-exposure bake (PEB)) treatment is optionally performed, for example, at a temperature condition of 80 to 150 ° C. for 40 to 1200 seconds, preferably 40 to 1000 seconds, more preferably Apply for 60-900 seconds.
- PEB post-exposure bake
- the wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays having a wavelength of 300 to 500 nm, g-line, h-line, i-line (wavelength 365 nm), or visible light is selectively irradiated (exposed).
- Low-pressure mercury lamps, high-pressure mercury lamps, extra-high pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as sources of these radiations.
- Radiation here means ultraviolet rays, visible rays, deep ultraviolet rays, X-rays, electron beams, and the like.
- the dose of radiation varies depending on the type and blending amount of each component in the composition, the film thickness of the coating film, etc., but is 100 to 2000 mJ/cm 2 in the case of using an ultra-high pressure mercury lamp, for example.
- the method of exposing the photocurable film may be normal exposure (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion lithography.
- the photocurable film after the exposure step has high transparency and, for example, a haze value when irradiated with i-line (wavelength 365 nm) is preferably 3% or less, more preferably 1.0 to 2.7%. .
- the haze value of the photocurable film after the exposure process is measured using a method based on JIS K 7136 (2000).
- the photocurable film after exposure is developed with a developer containing an organic solvent (organic developer). After development, a rinse treatment is preferably performed. Baking (post-baking) may be performed as necessary.
- the organic solvent contained in the organic developer may be any one capable of dissolving the (A) component and (AC) component before exposure, and can be appropriately selected from known organic solvents.
- Specific examples include polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
- ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone.
- methyl amyl ketone (2-heptanone) is preferable as the ketone solvent.
- ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, Ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol mono Ethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl
- nitrile-based solvents examples include acetonitrile, propionitrile, valeronitrile, and butyronitrile.
- additives can be added to the organic developer as needed.
- additives include surfactants.
- the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used.
- a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
- a surfactant When a surfactant is blended, its blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.5% by mass, relative to the total amount of the organic developer. 5% by mass is more preferred.
- the development treatment can be carried out by a known developing method.
- a stationary method (paddle method), a method of spraying the developer onto the surface of the support (spray method), and a developer coating nozzle that is scanned at a constant speed onto the support rotating at a constant speed to apply the developer.
- a method of continuously dispensing (dynamic dispensing method) and the like can be mentioned.
- Rinsing treatment (cleaning treatment) using a rinse liquid can be performed by a known rinsing method.
- the rinsing method include a method of continuously applying a rinse solution onto a support rotating at a constant speed (rotation coating method), a method of immersing a support in a rinse solution for a given period of time (dip method), A method of spraying a rinsing liquid onto the support surface (spray method) and the like can be mentioned.
- a rinsing liquid containing an organic solvent it is preferable to use a rinsing liquid containing an organic solvent.
- a pattern can be formed by the film formation process, the exposure process, and the development process described above.
- the photocurable composition of the above-described embodiment is used, so that a resin pattern with improved chemical resistance, in which peeling due to treatment with a chemical solution such as a solvent is suppressed, can be obtained. can be formed.
- the resin pattern is formed with high resolution and good shape, and is excellent in lithography properties.
- the cured film of the present embodiment is obtained by curing the photocurable composition of the embodiment described above.
- the method for producing a cured film of the present embodiment includes the step (i) of forming a photocurable film on a support using the photocurable composition of the embodiment described above, and curing the photocurable film. and a step (ii) of obtaining a cured film.
- the operation of step (i) can be performed in the same manner as in the [film formation step] described above.
- the baking treatment can be performed, for example, at a temperature of 80 to 150° C. for 40 to 600 seconds.
- the curing treatment in step (ii) can be performed, for example, at a temperature of 100 to 250° C. for 0.5 to 2 hours.
- the method for producing a cured film of the embodiment may have other steps in addition to steps (i) and (ii).
- the above-described [exposure step] may be included between step (i) and step (ii), and the photocurable film formed in step (i) is selectively exposed to light
- a cured film can also be obtained by curing a photocurable film (pre-cured film) that has been subjected to a baking (PEB) treatment, if necessary.
- PEB baking
- Acrylic resins (AC)-1 to (AC)-14 were obtained by performing known radical polymerization using “monomers from which structural units are derived” shown in Table 1.
- Table 1 shows the ratio of each structural unit constituting the acrylic resin, the glass transition point Tg (° C.) of the acrylic resin as characteristics of the acrylic resin, the content ratio (% by mass) of the structural unit (ac1) in the acrylic resin, and the weight average molecular weight Mw of the acrylic resin.
- Tg Glass transition point (° C.) of the copolymer that is an acrylic resin
- Tg1 Glass transition point (°C) of homopolymer consisting of repeating structure of structural unit (1) derived from monomer (1)
- Tg2 Glass transition point (°C) of homopolymer consisting of repeating structure of structural unit (2) derived from monomer (2)
- the glass transition point Tg (° C.) of acrylic resin (AC)-2 was calculated as follows.
- Acrylic resin (AC)-2 is a copolymer of structural units derived from 2-methoxyethyl acrylate and structural units derived from n-butyl acrylate.
- the monomer (1) is 2-methoxyethyl acrylate
- the glass transition point of the homopolymer consisting of the repeating structure of the structural unit (1) is ⁇ 50° C.
- the proportion of the structural unit (1) is 73% by mass.
- the monomer (2) is n-butyl acrylate
- the homopolymer consisting of the repeating structure of the structural unit (2) has a glass transition point of ⁇ 56° C.
- the copolymerization composition ratio of the acrylic resin (proportion (% by mass) of each structural unit constituting the acrylic resin) was determined by 13 C-NMR.
- the weight average molecular weight (Mw) of the acrylic resin was obtained by gel permeation chromatography GPC measurement and shown as a standard polystyrene conversion value.
- (A1)-1 A solid novolac epoxy resin represented by the following chemical formula (anv0-1). Trade name “jER-157S70”, manufactured by Mitsubishi Chemical Corporation. Softening point 70°C, glass transition point 210°C, epoxy equivalent 200-220g/eq.
- (A2)-1 A solid bisphenol epoxy resin represented by the following chemical formula (abp1-0). Trade name “jER-1002”, manufactured by Mitsubishi Chemical Corporation. Softening point 78°C, weight average molecular weight 1200, epoxy equivalent 600-700 g/eq.
- (A2)-2 Solid bisphenol type epoxy resin represented by the following chemical formula (abp1-0). Trade name "jER-1003”, manufactured by Mitsubishi Chemical Corporation. Softening point 89°C, weight average molecular weight 1300, epoxy equivalent 670-770 g/eq.
- (I)-1 A cationic polymerization initiator represented by the following chemical formula (I2-1-2).
- shear strength Under room temperature (23 ° C.) conditions, using a bond tester (XYZTEC, Condor Sigma), the substrate for measurement is fixed, a shearing force is applied to the 5 mm square silicon chip portion, and from the cured film A force (shear strength, N/mm 2 ) required to peel off a 5 mm square silicon chip was measured.
- Adhesiveness was evaluated by observing the bonding state according to the following evaluation criteria, using the shear strength between the cured film and the 5 mm square silicon chip as an index. Evaluation Criteria ⁇ : Shear strength was 5 N/mm 2 or more, and both were firmly joined. x: The shear strength was less than 5 N/mm 2 , the adhesive strength was weak, and the 5 mm square silicon chip was easily peeled off from the cured film.
- DMSO dimethyl sulfoxide
- NMP N-methylpyrrolidone
- TMAHaq. 2% tetramethylammonium hydroxide aqueous solution
- a photocurable resin pattern was formed by the following film formation process, exposure process and development process.
- Film formation process The photocurable composition of each example was applied onto a silicon substrate by spin coating. Next, baking treatment was performed in an oven at 60° C. for 5 minutes, 70° C. for 5 minutes, and 80° C. for 10 minutes in this order to form a photocurable film having a thickness of 20 ⁇ m.
- Exposure process Next, the photocurable film was irradiated with g, h and i rays using an exposure machine (Prisma ghi). Next, the photocurable film after exposure was subjected to post-exposure heating on a hot plate at 90° C. for 5 minutes.
- L/S pattern a line-and-space pattern having a line width of 100 ⁇ m and a space width of 300 ⁇ m as a photocurable resin pattern through the above-described film formation process, exposure process and development process.
- the photocurable resin pattern was immersed in the mixed solvent at room temperature (23° C.) for 30 minutes. Thereafter, chemical resistance was evaluated by observing the peeling state of the photocurable resin pattern from the silicon substrate according to the following evaluation criteria. Evaluation Criteria ⁇ : No peeling of the photocurable resin pattern. ⁇ : Partial peeling of the photocurable resin pattern. x: There is peeling in the whole photocurable resin pattern.
- Pattern formation was performed using the photocurable composition of each example.
- Film formation process The photocurable composition of each example was applied onto a silicon substrate by spin coating. Next, baking treatment was performed in an oven at 60° C. for 5 minutes, 70° C. for 5 minutes, and 80° C. for 10 minutes in this order to form a photocurable film having a thickness of 20 ⁇ m.
- Exposure process Next, the photocurable film was irradiated with g, h and i rays using an exposure machine (Prisma ghi). Next, the photocurable film after exposure was subjected to post-exposure heating on a hot plate at 90° C. for 5 minutes.
- L/S pattern a line-and-space pattern having a line width of 100 ⁇ m and a space width of 300 ⁇ m through the film formation process, exposure process and development process described above. Then, the lithography characteristics were evaluated by observing the state of the L/S pattern according to the following evaluation criteria. Evaluation Criteria ⁇ : A line with a width of 100 ⁇ m was formed in a good shape. x: The shape of the L/S pattern was unsatisfactory.
- the photocurable compositions of Examples 1 to 11 to which the present invention is applied can improve the adhesion to the object when formed into a cured film, and have excellent chemical resistance. can be confirmed. In addition, it can be confirmed that the photocurable compositions of Examples 1 to 11 form patterns of good shape and have excellent lithography properties. On the other hand, the photocurable compositions of Comparative Examples 1 to 7, which are outside the scope of the present invention, gave poor evaluation results in one or both of adhesiveness and chemical resistance.
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Abstract
Description
本願は、2021年12月20日に日本に出願された、特願2021-206080号に基づき優先権主張し、その内容をここに援用する。
電極を囲むように配線基板上に感光性組成物を塗布した後、フォトマスクを介して露光、ポストエクスポージャーベーク(PEB)、現像をこの順に行い、スペーサとなる側壁を形成する。次に、前記側壁上に、天板部を接合することにより、中空構造体を作製する。次いで、モールド成型することにより、中空パッケージが製造される。
上記の中空パッケージを製造する際、感光性組成物は、スペーサとなる側壁の材料として用いられている。この側壁においては、天板部との接着性が必要とされる。また、電子部品の製造では、薬液処理工程が含まれる場合が多く、この側壁においてはその薬液に対する耐薬品性も必要とされる。
しかしながら、接着性と耐薬品性との両立の点で、従来の光硬化性接着材料においては、更なる特性の向上が求められる。
「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。
本実施形態の光硬化性組成物は、アクリル樹脂(AC)と、エポキシ基含有化合物(A)(但し、前記アクリル樹脂(AC)に該当するものを除く)と、カチオン重合開始剤(I)と、を含有する。
以下、アクリル樹脂(AC)、エポキシ基含有化合物(A)、カチオン重合開始剤(I)をそれぞれ(AC)成分、(A)成分、(I)成分ともいう。
本実施形態の光硬化性組成物が含有するアクリル樹脂(AC)は、ガラス転移点が0℃以下であり、かつ、エポキシ基含有アクリルモノマーから誘導される構成単位(ac1)を有する。
前記構成単位(ac1)の含有割合は、前記(AC)成分を構成する全構成単位の合計(100質量%)に対して、0質量%超え50質量%未満である。すなわち、(AC)成分は、構成単位(ac1)と、これ以外の構成単位(ac2)とを有する。
「エポキシ基含有アクリルモノマー」とは、側鎖にエポキシ基を含むアクリル酸エステルをいう。
「アクリル酸エステル」は、α位の炭素原子に結合した水素原子が置換基で置換されていてもよい。該α位の炭素原子に結合した水素原子を置換する置換基(Rαx)は、水素原子以外の原子又は基である。なお、アクリル酸エステルのα位の炭素原子とは、特に断りがない限り、アクリル酸のカルボニル基が結合している炭素原子のことである。
置換基(Rαx)としては、炭素原子数1~5のアルキル基、ハロゲン原子又は炭素原子数1~5のハロゲン化アルキル基などが挙げられる。
1/(Tg+273)
={W1/(Tg1+273)+W2/(Tg2+273)+・・・}/100
Tg:アクリル樹脂である共重合体のガラス転移点(℃)
Tg1:モノマー(1)から誘導される構成単位(1)の繰り返し構造からなるホモポリマーのガラス転移点(℃)
Tg2:モノマー(2)から誘導される構成単位(2)の繰り返し構造からなるホモポリマーのガラス転移点(℃)
W1:アクリル樹脂を構成する構成単位(1)の割合(質量%)
W2:アクリル樹脂を構成する構成単位(2)の割合(質量%)
W1+W2+・・・=100
モノマー(1)をアクリル酸2-メトキシエチルとする。このモノマー(1)から誘導される構成単位(1)の繰り返し構造からなるホモポリマーのガラス転移点は-50℃であり、構成単位(1)の割合を73質量%とする。
モノマー(2)をアクリル酸n-ブチルとする。このモノマー(2)から誘導される構成単位(2)の繰り返し構造からなるホモポリマーのガラス転移点は-56℃であり、構成単位(2)の割合を27質量%とする。
かかる構成単位(1)と構成単位(2)との共重合体であるアクリル樹脂のガラス転移点Tg(℃)は、下式より算出される。
1/(Tg+273)
={73/(-50+273)+27/(-56+273)}/100
Tg≒-52℃
(AC)成分のガラス転移点Tgが、前記範囲の上限値以下であれば、硬化膜とした際に対象物との接着性を高められ、また、信頼性が向上する。一方、前記範囲の下限値以上であれば、樹脂パターンの耐薬品性をより高められ、また、パターン形成の際のリソグラフィー特性が向上する。
(AC)成分は、エポキシ基含有アクリルモノマーから誘導される構成単位(ac1)を有する。
「エポキシ基含有アクリルモノマーから誘導される構成単位」とは、エポキシ基含有アクリルモノマーのエチレン性二重結合が開裂して構成される構成単位を意味する。
脂環式エポキシ基の基本骨格となる脂環式基としては、単環であっても多環であってもよい。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いてもよい。
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あってもよく、芳香族炭化水素基であってもよい。
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。
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、炭素原子数が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、炭素原子数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、炭素原子数が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、炭素原子数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、炭素原子数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原子数は、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、置換基を有していてもよく、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原子数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、炭素原子数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、炭素原子数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、炭素原子数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、ハロゲン原子およ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、炭素原子およ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いてもよい。該置換基(アルキル基、アシル基等)は、炭素原子数が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およびY22は、それぞれ独立して、置換基を有していてもよい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「置換基を有していてもよい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、炭素原子数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、炭素原子数1~5の直鎖状のアルキル基が好ましく、炭素原子数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。
Rにおける、炭素原子数1~5のハロゲン化アルキル基は、前記炭素原子数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、炭素原子数1~5のアルキル基又は炭素原子数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より好ましい。
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。
前記脂肪族炭化水素基としては、直鎖状もしくは分岐鎖状の脂肪族炭化水素基、構造中に環を含む脂肪族炭化水素基、又は、直鎖状もしくは分岐鎖状の脂肪族炭化水素基と構造中に環を含む脂肪族炭化水素基とを組み合わせた基が挙げられる。
下記の式中、Rαは、水素原子、メチル基又はトリフルオロメチル基を示す。
Ra51は、炭素原子数1~8の2価の炭化水素基を示す。Ra52は、炭素原子数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。
構成単位(ac1)としては、上記一般式(a1-1)で表されるエポキシ基含有単位が好ましい。
構成単位(ac1)の含有割合が、前記範囲の下限値超えであれば、樹脂パターンの耐薬品性をより高められ、硬化膜の強度が高まり、また、パターン形成の際のリソグラフィー特性が向上する。一方、前記範囲の上限値未満であれば、樹脂パターンの耐薬品性をより高められ、硬化膜とした際に対象物との接着性を高められ、また、信頼性が向上する。
(AC)成分は、上述の構成単位(ac1)に加え、これ以外の構成単位(ac2)を有する。
構成単位(ac2)としては、構成単位(ac1)との共重合体である(AC)成分のガラス転移点が0℃以下となるものであればよく、エポキシ基含有アクリルモノマー以外のアクリル酸エステルから誘導される構成単位、アクリル酸から誘導される構成単位、その他重合性化合物から誘導される構成単位などが挙げられる。
なお、「(メタ)アクリル酸」との表記は、アクリル酸及びメタクリル酸の一方又は両方を意味する。
上述した中でも、構成単位(ac2)が由来するモノマーとしては、(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸ヒドロキシアルキルエステル、(メタ)アクリル酸アルコキシアルキルエステルが好ましい。
(メタ)アクリル酸アルキルエステルにおいて、アルキルエステル部のアルキルの炭素原子数は、好ましくは1~5である。
(メタ)アクリル酸ヒドロキシアルキルエステルにおいて、ヒドロキシアルキルエステル部のアルキルの炭素原子数は、好ましくは1~5である。
(メタ)アクリル酸アルコキシアルキルエステルにおいて、アルコキシアルキルエステル部のアルコキシの炭素原子数は、好ましくは1~3であり、アルキルの炭素原子数は、好ましくは1~5である。
構成単位(ac2)の含有割合が、前記範囲の下限値以上であれば、樹脂パターンの耐薬品性をより高められる。一方、前記範囲の上限値以下であれば、樹脂パターンの耐薬品性をより高められ、また、パターン形成の際のリソグラフィー特性が向上する。
かかる(AC)成分は、「アクリル酸エステル」から誘導される構成単位の含有割合が、(AC)成分を構成する全構成単位の合計(100質量%)に対して、50質量%以上であることが好ましく、80質量%以上であることがより好ましく、90質量%以上であることがさらに好ましく、100質量%であってもよい。
構成単位(ac1)の含有割合が0質量%超え50質量%未満である共重合体の好ましいものとしては、構成単位(ac1)と(メタ)アクリル酸アルキルエステルから誘導される構成単位とを有する共重合体、構成単位(ac1)と(メタ)アクリル酸ヒドロキシアルキルエステルから誘導される構成単位とを有する共重合体、構成単位(ac1)と(メタ)アクリル酸アルコキシアルキルエステルから誘導される構成単位とを有する共重合体が挙げられる。
あるいは、構成単位(ac1)の含有割合が0質量%超え50質量%未満である共重合体の好ましいものとしては、構成単位(ac1)と(メタ)アクリル酸アルコキシアルキルエステルから誘導される構成単位と(メタ)アクリル酸アルキルエステルから誘導される構成単位とを有する共重合体、構成単位(ac1)と(メタ)アクリル酸アルコキシアルキルエステルから誘導される構成単位と(メタ)アクリル酸ヒドロキシアルキルエステルから誘導される構成単位とを有する共重合体、構成単位(ac1)と(メタ)アクリル酸ヒドロキシアルキルエステルから誘導される構成単位と(メタ)アクリル酸アルキルエステルから誘導される構成単位とを有する共重合体が挙げられる。
(AC)成分の分散度(Mw/Mn)は、特に限定されないが、1.0~3.0が好ましく、1.0~2.5がより好ましく、1.0~2.0が特に好ましい。Mnは数平均分子量を示す。
本実施形態の光硬化性組成物が含有するエポキシ基含有化合物(A)は、露光によってネガ型のパターンを形成するのに充分なエポキシ基を1分子中に有する化合物が挙げられる。
かかる(A)成分としては、ノボラック型エポキシ樹脂(以下「(A1)成分」ともいう)、ビスフェノール型エポキシ樹脂(以下「(A2)成分」ともいう)、脂肪族エポキシ樹脂等が挙げられる。
前記(A)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。
但し、前記(A)成分は、上述のアクリル樹脂(AC)に該当するものを除くものとする。
ノボラック型エポキシ樹脂((A1)成分)としては、下記一般式(anv0)で表されるエポキシ樹脂が好適に挙げられる。
なかでもRp1、Rp2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特に好ましい。
式(anv0)中、複数のRp1は、互いに同一であってもよく異なっていてもよい。複数のRp2は、互いに同一であってもよく異なっていてもよい。
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。
REPのエポキシ基含有基についての説明は、上述の「エポキシ基含有基」についての説明と同様である。
なかでも、REPにおけるエポキシ基含有基としては、グリシジル基が好ましい。
Ra22、Ra23のハロゲン原子は、塩素原子又は臭素原子であることが好ましい。
前記式(anv1)中、REPは、前記式(anv0)中のREPと同様であって、グリシジル基が好ましい。
この他の構成単位としては、例えば、下記一般式(anv2)~(anv3)でそれぞれ表される構成単位が挙げられる。
該直鎖状のアルキル基は、炭素原子数が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、炭素原子数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、炭素原子数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。芳香環の炭素原子数は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原子数は、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。
炭素原子数1~5のアルキル基、ハロゲン原子は、それぞれ、前記Ra22、Ra23と同様である。
本実施形態の光硬化性組成物中、(A1)成分の含有量は、(A)成分の総量100質量%に対して、25質量%以上であることが好ましく、40質量%以上であることがより好ましく、50質量%以上でもよいし、75質量%以上でもよいし、90質量%以上でもよいし、100質量%でもよい。
ビスフェノール型エポキシ樹脂(以下「(A2)成分」ともいう)としては、ビスフェノール骨格を含む構成単位を有する樹脂であればよく、そのなかでも固形ビスフェノール型エポキシ樹脂が好ましい。
固形ビスフェノール型エポキシ樹脂とは、25℃において固体状の、ビスフェノール骨格を含む構成単位を有する樹脂をいう。
(A2)成分におけるエポキシ当量は、例えば、500g/eq.以上であることが好ましく、550~1200g/eq.がより好ましく、600~1000g/eq.がさらに好ましい。
前記式(abp1)中、Ra31、Ra32における炭素原子数1~5のアルキル基は、前記式(anv0)中のRp1、Rp2における炭素原子数1~5のアルキル基と同様である。なかでもRa31、Ra32としては、それぞれ、水素原子又はメチル基が好ましい。
Ra31、Ra32における炭素原子数1~5のフッ素化アルキル基は、前記のRa31、Ra32における炭素原子数1~5の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が挙げられる。
前記式(abp1)中、na31は、1~50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。
本実施形態の光硬化性組成物中、(A2)成分の含有量は、(A)成分の総量100質量%に対して、50質量%以上であることが好ましく、60質量%以上であることがより好ましく、70質量%以上でもよいし、80質量%以上でもよいし、90質量%以上でもよいし、100質量%でもよい。
かかる質量比が前記の好ましい範囲内であれば、耐薬品性が向上しやすくなり、また、解像性がより高められる。
脂肪族エポキシ樹脂としては、例えば、下記一般式(ta1)で表される化合物(以下この化合物を「(A3)成分」ともいう)が好適に挙げられる。
(A3)成分としては、1種を単独で用いてもよく、2種以上を併用してもよい。
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価の連結基が好適なものとして挙げられる。
ここでの、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、上述の「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価の連結基とそれぞれ同様であり、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、炭素原子数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。
下記化学式(A4-1)で表される化合物として使用可能な市販品は、例えば、TECHMORE VG-3101L(プリンテック株式会社製)等が挙げられる。
下記化学式(A4-2)で表される化合物として使用可能な市販品は、例えば、ショウフリー(登録商標)BATG(昭和電工株式会社製)等が挙げられる。
この中でも、(A)成分としては、固形ビスフェノール型エポキシ樹脂と(A1)成分とを含むものがより好ましく、一般式(abp1)で表されるエポキシ樹脂と、一般式(anv0)で表されるエポキシ樹脂とを含むものがさらに好ましい。
本実施形態の光硬化性組成物中、(A)成分の含有量は、光硬化性組成物の固形分総量(100質量%)に対して、40~99質量%であることが好ましく、50~95質量%であることがより好ましく、60~90質量%であることがさらに好ましい。
かかる質量比が、前記の好ましい範囲の下限値以上であると、樹脂パターンの耐薬品性が高められやすくなり、形成される硬化膜の強度が充分に高められ、一方、前記の好ましい範囲の上限値以下であると、硬化膜とした際に対象物との接着性をより高められやすくなる。
本実施形態の光硬化性組成物が含有するカチオン重合開始剤(I)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。
この(I)成分としては、オニウムボレート塩(以下「(I1)成分」ともいう)、後述の一般式(I2-1)又は(I2-2)で表される化合物(以下「(I2)成分」ともいう)、後述の一般式(I3-1)又は(I3-2)で表される化合物(以下「(I3)成分」ともいう)が挙げられる。
オニウムボレート塩((I1)成分)は、露光により比較的に強い酸を発生する。このため、(I1)成分を含有する光硬化性組成物を用いてパターンを形成することにより、充分な感度が得られて良好なパターンが形成される。また、(I1)成分の使用は、毒性や金属腐食のおそれも低い。
(I1)成分としては、例えば、下記一般式(I1)で表される化合物が好適に挙げられる。
前記式(I1)中、Rb01~Rb04におけるアリール基は、炭素原子数が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、炭素原子数は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原子数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原子数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。
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。
前記式(I1)中、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、および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、および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、炭素原子数1~30のものが好ましい。
R201~R207、およびR211~R212におけるアルケニル基としては、炭素原子数が2~10であることが好ましい。
R201~R207、および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、下記の式(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)の炭素原子数は、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、炭素原子数が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、炭素原子数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、炭素原子数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、炭素原子数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、炭素原子数が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、炭素原子数が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、炭素原子数が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、炭素原子数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、炭素原子数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、炭素原子数が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、上述の「エポキシ基含有基」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。
(I2)成分は、下記一般式(I2-1)又は(I2-2)で表される化合物である。
(I2)成分は、露光により比較的に強い酸を発生するため、(I)成分を含有する光硬化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。
前記式(I2-1)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。
式(b0-2a)中、nb1は、1~4の整数が好ましく、2~4の整数がより好ましく、3が最も好ましい。
Rb06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、Rb06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、フッ素原子がさらに好ましい。
式(I2-1)、式(I2-2)中、qは1以上の整数であって、Qq+は、q価の有機カチオンである。
このQq+としては、上記式(I1)中のQq+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-1-48)でそれぞれ表されるカチオンがより好ましく、式(ca-1-25)で表されるカチオン、式(ca-1-29)で表されるカチオン、式(ca-1-35)で表されるカチオン、式(ca-1-47)で表されるカチオンがさらに好ましい。
(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、炭素原子数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原子数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)における炭素原子数は、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。
なお、下記一般式(y-al-1)~(y-al-7)において、上記式(I3-2)中のRb11と結合するのが、下記一般式(y-al-1)~(y-al-7)中のV’101である。
V’101および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、炭素原子数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、炭素原子数が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。
以下に、(I3-2)成分のアニオン部の好ましい具体例を示す。
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。
本実施形態の光硬化性組成物において、(I)成分は、(I1)成分、(I2)成分及び(I3)成分からなる群より選択される少なくとも一種を含むことが好ましく、(I1)成分及び(I2)成分からなる群より選択される少なくとも一種を含むことがより好ましい。
(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、充分な感度が得られて、レジストパターンのリソグラフィー特性がより向上する。加えて、樹脂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、良好な形状のレジストパターンが得られやすくなる。
本実施形態の光硬化性組成物は、上述した(AC)成分、(A)成分及び(I)成分以外に、必要に応じてその他成分(任意成分)を含有してもよい。
実施形態の光硬化性組成物には、所望により、混和性のある添加剤、例えば金属酸化物(M)、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。
本実施形態の光硬化性組成物は、(AC)成分、(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。(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。
(M)成分の形状は、粒子状であることが好ましい。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。
本実施形態の光硬化性組成物は、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。
本実施形態の光硬化性組成物は、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。
例えば、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、あるいは、固形分濃度が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。
本実施形態の光硬化性組成物は、接着性と耐薬品性との両立など、種々の特性が求められる電子部品(例えばMEMS、バイオ用など)の製造において使用される光硬化性接着材料として有用である。
本実施形態のパターン形成方法は、上述した実施形態の光硬化性組成物を用いて、支持体上に光硬化性膜を形成する工程(以下「膜形成工程」という)と、前記光硬化性膜を露光する工程(以下「露光工程」という)と、前記露光後の光硬化性膜を、有機溶剤を含有する現像液で現像して、ネガ型パターンを形成する工程(以下「現像工程」という)と、を有する。
本実施形態のパターン形成方法は、例えば以下のようにして行うことができる。
まず、支持体上に、上述した実施形態の光硬化性組成物を、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、光硬化性膜を形成する。
配線パターンの材料としては、例えば銅、アルミニウム、ニッケル、金等が使用可能である。
次に、形成された光硬化性膜に対し、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。
これらの放射線の線源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、アルゴンガスレーザーなどを用いることができる。
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。
かかる露光工程後の光硬化性膜のヘーズ値は、JIS K 7136(2000)に準拠した方法を用いて測定される。
次に、前記露光後の光硬化性膜を、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。
本実施形態の硬化膜は、上述した実施形態の光硬化性組成物が硬化したものである。
本実施形態の硬化膜の製造方法は、上述した実施形態の光硬化性組成物を用いて、支持体上に光硬化性膜を形成する工程(i)と、前記光硬化性膜を硬化させて硬化膜を得る工程(ii)と、を有する。
工程(i)の操作は、上述した[膜形成工程]と同様にして行うことができる。ベーク処理は、例えば温度80~150℃の温度条件にて40~600秒間の条件で行うことができる。
工程(ii)での硬化処理は、例えば温度100~250℃、0.5~2時間の条件で行うことができる。
上述した実施形態の硬化膜の製造方法によれば、上述した実施形態の光硬化性組成物が用いられているため、対象物とされるシリコンチップ等の電子部品との接着性が高められた硬化膜を製造することができる。
表1に示す「構成単位が由来するモノマー」を用い、公知のラジカル重合を行うことにより、アクリル樹脂(AC)-1~(AC)-14をそれぞれ得た。
1/(Tg+273)
={W1/(Tg1+273)+W2/(Tg2+273)+・・・}/100
Tg:アクリル樹脂である共重合体のガラス転移点(℃)
Tg1:モノマー(1)から誘導される構成単位(1)の繰り返し構造からなるホモポリマーのガラス転移点(℃)
Tg2:モノマー(2)から誘導される構成単位(2)の繰り返し構造からなるホモポリマーのガラス転移点(℃)
W1:アクリル樹脂を構成する構成単位(1)の割合(質量%)
W2:アクリル樹脂を構成する構成単位(2)の割合(質量%)
W1+W2+・・・=100
アクリル樹脂(AC)-2は、アクリル酸2-メトキシエチルから誘導される構成単位と、アクリル酸n-ブチルから誘導される構成単位と、の共重合体である。
モノマー(1)をアクリル酸2-メトキシエチルとすると、構成単位(1)の繰り返し構造からなるホモポリマーのガラス転移点は-50℃、構成単位(1)の割合は73質量%である。
モノマー(2)をアクリル酸n-ブチルとすると、構成単位(2)の繰り返し構造からなるホモポリマーのガラス転移点は-56℃、構成単位(2)の割合は27質量%である。
アクリル樹脂(AC)-2のガラス転移点Tg(℃)は、下式より算出される。
1/(Tg+273)
={73/(-50+273)+27/(-56+273)}/100
Tg≒-52℃
該アクリル樹脂の重量平均分子量(Mw)は、ゲル浸透クロマトグラフィーGPC測定により求め、標準ポリスチレン換算値として示した。
(実施例1~11、比較例1~7)
表2及び表3に示す各成分を、メチルエチルケトンに混合して溶解し、PTFEフィルター(孔径1μm、PALL社製)を用いて濾過を行い、各例の光硬化性組成物(固形分濃度73質量%の溶液、23℃における粘度1500mPa・s)をそれぞれ調製した。
(A2)-2:下記化学式(abp1-0)で表される固形ビスフェノール型エポキシ樹脂。商品名「jER-1003」、三菱ケミカル株式会社製。軟化点89℃、重量平均分子量1300、エポキシ当量670~770g/eq.
各例の光硬化性組成物について、以下に示す評価方法により、接着性、耐薬品性、リソグラフィー特性(リソ特性)をそれぞれ評価した。これらの結果を表4及び表5に示した。
測定用基板の作製:
シリコン基板上に、各例の光硬化性組成物をそれぞれ、スピンコートにより塗布した後、オーブンにて、60℃で5分間、70℃で5分間、80℃で10分間のベーク処理をこの順に行うことにより、膜厚20μmの硬化膜を形成した。
次いで、シリコン基板上に形成された硬化膜と、5mm角シリコンチップとを貼り合わせた。この後、チップボンダー(TRESKY社製、ダイボンダー)を用い、150℃に加温した状態で、3500gの荷重にて60秒間、硬化膜と5mm角シリコンチップとを熱圧着することにより、測定用基板を作製した。
室温(23℃)の条件下、ボンドテスター(XYZTEC社、Condor Sigma)を用いて、前記測定用基板を固定し、その5mm角シリコンチップ部分にせん断力をかけ、硬化膜から5mm角シリコンチップを剥がすために必要な力(シェア強度、N/mm2)を測定した。
硬化膜と5mm角シリコンチップとの間のシェア強度を指標とし、下記の評価基準に従い、接合状態を観察することにより、接着性の評価を行った。
評価基準
〇:シェア強度が5N/mm2以上であり、両者は強固に接合していた。
×:シェア強度が5N/mm2未満であり、接着力が弱く、硬化膜から5mm角シリコンチップが簡単に剥がれた。
ジメチルスルホキシド(DMSO)と、N-メチルピロリドン(NMP)と、2%テトラメチルアンモニウムヒドロキシド水溶液(TMAHaq.)とを混合して、混合体積比がDMSO/NMP/TMAHaq.=80/10/10の混合溶剤を調製した。
膜形成工程:
シリコン基板上に、各例の光硬化性組成物をそれぞれ、スピンコートにより塗布した。次に、オーブンにて、60℃で5分間、70℃で5分間、80℃で10分間のベーク処理をこの順に行うことにより、膜厚20μmの光硬化性膜をそれぞれ形成した。
次に、露光機(Prisma ghi)を用い、前記光硬化性膜に対し、g,h,i線を照射した。
次に、露光後の光硬化性膜に対し、90℃のホットプレート上で、5分間の露光後加熱を行った。
次に、露光後加熱を行った後の光硬化性膜に対し、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(PGMEA)を用いて、室温(23℃)で15分間のパドル現像を行った。
前記光硬化性樹脂パターンを、室温(23℃)の前記混合溶剤に30分間浸漬した。この後、下記の評価基準に従い、シリコン基板からの光硬化性樹脂パターンの剥がれ状態を観察することにより、耐薬品性の評価を行った。
評価基準
〇:光硬化性樹脂パターンの剥がれ無し。
△:光硬化性樹脂パターンの部分的に剥がれ有り。
×:光硬化性樹脂パターンの全体に剥がれ有り。
各例の光硬化性組成物を用いて、それぞれパターン形成を行った。
膜形成工程:
シリコン基板上に、各例の光硬化性組成物をそれぞれ、スピンコートにより塗布した。次に、オーブンにて、60℃で5分間、70℃で5分間、80℃で10分間のベーク処理をこの順に行うことにより、膜厚20μmの光硬化性膜をそれぞれ形成した。
次に、露光機(Prisma ghi)を用い、前記光硬化性膜に対し、g,h,i線を照射した。
次に、露光後の光硬化性膜に対し、90℃のホットプレート上で、5分間の露光後加熱を行った。
次に、露光後加熱を行った後の光硬化性膜に対し、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(PGMEA)を用いて、室温(23℃)で15分間のパドル現像を行った。
評価基準
〇:幅100μmのラインが良好な形状で形成された。
×:L/Sパターンの形状は不良であった。
加えて、実施例1~11の光硬化性組成物は、パターン形成において、良好な形状のパターンが形成され、リソ特性に優れることも確認できる。
一方、本発明の範囲外である比較例1~7の光硬化性組成物は、接着性及び耐薬品性の一方又は両方が悪い評価結果であった。
Claims (5)
- アクリル樹脂(AC)と、エポキシ基含有化合物(A)(但し、前記アクリル樹脂(AC)に該当するものを除く)と、カチオン重合開始剤(I)と、を含有する光硬化性組成物であって、
前記アクリル樹脂(AC)は、ガラス転移点が0℃以下であり、かつ、エポキシ基含有アクリルモノマーから誘導される構成単位(ac1)を有し、
前記構成単位(ac1)の含有割合が、前記アクリル樹脂(AC)を構成する全構成単位の合計(100質量%)に対して、0質量%超え50質量%未満である、光硬化性組成物。 - 前記アクリル樹脂(AC)と前記エポキシ基含有化合物(A)との混合比率が、質量比として、エポキシ基含有化合物(A)/アクリル樹脂(AC)=60/40~95/5である、請求項1に記載の光硬化性組成物。
- 前記エポキシ基含有化合物(A)は、ビスフェノール型エポキシ樹脂及びノボラック型エポキシ樹脂からなる群より選択される少なくとも一種のエポキシ樹脂を含む、請求項1又は2に記載の光硬化性組成物。
- 前記カチオン重合開始剤(I)の含有量が、前記アクリル樹脂(AC)と前記エポキシ基含有化合物(A)との合計の含有量100質量部に対して、0.05~5質量部である、請求項1又は2に記載の光硬化性組成物。
- 請求項1又は2に記載の光硬化性組成物を用いて、支持体上に光硬化性膜を形成する工程と、
前記光硬化性膜を露光する工程と、
前記露光後の光硬化性膜を、有機溶剤を含有する現像液で現像して、ネガ型パターンを形成する工程と、
を有する、パターン形成方法。
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JP2004347874A (ja) * | 2003-05-22 | 2004-12-09 | Jsr Corp | 感光性絶縁樹脂組成物およびその硬化物 |
WO2013118680A1 (ja) * | 2012-02-07 | 2013-08-15 | 日立化成株式会社 | 感光性樹脂組成物、パターン硬化膜の製造方法及び電子部品 |
WO2017030070A1 (ja) * | 2015-08-20 | 2017-02-23 | 東レ株式会社 | アンテナ基板の製造方法、配線と電極付きアンテナ基板の製造方法およびrfid素子の製造方法 |
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JP2002097443A (ja) | 2000-09-21 | 2002-04-02 | Hitachi Chem Co Ltd | 接着剤組成物及びこれを用いた回路接続材料並びに接続体 |
JP2004347874A (ja) * | 2003-05-22 | 2004-12-09 | Jsr Corp | 感光性絶縁樹脂組成物およびその硬化物 |
WO2013118680A1 (ja) * | 2012-02-07 | 2013-08-15 | 日立化成株式会社 | 感光性樹脂組成物、パターン硬化膜の製造方法及び電子部品 |
WO2017030070A1 (ja) * | 2015-08-20 | 2017-02-23 | 東レ株式会社 | アンテナ基板の製造方法、配線と電極付きアンテナ基板の製造方法およびrfid素子の製造方法 |
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