WO2017141734A1 - Photosensitive resin composition, dry film, cured product, printed circuit board, and photobase generator - Google Patents

Photosensitive resin composition, dry film, cured product, printed circuit board, and photobase generator Download PDF

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Publication number
WO2017141734A1
WO2017141734A1 PCT/JP2017/004015 JP2017004015W WO2017141734A1 WO 2017141734 A1 WO2017141734 A1 WO 2017141734A1 JP 2017004015 W JP2017004015 W JP 2017004015W WO 2017141734 A1 WO2017141734 A1 WO 2017141734A1
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group
resin composition
photosensitive resin
photobase generator
general formula
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PCT/JP2017/004015
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French (fr)
Japanese (ja)
Inventor
揚眉 郭
崇夫 三輪
有光 晃二
克起 岡安
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太陽ホールディングス株式会社
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Priority to JP2018500038A priority Critical patent/JP6767470B2/en
Priority to CN201780011878.7A priority patent/CN108700805B/en
Priority to KR1020187026536A priority patent/KR20180107270A/en
Publication of WO2017141734A1 publication Critical patent/WO2017141734A1/en

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/56Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups bound to carbon atoms of six-membered aromatic rings and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D233/00Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D487/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/28Applying non-metallic protective coatings

Definitions

  • the present invention relates to a photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a photobase generator.
  • Patent Document 1 contains a photobase generator composed of a salt of a carboxylic acid that is photodecarboxylated and a tertiary amine, and a polyimide precursor and / or a polybenzoxazole precursor.
  • a functional resin composition is described.
  • an object of the present invention is to provide a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a print having the cured product. It is to provide a wiring board and a photobase generator excellent in sensitivity.
  • the photosensitive resin composition of the present invention is characterized by containing an ionic photobase generator of carboxylic acid and base represented by the following general formula (1).
  • R 1 to R 4 , X 1 and X 2 are each independently a hydrogen atom or a substituent, and at least one of X 1 and X 2 is an electron-withdrawing group; Is an electron donating group, and B is a base.
  • the photoabsorber preferably has a molar extinction coefficient of 300 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
  • the electron attractive group is —C ⁇ N, —NO 2 , —COCH 3 , —F, —Cl, —Br, and —I.
  • it is selected from the group consisting of
  • the electron donating group is —CH 3 , —C 2 H 5 , —CH (CH 3 ) 2 , —C (CH 3 ) 3 , It is preferably selected from the group consisting of —C 6 H 5 , —OH, —OCH 3 , and —OC 6 H 5 .
  • the photosensitive resin composition of the present invention preferably further contains a polymer precursor.
  • the polymer precursor is preferably at least one of polyamic acid and polyamic acid ester.
  • the polymer precursor is preferably a polyamic acid ester having a structure represented by the following general formula (4-1).
  • R 7 is a tetravalent organic group
  • R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene.
  • R 9-1 and R 10-1 may be the same or different from each other, and may be a monovalent organic group or a functional group having silicon
  • R 11 may be a divalent organic group.
  • M is an integer of 1 or more
  • n is 0 or an integer of 1 or more.
  • R 7 in the general formula (4-1) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, an aromatic group and an aliphatic group.
  • a tetravalent organic group containing a cyclic hydrocarbon group or a tetravalent organic group containing a fluorine atom is preferable.
  • the photosensitive resin composition of the present invention is a polyamic acid ester in which the polymer precursor has a structure represented by at least one of the following general formulas (4-1-1) and (4-1-2): It is preferable that (In the formula (4-1-1), R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R 9 -1 and R 10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R 11 is a divalent organic group, and m is an integer of 1 or more.
  • R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group
  • R 9 -1 and R 10-1 may be the same or different from each other, and are a monovalent organic group or
  • R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group
  • R 9 -1 and R 10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon
  • R 11 is a divalent organic group
  • m is an integer of 1 or more.
  • n is 0 or an integer of 1 or more.
  • the dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to a film and drying it.
  • the cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of the dry film.
  • the printed wiring board of the present invention is characterized by having the cured product.
  • the photobase generator of the present invention is an ionic type of a carboxylic acid and a base represented by the following general formula (1).
  • R 1 to R 4 , X 1 and X 2 are each independently a hydrogen atom or a substituent, and at least one of X 1 and X 2 is an electron-withdrawing group; Is an electron donating group, and B is a base.
  • the electron-withdrawing group is represented by —C ⁇ N, —COCH 3 , —NO 2 , —F, —Cl, —Br, and —I. Preferably there is.
  • the electron donating group is —CH 3 , —C 2 H 5 , —CH (CH 3 ) 2 , —C (CH 3 ) 3 , — C 6 H 5 , —OH, —OCH 3 , and —OC 6 H 5 are preferred.
  • a photosensitive resin composition having excellent sensitivity a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring having the cured product
  • a photobase generator excellent in plate and sensitivity can be provided.
  • 2 is a chart showing the 1 H-NMR spectrum of the photobase generator MONPA-TBD synthesized in Example 1-1.
  • the horizontal axis represents chemical shift ( ⁇ ), and the vertical axis represents relative intensity (ppm).
  • 2 is a chart showing the 1 H-NMR spectrum of the photobase generator MONPA-DBU synthesized in Example 1-2.
  • the horizontal axis represents chemical shift ( ⁇ ), and the vertical axis represents relative intensity (ppm).
  • 2 is a chart showing the 1 H-NMR spectrum of the photobase generator MONPA-2E4MZ synthesized in Example 1-3.
  • the horizontal axis represents chemical shift ( ⁇ ), and the vertical axis represents relative intensity (ppm).
  • 2 is a chart showing the 1 H-NMR spectrum of the photobase generator MONPA-DBA synthesized in Example 1-4.
  • the horizontal axis represents chemical shift ( ⁇ ), and the vertical axis represents relative intensity (ppm).
  • Photobase generator In the present invention, an ionic photobase generator of a carboxylic acid and a base represented by the following general formula (1) is used.
  • R 1 to R 4 , X 1 and X 2 are each independently a hydrogen atom or a substituent, and at least one of X 1 and X 2 is an electron-withdrawing group; Is an electron donating group and B is a base, where the substituent is a group other than a hydrogen atom.
  • the photobase generator has a structure in which an electron-withdrawing group and an electron-donating group are directly bonded to a meta position and a para position of a benzene ring derived from phenylacetic acid, respectively.
  • a base can be generated depending on such a structure.
  • the above structure makes it possible to produce a photobase generator having high sensitivity even at i-line (365 nm).
  • the molar extinction coefficient at the i-line of the photobase generator is 300L ⁇ mol -1 ⁇ cm -1 or more, more preferably 500L ⁇ mol -1 ⁇ cm -1 or more, 1100L ⁇ mol - More preferably, it is 1 ⁇ cm ⁇ 1 or more.
  • the upper limit of the molar extinction coefficient is not particularly limited, but is, for example, 20000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less from the viewpoint of light stability and storage stability.
  • the photobase generator has a high thermal decomposition temperature (Td), it is excellent in thermal stability when, for example, the coating film is dried.
  • the Td of the photobase generator is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and most preferably 180 ° C. or higher.
  • the thermal decomposition temperature (Td) refers to the temperature at which the weight loss rate becomes 10%.
  • ultraviolet rays particularly 248 nm, 365 nm, 405 nm, and 436 nm are preferably used.
  • R 1 , R 2 , X 1 and X 2 are each independently a hydrogen atom or a substituent.
  • substituents include halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphonyl group. , Phosphono group, phosphonate group, alkoxy group, amide group or organic group.
  • the organic group is a group containing a carbon atom, for example, a group having 10 or less carbon atoms, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom).
  • a fluorine atom, a chlorine atom, etc. A fluorine atom, a chlorine atom, etc.
  • the electron-withdrawing group that X 1 and X 2 can take is not particularly limited, and examples thereof include —C ⁇ N, —COCH 3 , —NO 2 , and halogens such as —F, —Cl, —Br, and —I. Atom.
  • —NO 2 is preferred.
  • the other is not particularly limited.
  • the electron-donating group that Y can take is not particularly limited.
  • —OCH 3 is preferable.
  • R ⁇ 1 > and R ⁇ 2 > can take is not specifically limited, For example, an electron-donating group is mentioned.
  • R 1 and R 2 are each preferably a hydrogen atom.
  • R 3 and R 4 can take are not particularly limited. For example, halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, cyano groups, nitro groups, nitroso groups, sulfino groups, sulfo groups , Sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups or organic groups, which may be the same or different.
  • R 3 and R 4 are each preferably a hydrogen atom. Note that R 1 , R 2 , X 1 , X 2 and Y preferably do not form a cyclic structure.
  • the base which B shows is not specifically limited, For example, primary amines, secondary amines, amines such as tertiary amines (amine compounds), nitrogen-containing cyclic compounds such as pyridine, hydrazine compounds, amide compounds, water An oxide quaternary ammonium salt or the like can be used.
  • a base such as an amine disclosed in International Publication No. WO2009 / 19979 may be used.
  • secondary amines, tertiary amines, and nitrogen-containing cyclic compounds are preferable.
  • the base represented by B is preferably a strong base.
  • Examples of the base include 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethyl-4-aminopyridine (DMAP), 1-azabicyclo [2.2, as shown below. .2] Octane (ABCO), 1,8-bis (dimethylamino) naphthalene (DMAN), diazabicycloundecene (DBU), diazabicyclononene (DBN), 1,1,3,3-tetramethylguanidine (TMG), 2-ethyl-4-methylimidazole (2E4MZ), piperidine (PPD), 1-ethyl-piperidine (EPPD), dibutylamine (DBA), 1,5,7-triazabicyclo [4.4. 0] Dec-5-ene (TBD) and the like.
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • DMAP N, N-dimethyl-4-aminopyridine
  • the base preferably has a pKa of 8 to 20, more preferably 10 to 16.
  • the base is preferably DMAP, DMAN, DBU, TMG, 2E4MZ, PPD, EPPD, DBA and TBD.
  • the photobase generator is preferably a photobase generator represented by the following general formula (2).
  • the photobase generator is more preferably a photobase generator represented by the following general formula (3).
  • photobase generators prepared with 4-methoxy-3-nitrophenylacetic acid (MONPA) and various bases, but are not limited thereto.
  • MONPA 4-methoxy-3-nitrophenylacetic acid
  • the photobase generator may be used alone or in combination of two or more.
  • the blending amount of the photobase generator is preferably 3 to 50% by mass, and more preferably 10 to 30% by mass based on the total amount of the photosensitive resin composition.
  • the photosensitive resin composition of the present invention may contain a photobase generator other than the photobase generator as long as the effects of the present invention are not impaired.
  • the photosensitive resin composition of the present invention can contain a polymer precursor as a resin component that is modified using a base generated from the photobase generator as a catalyst.
  • the polymer precursor include a polymer precursor having a repeating unit of polyamic acid or polyamic acid ester as a polyimide precursor.
  • the polymer precursor having a repeating unit of polyamic acid or polyamic acid ester is preferably represented by the following general formula (4).
  • R 7 is a tetravalent organic group
  • R 8 is a divalent organic group
  • R 11 is a divalent organic group.
  • R 11 include a phenol group, an alkylphenol group, a (meth) acrylate group, a cyclic alkyl group, a cyclic alkenyl group, a hydroxyamidic acid group, an aromatic or aliphatic ester group, an amide group, an amideimide group, a carbonate ester group, Examples thereof include a group containing a siloxane group, an alkylene oxide, a urethane group, an epoxy group, an oxetanyl group, or the like as a constituent component.
  • the organic group is a group containing a carbon atom.
  • M is an integer of 1 or more, and n is 0 or an integer of 1 or more.
  • the preferred number average molecular weight of the polymer precursor is 1,000 to 1,000,000, more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000.
  • R 7 and R 8 are aromatic groups, preferably aromatic groups having 6 to 32 carbon atoms, or aliphatic groups, preferably aliphatic groups having 4 to 20 carbon atoms, depending on applications. Selected from the group. R 7 and R 8 are preferably the following acid dianhydrides used in the production of the polymer precursor and substituents R 7 and R 8 contained in the diamine.
  • R 7 and R 8 when patterning the photosensitive resin composition with short wavelength light, it is preferable to use an aliphatic group as R 7 and R 8 from the viewpoint of the absorption characteristics of the polymer.
  • R 7 and R 8 when a group containing fluorine is used as R 7 and R 8 , the wavelength of light absorption can be reduced or the dielectric characteristics can be improved.
  • the structure of the polymer precursor can be selected according to the application.
  • tetravalent R 7 shows only valence for bonding with the acid but, R 7 may have a substituent.
  • divalent value of R 8 indicates only the valency for bonding to the amine, but may have other substituents.
  • R 9 and R 10 are a hydrogen atom, a monovalent organic group, or a functional group having silicon.
  • R 9 and R 10 are monovalent organic groups, examples thereof include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
  • R 9 and R 10 are a functional group having monovalent silicon, examples thereof include a siloxane group, a silane group, and a silanol group.
  • only a part of R 9 and R 10 can be hydrogen or a monovalent organic group, whereby the solubility can be controlled.
  • a polyamic acid in which R 9 and R 10 are hydrogen atoms is preferably used as the polymer precursor. Thereby, alkali developability becomes favorable and a favorable pattern is obtained.
  • the polyamic acid can be prepared by applying a conventionally known method. For example, it can be prepared simply by mixing acid dianhydride and diamine in a solution. It is preferably used because it can be synthesized by a one-step reaction, can be obtained easily and at low cost, and does not require further modification.
  • the method for synthesizing the polymer precursor is not particularly limited, but a known method can be applied.
  • Examples of tetracarboxylic dianhydrides that can be used in the present invention include those represented by the following general formula (5). However, the specific examples shown below are merely examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.
  • R 7 groups in the repeating units in the polyamic acid according to the present embodiment is preferably derived from the R 7 of the tetracarboxylic dianhydride used as a raw material for polyamic acid production.
  • acid dianhydrides applicable to the production of the polymer precursor include 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [ 1,2-c] furan-1,3-dione, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides; pyromellitic dianhydrides, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydrides, 2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4'-benzophenone tetracarboxylic
  • tetracarboxylic dianhydride 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan -1,3-dione, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1, Examples include 1,1,3,3,3-hexafluoropropane dianhydride.
  • the physical properties such as solubility and thermal expansion coefficient are adjusted without significantly impairing transparency. It is possible. Also, rigid acid dianhydrides such as pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copolymerization ratio.
  • rigid acid dianhydrides such as pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copo
  • a plurality of carboxyl groups of the acid dianhydride may be present on a single aromatic ring or a plurality of aromatic rings.
  • an acid dianhydride represented by the following formula is used. be able to.
  • Examples of amines that can be used in the present invention include diamines represented by the following general formula (6). However, the following are examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention. (R 8 in the formula is as described above.)
  • diamines when the R 8 group is a divalent aromatic group include paraphenylenediamine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4 ′. -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,4 '-Diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis (3-aminophenoxy) benzene, bis [4 -(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy
  • Examples of diamines when the R 8 group is a divalent aliphatic group include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, Octamethylenediamine, Nonamethylenediamine, 4,4-Diaminoheptamethylenediamine, 1,4-Diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentadienylenediamine, Hexahydro-4,7-methanoindanylenediethylenediamine And tricyclo [6.2.1.02,7] -undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine), and isophoronediamine.
  • diaminopolysiloxane represented by the following general formula (11).
  • R 28 and R 29 each independently represent a divalent hydrocarbon group
  • R 30 and R 31 each independently represent a monovalent hydrocarbon group.
  • p is 1 or more, preferably an integer of 1 to 10.
  • R 28 and R 29 in the formula (11) are an alkylene group having 1 to 7 carbon atoms such as a methylene group, an ethylene group or a propylene group, or an arylene group having 6 to 18 carbon atoms such as a phenylene group.
  • R 30 and R 31 include an alkyl group having 1 to 7 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 12 carbon atoms such as a phenyl group.
  • polyamic acid ester can be suitably used as the polymer precursor.
  • the polyamic acid ester can be obtained by a known method.
  • an acid anhydride such as 3,3'-benzophenone tetracarboxylic dianhydride and an alcohol such as ethanol are reacted to form a half ester.
  • the half ester is converted to diester diacid chloride using thionyl chloride.
  • An ester of polyamic acid can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.
  • a polymer precursor having at least a part of a polyamic acid or a polyamic acid ester repeating unit a single type of material may be used, or a plurality of types may be used as a mixture. Also good. Further, it may be a copolymer in which at least one of R 7 and R 8 has a plurality of structures.
  • diisocyanates such as isophorone diisocyanate.
  • the synthetic method using diisocyanate can synthesize
  • diisocyanate that can be used for obtaining the polyamic acid ester include diisocyanates represented by the following general formula (7). However, the following are examples, and known ones can be used as long as they do not contradict the gist of the present invention.
  • diisocyanate examples include isophorone diisocyanate (ITI), toluene diisocyanate (TDI), methylene diphenyl 4,4′-diisocyanate (MDI), 2,2-bis (4-isocyanatophenyl) hexafluoropropane, hexa And methylene diisocyanate (HMDI).
  • ITI isophorone diisocyanate
  • TDI toluene diisocyanate
  • MDI methylene diphenyl 4,4′-diisocyanate
  • HMDI 2,2-bis (4-isocyanatophenyl) hexafluoropropane
  • the polymer precursor is preferably a polyamic acid ester having a structure represented by the following general formula (4-1).
  • R 7 is a tetravalent organic group
  • R 8 is a divalent organic group
  • R 11 is a divalent organic group.
  • M is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • R 9-1 and R 10-1 may be the same or different from each other, and may be a monovalent organic group or silicon.
  • R 8 is preferably any one of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group.
  • the tetravalent organic group represented by R 7 is not particularly limited, and may be selected according to the application.
  • an aromatic group preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, preferably an aliphatic group having 4 to 20 carbon atoms.
  • R 7 is preferably a substituent R 7 contained in the acid dianhydride represented by the general formula (5) used in the production of the polymer precursor.
  • R 7 is a tetravalent containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring.
  • the organic group is preferably a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a tetravalent organic group containing a fluorine atom.
  • the tetravalent organic group containing a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthalene group, particularly a phenyl group), and preferably has a trifluoromethyl group and an aromatic group.
  • the polyamic acid ester having the structure represented by the general formula (4-1) has a structure represented by at least one of the following general formulas (4-1-1) and (4-1-2). It is preferable.
  • R 8 , R 9-1 , R 10-1 , R 11 , m and n are the same as in the formula (4-1).
  • R 8 , R 9-1 , R 10-1 , R 11 , m and n are the same as in formula (4-1).
  • R 8 in formula (4-1) is preferably any of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group.
  • the phenylene group and the alkylene group are directly bonded to the two nitrogen atoms bonded to R 8 in the formula (4-1).
  • the alicyclic skeleton and the bisphenylene skeleton bonded by the alkylene group may be directly bonded to the two nitrogen atoms bonded to R 8 in the formula (4-1) or not.
  • R 8 is preferably a substituent R 8 contained in the diamine represented by the general formula (6) or the diisocyanate represented by the general formula (7) used in the production of the polymer precursor.
  • the group having the alicyclic skeleton in R 8 may have a substituent and may form a condensed ring.
  • the group having an alicyclic skeleton is preferably represented by the following general formula (8A).
  • n1 represents an integer of 0 to 10
  • R 8A1 represents an aliphatic group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group
  • R 8A2 represents Each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group.
  • the phenylene group for R 8 may have a substituent and may form a condensed ring.
  • the phenylene group is preferably represented by the following general formula (8B).
  • n2 represents an integer of 0 to 4
  • R 8B1 each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group.
  • the group having a bisphenylene skeleton bonded to the alkylene group in R 8 may have a substituent and may form a condensed ring.
  • the group having a bisphenylene skeleton bonded with the alkylene group is preferably represented by the following general formula (8C).
  • n3 and n4 each independently represents an integer of 0 to 4
  • R 8C1 and R 8C2 are each independently an aliphatic group or an aromatic group, preferably a methyl group, an ethyl group, etc.
  • R 8C3 represents an alkylene group having 1 to 5 carbon atoms.
  • the alkylene group represented by R 8C3 in formula (8C) may have a substituent such as an aliphatic group or an aromatic group.
  • the alkylene group for R 8 is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms.
  • the alkylene group in R 8 may have a substituent such as an aliphatic group or an aromatic group.
  • R 8 is preferably a group having an alicyclic skeleton because of excellent resolution, and more preferably a group having an alicyclic skeleton and no aromatic skeleton.
  • R 9-1 and R 10-1 in formula (4-1) are each independently a monovalent organic group or a functional group having silicon.
  • the monovalent organic group in R 9-1 and R 10-1 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
  • the functional group having monovalent silicon in R 9-1 and R 10-1 include a siloxane group, a silane group, and a silanol group.
  • R 9-1 and R 10-1 in the formula (4-1) are preferably alkyl groups from the viewpoint of solubility during the synthesis of the polyamic acid ester.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • the alkyl group is preferably a butyl group, a pentyl group, or a hexyl group.
  • R 11 in the formula (4-1) is a divalent organic group such as an aromatic or aliphatic ester group, an amide group, an amidoimide group, a siloxane group, an epoxy group, or an oxetanyl group.
  • a group included as at least a part of the structure can be given.
  • the solvent that can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve a photobase generator, a polymer precursor, and other additives.
  • Examples include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ - Examples include butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, ⁇ -butyrolactone, and diethylene glycol monomethyl ether.
  • the amount of the solvent to be used is not particularly limited.
  • the solvent may be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the polymer precursor depending on the coating film thickness and viscosity.
  • a sensitizer can also be added to the photosensitive resin composition of the present invention in order to further improve the photosensitivity.
  • the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal) cyclohexanone.
  • thioxanthones such as 9H-thioxanthen-9-one. These can be used alone or in combination of 2 to 5 kinds.
  • the sensitizer is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer precursor.
  • an adhesion aid can be blended with the photosensitive resin composition of the present invention in order to improve the adhesion to the substrate.
  • Any known adhesion assistant can be used as long as it is not contrary to the gist of the present invention.
  • the blending amount of the adhesion assistant is preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer precursor.
  • a base proliferating agent may be added to the photosensitive resin composition of the present invention.
  • the decomposition rate of the same amount of photobase generator is required from the surface to the bottom.
  • the addition of a base proliferating agent is preferable.
  • the base proliferating agents disclosed in JP 2012-237776 A, JP 2006-282657 A, and the like can be used.
  • photosensitive resin composition of this invention may be added to the photosensitive resin composition of this invention the other photosensitive component which generates an acid with light in the range which does not impair the film
  • a photo radical generator may be added.
  • various other organic or inorganic low-molecular or high-molecular compounds may be blended.
  • dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used.
  • the fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure.
  • Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers, fibers, and the like.
  • the dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film (support).
  • the dry film is formed by diluting the photosensitive resin composition of the present invention with the above-mentioned organic solvent and adjusting the viscosity to an appropriate viscosity, followed by comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer Apply a uniform thickness on a carrier film with a roll coater, gravure coater, spray coater, etc. Thereafter, the applied photosensitive resin composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer.
  • the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 ⁇ m, preferably 20 to 60 ⁇ m.
  • a plastic film As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used.
  • the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
  • a peelable cover film is further formed on the film surface for the purpose of preventing dust from adhering to the film surface. It is preferable to laminate.
  • the peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
  • a cover film what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.
  • Step 1 a photosensitive resin composition is applied on a substrate and dried to obtain a coating film.
  • a method for coating the photosensitive resin composition on the substrate methods conventionally used for coating the photosensitive resin composition, such as spin coater, bar coater, blade coater, curtain coater, screen printer, etc.
  • coating, the method of spray-coating with a spray coater, Furthermore, the inkjet method etc. can be used.
  • a method for drying the coating film methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used.
  • natural drying, blast drying, or heat drying can be performed at 20 to 140 ° C. for 1 minute to 1 hour.
  • drying is performed on a hot plate for 1 to 20 minutes.
  • Vacuum drying is also possible, and in this case, it can be carried out at room temperature for 1 minute to 1 hour.
  • the base material is not particularly limited, and can be widely applied to silicon wafers, wiring boards, various resins, metals, and passivation protective films for semiconductor devices.
  • step 2 the coating film is exposed through a photomask having a pattern or directly.
  • the exposure light having a wavelength capable of activating the photobase generator to generate a base is used.
  • the photosensitivity can be adjusted by appropriately using a sensitizer.
  • a contact aligner, mirror projection, stepper, laser direct exposure apparatus, or the like can be used.
  • step 3 heating is performed so as to promote imidization of the coating film by the base generated in the coating film.
  • the base generated in the exposed portion in Step 2 serves as a catalyst, and the polyamic acid ester is partially imidized.
  • the heating time and heating temperature are appropriately changed depending on the polyamic acid ester used, the coating film thickness, and the type of photobase generator. Typically, in the case of a coating film thickness of about 10 ⁇ m, it is about 2 to 10 minutes at 110 to 200 ° C. If the heating temperature is too low, partial imidization cannot be achieved efficiently. On the other hand, if the heating temperature is too high, imidization of the unexposed area proceeds to reduce the difference in solubility between the exposed area and the unexposed area, which may cause a problem in pattern formation.
  • step 4 the coating film is treated with a developer.
  • the pattern film which consists of a polyamic acid ester and the partially imidized polyimide can be formed on a base material.
  • an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment.
  • Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide.
  • aqueous solution of quaternary ammonium salts such as Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant can be used in an appropriate amount as an aqueous solution. Thereafter, the coating film is washed with a rinse liquid as necessary to obtain a pattern film.
  • a rinse liquid as necessary to obtain a pattern film.
  • distilled water, methanol, ethanol, isopropanol or the like can be used alone or in combination.
  • Examples of the developer include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, hexamethylphosphoryl tri Amide, methanol, ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropio Organic solvents such as nate, 2-heptanone, ethyl acetate, diacetone alcohol may be used.
  • the pattern film is heated.
  • the heating temperature is appropriately set so that the polyimide pattern film can be cured.
  • heating is performed in an inert gas at 150 to 300 ° C. for about 5 to 120 minutes.
  • a more preferable range of the heating temperature is 150 to 250 ° C, and a more preferable range is 180 to 220 ° C.
  • the heating is performed by using, for example, a hot plate, an oven, or a temperature rising oven in which a temperature program can be set.
  • the atmosphere (gas) may be air, or an inert gas such as nitrogen or argon.
  • the use of the photosensitive resin composition of the present invention is not particularly limited. For example, printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, optical member, etc. And various known fields and products in which resin materials are used.
  • the photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern film formed thereby is a permanent film made of polyimide.
  • a pattern forming material resist
  • the pattern film formed thereby is a permanent film made of polyimide.
  • Functions as a component that imparts heat resistance and insulation as a film such as color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films such as solder resists and coverlay films, solder dams, It is suitable for forming an optical circuit, an optical circuit component, an antireflection film, other optical members or electronic members.
  • the base generator can be produced by mixing a carboxylic acid represented by the following general formula (8) and a base.
  • the carboxylic acid is more preferably a carboxylic acid represented by the following general formula (9), further 4-methoxy-3-nitrophenylacetic acid (MONPA) represented by the following formula (10). preferable.
  • MONPA 4-methoxy-3-nitrophenylacetic acid
  • R 1 to R 4 , X 1 , X 2 and Y are the same as those in the general formula (1).
  • a base represented by B in the general formula (1) can be used as the base.
  • the mixing of the carboxylic acid and the base is preferably carried out by dripping the base solution into the carboxylic acid solution in the dark.
  • Example 1-2 Synthesis of MOMPA-DBU 0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) in Synthesis Example 1 was added to 0.216 g of diazabicycloundecene (DBU) ( MOMPA-DBU was obtained as an orange viscous liquid in the same manner as in Synthesis Example 1 except for changing to 1.42 mmol) (yield: 0.419 g, yield: 81%).
  • a chart of 1 H-NMR (300 MHz, CDCl 3 ) is shown in FIG. 2, and peak analysis results are shown below.
  • Example 1-3 Synthesis of MOMPA-2E4MZ
  • 2E4MZ 2-ethyl-4-methylimidazole
  • MOMPA-2E4MZ was obtained as an orange viscous liquid in the same manner as in Synthesis Example 1 except that the amount was changed to .156 g (1.42 mmol) (yield: 0.186 g, yield: 41%).
  • a chart of 1 H-NMR (300 MHz, CDCl 3 ) is shown in FIG. 3, and peak analysis results are shown below.
  • the photobase generator (MONPA-TBD) of Example 1-1 was measured using a TG-DTA2000S manufactured by Mac Science Co., Ltd. (TG-DTA measurement (temperature increase rate 5 ° C./min)) and stable up to about 200 ° C. I confirmed that there was.
  • the solution including the precipitate was filtered and dried to obtain a polymer precursor polymer.
  • the obtained polymer was dissolved in DMAc (N, N-dimethylacetamide) and reprecipitated with MeOH. Filtration and drying were performed to prepare a 15% by mass polyamic acid ester A-1 solution using dehydrated DMAc as a solvent.
  • Example 2-1 Photobase generators are blended and dissolved in the polyamic acid ester solution obtained above at the blending ratio (mass ratio) described in the following table, and the photosensitive resin compositions of Examples and Comparative Examples are used. Got. In addition, the compounding quantity of the polyamic acid ester in a table
  • the photosensitive resin composition of Example 2-1 in the following table was applied on a 4-inch silicon wafer by spin coating, and heated on a hot plate at 80 ° C. for 20 minutes to form a photosensitive resin composition having a thickness of 10 ⁇ m.
  • a material film was formed.
  • the film was exposed with a light amount in the range of 0 to 1000 mJ / cm 2 through a mask pattern by a high pressure mercury lamp exposure apparatus equipped with an i-line filter. After the exposure, it was heated on a hot plate at 140 ° C. for 10 minutes, and then immersed in a developer mixed with a tetramethylammonium hydroxide 2.38% aqueous solution and 2-propanol at a weight ratio of 1: 1 for 90 seconds. Pattern development was performed by washing with water for 20 seconds.
  • Example 2-2 to 2-9 Comparative Examples 2-1 to 2-3
  • a development test was carried out with the blending ratio (mass ratio) and exposure amount shown in the following table, and the exposure amount in which a pattern was formed was confirmed.
  • a pattern could not be formed even at 1000 mJ / cm 2 .
  • the photosensitive resin compositions of the examples containing the photobase generator satisfying the general formula (1) are excellent in sensitivity and excellent in pattern formability despite low-temperature curing conditions.

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Abstract

Provided are a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the dry film resin layer, a printed circuit board having the cured product, and a photobase generator having excellent sensitivity. The photosensitive resin composition and the like are characterized in comprising an ion-type photobase generator that contains a carboxylic acid and a base and is represented by general formula (1). (In formula (1), R1 through R4 and X1 and X2 are each independently a hydrogen atom or substitution group, at least one of X1 and X2 is an electron-attracting group, Y is an electron-releasing group, and B is a base.)

Description

感光性樹脂組成物、ドライフィルム、硬化物、プリント配線板および光塩基発生剤Photosensitive resin composition, dry film, cured product, printed wiring board, and photobase generator
 本発明は、感光性樹脂組成物、ドライフィルム、硬化物、プリント配線板および光塩基発生剤に関する。 The present invention relates to a photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a photobase generator.
 光の作用によって塩基を発生する光塩基発生剤を触媒として利用して樹脂を化学変性させる方法がフォトレジスト材料や光硬化材料等の分野に応用されている。例えば、特許文献1には、光脱炭酸をするカルボン酸と3級アミンとの塩からなる光塩基発生剤と、ポリイミド前駆体および/またはポリベンゾオキサゾール前駆体を含有することを特徴とする感光性樹脂組成物が記載されている。 A method of chemically modifying a resin using a photobase generator that generates a base by the action of light as a catalyst has been applied to the fields of photoresist materials and photocuring materials. For example, Patent Document 1 contains a photobase generator composed of a salt of a carboxylic acid that is photodecarboxylated and a tertiary amine, and a polyimide precursor and / or a polybenzoxazole precursor. A functional resin composition is described.
特許4830435号公報Japanese Patent No. 4830435
 光塩基発生剤を含有する感光性樹脂組成物の感度の向上が求められている。感度が向上すれば、塩基を発生するための光照射の条件や塩基を利用して熱硬化を行う場合の熱処理の条件等の反応条件が緩和されていても、良好な解像性でパターニングできることが期待される。また、感度が向上すれば、上記のような反応条件の選択の幅が広がり、感光性樹脂組成物中の他の成分や、感光性樹脂組成物を塗布する基材等の他の材料の耐熱性等の特性を考慮した上で、従来よりも最適な反応条件を選択できることが期待される。しかしながら、特許文献1に記載の光脱炭酸をするカルボン酸と3級アミンとの塩からなる光塩基発生剤では、十分な感度が得られなかった。 There is a demand for improvement in the sensitivity of photosensitive resin compositions containing a photobase generator. If sensitivity is improved, patterning can be performed with good resolution even if reaction conditions such as light irradiation conditions for generating bases and heat treatment conditions when using bases for thermal curing are relaxed. There is expected. In addition, if the sensitivity is improved, the range of selection of the reaction conditions as described above is expanded, and the heat resistance of other components such as the base material on which the photosensitive resin composition is applied, and other components in the photosensitive resin composition. It is expected that optimum reaction conditions can be selected compared to the conventional ones in consideration of characteristics such as properties. However, the photobase generator composed of a salt of a carboxylic acid and a tertiary amine that performs photodecarboxylation described in Patent Document 1 cannot provide sufficient sensitivity.
 そこで本発明の目的は、感度に優れた感光性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、該組成物または該ドライフィルムの樹脂層の硬化物、該硬化物を有するプリント配線板、感度に優れた光塩基発生剤を提供することにある。 Accordingly, an object of the present invention is to provide a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a print having the cured product. It is to provide a wiring board and a photobase generator excellent in sensitivity.
 本発明者等は上記に鑑み鋭意検討した結果、特定の構造を有する化合物を光塩基発生剤として用いることによって、上記課題を解決しうることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above, the present inventors have found that the above problem can be solved by using a compound having a specific structure as a photobase generator, and have completed the present invention.
 即ち、本発明の感光性樹脂組成物は、下記一般式(1)で表されるカルボン酸と塩基のイオン型の光塩基発生剤を含有することを特徴とするものである。
Figure JPOXMLDOC01-appb-I000006
(式(1)中、R~R、XおよびXは、それぞれ独立して、水素原子または置換基であり、XおよびXの少なくとも一方は電子吸引性基であり、Yは電子供与性基であり、Bは塩基を示す。)
That is, the photosensitive resin composition of the present invention is characterized by containing an ionic photobase generator of carboxylic acid and base represented by the following general formula (1).
Figure JPOXMLDOC01-appb-I000006
(In the formula (1), R 1 to R 4 , X 1 and X 2 are each independently a hydrogen atom or a substituent, and at least one of X 1 and X 2 is an electron-withdrawing group; Is an electron donating group, and B is a base.)
 本発明の感光性樹脂組成物は、前記光塩基発生剤のモル吸光係数が、300L・mol-1・cm-1以上であることが好ましい。 In the photosensitive resin composition of the present invention, the photoabsorber preferably has a molar extinction coefficient of 300 L · mol −1 · cm −1 or more.
 本発明の感光性樹脂組成物は、前記一般式(1)において、電子吸引性基が、-C≡N、-NO、-COCH、-F、-Cl、-Br、および、-Iからなる群から選択されることが好ましい。 In the photosensitive resin composition of the present invention, in the general formula (1), the electron attractive group is —C≡N, —NO 2 , —COCH 3 , —F, —Cl, —Br, and —I. Preferably it is selected from the group consisting of
 本発明の感光性樹脂組成物は、前記一般式(1)において、電子供与性基が、-CH、-C、-CH(CH、-C(CH、-C、-OH、-OCH、および、-OCからなる群から選択されることが好ましい。 In the photosensitive resin composition of the present invention, in the general formula (1), the electron donating group is —CH 3 , —C 2 H 5 , —CH (CH 3 ) 2 , —C (CH 3 ) 3 , It is preferably selected from the group consisting of —C 6 H 5 , —OH, —OCH 3 , and —OC 6 H 5 .
 本発明の感光性樹脂組成物は、さらに、高分子前駆体を含有することが好ましい。 The photosensitive resin composition of the present invention preferably further contains a polymer precursor.
 本発明の感光性樹脂組成物は、前記高分子前駆体が、ポリアミック酸、および、ポリアミック酸エステルの少なくとも何れか一方であることが好ましい。 In the photosensitive resin composition of the present invention, the polymer precursor is preferably at least one of polyamic acid and polyamic acid ester.
 本発明の感光性樹脂組成物は、前記高分子前駆体が、下記一般式(4-1)で表される構造を有するポリアミック酸エステルであることが好ましい。
Figure JPOXMLDOC01-appb-I000007
(式(4-1)中、Rは4価の有機基であり、Rは脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、R9-1およびR10-1は、相互に同一でも異なってもよく、1価の有機基またはケイ素を有する官能基であり、R11は2価の有機基であり、mは1以上の整数であり、nは0または1以上の整数である。)
In the photosensitive resin composition of the present invention, the polymer precursor is preferably a polyamic acid ester having a structure represented by the following general formula (4-1).
Figure JPOXMLDOC01-appb-I000007
(In formula (4-1), R 7 is a tetravalent organic group, R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene. R 9-1 and R 10-1 may be the same or different from each other, and may be a monovalent organic group or a functional group having silicon, and R 11 may be a divalent organic group. M is an integer of 1 or more, and n is 0 or an integer of 1 or more.)
 本発明の感光性樹脂組成物は、前記一般式(4-1)中のRが、芳香族環と脂肪族炭化水素環との縮合環を含む4価の有機基、芳香族基と脂環式炭化水素基とを含む4価の有機基、またはフッ素原子を含む4価の有機基であることが好ましい。 In the photosensitive resin composition of the present invention, R 7 in the general formula (4-1) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, an aromatic group and an aliphatic group. A tetravalent organic group containing a cyclic hydrocarbon group or a tetravalent organic group containing a fluorine atom is preferable.
 本発明の感光性樹脂組成物は、前記高分子前駆体が、下記一般式(4-1-1)および(4-1-2)の少なくともいずれか一方で表される構造を有するポリアミック酸エステルであることが好ましい。
Figure JPOXMLDOC01-appb-I000008
(式(4-1-1)中、Rは脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、R9-1およびR10-1は、相互に同一でも異なってもよく、1価の有機基またはケイ素を有する官能基であり、R11は2価の有機基であり、mは1以上の整数であり、nは0または1以上の整数である。)
Figure JPOXMLDOC01-appb-I000009
(式(4-1-2)中、Rは脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、R9-1およびR10-1は、相互に同一でも異なってもよく、1価の有機基またはケイ素を有する官能基であり、R11は2価の有機基であり、mは1以上の整数であり、nは0または1以上の整数である。)
The photosensitive resin composition of the present invention is a polyamic acid ester in which the polymer precursor has a structure represented by at least one of the following general formulas (4-1-1) and (4-1-2): It is preferable that
Figure JPOXMLDOC01-appb-I000008
(In the formula (4-1-1), R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R 9 -1 and R 10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R 11 is a divalent organic group, and m is an integer of 1 or more. And n is 0 or an integer of 1 or more.)
Figure JPOXMLDOC01-appb-I000009
(In the formula (4-1-2), R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R 9 -1 and R 10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R 11 is a divalent organic group, and m is an integer of 1 or more. And n is 0 or an integer of 1 or more.)
 本発明のドライフィルムは、前記感光性樹脂組成物を、フィルムに塗布、乾燥して得られる樹脂層を有することを特徴とするものである。 The dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to a film and drying it.
 本発明の硬化物は、前記感光性樹脂組成物または前記ドライフィルムの樹脂層を、硬化して得られることを特徴とするものである。 The cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of the dry film.
 本発明のプリント配線板は、前記硬化物を有することを特徴とするものである。 The printed wiring board of the present invention is characterized by having the cured product.
 本発明の光塩基発生剤は、下記一般式(1)で表されるカルボン酸と塩基のイオン型であることを特徴とするものである。
Figure JPOXMLDOC01-appb-I000010
(式(1)中、R~R、XおよびXは、それぞれ独立して、水素原子または置換基であり、XおよびXの少なくとも一方は電子吸引性基であり、Yは電子供与性基であり、Bは塩基を示す。)
The photobase generator of the present invention is an ionic type of a carboxylic acid and a base represented by the following general formula (1).
Figure JPOXMLDOC01-appb-I000010
(In the formula (1), R 1 to R 4 , X 1 and X 2 are each independently a hydrogen atom or a substituent, and at least one of X 1 and X 2 is an electron-withdrawing group; Is an electron donating group, and B is a base.)
 本発明の光塩基発生剤は、前記一般式(1)において、電子吸引性基が、-C≡N、-COCH、-NO、-F、-Cl、-Br、および、-Iであることが好ましい。 In the photobase generator of the present invention, in the general formula (1), the electron-withdrawing group is represented by —C≡N, —COCH 3 , —NO 2 , —F, —Cl, —Br, and —I. Preferably there is.
 本発明の光塩基発生剤は、前記一般式(1)において、電子供与性基が、-CH、-C、-CH(CH、-C(CH、-C、-OH、-OCH、および、-OCであることが好ましい。 In the photobase generator of the present invention, in the general formula (1), the electron donating group is —CH 3 , —C 2 H 5 , —CH (CH 3 ) 2 , —C (CH 3 ) 3 , — C 6 H 5 , —OH, —OCH 3 , and —OC 6 H 5 are preferred.
 本発明によれば、感度に優れた感光性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、該組成物または該ドライフィルムの樹脂層の硬化物、該硬化物を有するプリント配線板、感度に優れた光塩基発生剤を提供することができる。 According to the present invention, a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring having the cured product A photobase generator excellent in plate and sensitivity can be provided.
実施例1-1で合成した光塩基発生剤MONPA-TBDのH-NMRのスペクトルを示すチャートである。横軸は化学シフト(δ)、縦軸は相対強度(ppm)を示す。2 is a chart showing the 1 H-NMR spectrum of the photobase generator MONPA-TBD synthesized in Example 1-1. The horizontal axis represents chemical shift (δ), and the vertical axis represents relative intensity (ppm). 実施例1-2で合成した光塩基発生剤MONPA-DBUのH-NMRのスペクトルを示すチャートである。横軸は化学シフト(δ)、縦軸は相対強度(ppm)を示す。2 is a chart showing the 1 H-NMR spectrum of the photobase generator MONPA-DBU synthesized in Example 1-2. The horizontal axis represents chemical shift (δ), and the vertical axis represents relative intensity (ppm). 実施例1-3で合成した光塩基発生剤MONPA-2E4MZのH-NMRのスペクトルを示すチャートである。横軸は化学シフト(δ)、縦軸は相対強度(ppm)を示す。2 is a chart showing the 1 H-NMR spectrum of the photobase generator MONPA-2E4MZ synthesized in Example 1-3. The horizontal axis represents chemical shift (δ), and the vertical axis represents relative intensity (ppm). 実施例1-4で合成した光塩基発生剤MONPA-DBAのH-NMRのスペクトルを示すチャートである。横軸は化学シフト(δ)、縦軸は相対強度(ppm)を示す。2 is a chart showing the 1 H-NMR spectrum of the photobase generator MONPA-DBA synthesized in Example 1-4. The horizontal axis represents chemical shift (δ), and the vertical axis represents relative intensity (ppm).
 以下、本発明の感光性樹脂組成物が含有する成分について詳述する。 Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.
[光塩基発生剤]
 本発明において、下記一般式(1)で表されるカルボン酸と塩基のイオン型の光塩基発生剤を用いる。
Figure JPOXMLDOC01-appb-I000011
(式(1)中、R~R、XおよびXは、それぞれ独立して、水素原子または置換基であり、XおよびXの少なくとも一方は電子吸引性基であり、Yは電子供与性基であり、Bは塩基を示す。ここで、置換基とは、水素原子以外の基である。)
[Photobase generator]
In the present invention, an ionic photobase generator of a carboxylic acid and a base represented by the following general formula (1) is used.
Figure JPOXMLDOC01-appb-I000011
(In the formula (1), R 1 to R 4 , X 1 and X 2 are each independently a hydrogen atom or a substituent, and at least one of X 1 and X 2 is an electron-withdrawing group; Is an electron donating group and B is a base, where the substituent is a group other than a hydrogen atom.)
 前記光塩基発生剤は、フェニル酢酸由来のベンゼン環のメタ位およびパラ位にそれぞれ電子吸引性基と電子供与性基が直接に結合する構造を有する。このような構造に依拠して塩基を発生できる。 The photobase generator has a structure in which an electron-withdrawing group and an electron-donating group are directly bonded to a meta position and a para position of a benzene ring derived from phenylacetic acid, respectively. A base can be generated depending on such a structure.
 また、上記の構造によって、i線(365nm)においても感度が高い光塩基発生剤を製造が可能となる。前記光塩基発生剤のi線におけるモル吸光係数は300L・mol-1・cm-1以上であることが好ましく、500L・mol-1・cm-1以上であることがより好ましく1100L・mol-1・cm-1以上であることがさらに好ましい。モル吸光係数が高いほど感度が高くなる傾向にある。モル吸光係数の上限値は特に制限はないが、光安定性や保存安定性の観点から例えば、20000L・mol-1・cm-1以下である。 In addition, the above structure makes it possible to produce a photobase generator having high sensitivity even at i-line (365 nm). Preferably the molar extinction coefficient at the i-line of the photobase generator is 300L · mol -1 · cm -1 or more, more preferably 500L · mol -1 · cm -1 or more, 1100L · mol - More preferably, it is 1 · cm −1 or more. The higher the molar extinction coefficient, the higher the sensitivity. The upper limit of the molar extinction coefficient is not particularly limited, but is, for example, 20000 L · mol −1 · cm −1 or less from the viewpoint of light stability and storage stability.
 さらに、前記光塩基発生剤は、熱分解温度(Td)が高いので、例えば塗膜乾燥時の熱安定性にも優れる。前記光塩基発生剤のTdは、120℃以上であることが好ましく、150℃以上であることがより好ましく、180℃以上であることが最も好ましい。なお、熱分解温度(Td)とは、重量減少割合が10%になったときの温度を言う。 Furthermore, since the photobase generator has a high thermal decomposition temperature (Td), it is excellent in thermal stability when, for example, the coating film is dried. The Td of the photobase generator is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and most preferably 180 ° C. or higher. The thermal decomposition temperature (Td) refers to the temperature at which the weight loss rate becomes 10%.
 前記光塩基発生剤に対する活性光線として、可視光線、紫外線、電子線、X線等を照射することが可能であり、紫外線、特に、248nm、365nm、405nm、436nmの紫外線を用いることが好ましい。 As the actinic rays for the photobase generator, visible rays, ultraviolet rays, electron beams, X-rays and the like can be irradiated, and ultraviolet rays, particularly 248 nm, 365 nm, 405 nm, and 436 nm are preferably used.
 前記一般式(1)において、R、R、XおよびXは、それぞれ独立して、水素原子または置換基である。置換基としては、例えば、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、シアノ基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホニル基、ホスホノ基、ホスホナト基、アルコキシ基、アミド基または有機基が挙げられる。
 ここで、有機基とは、炭素原子を含む基であり、例えば、炭素数が10以下の基であり、炭素原子以外の原子(例えば、水素原子、酸素原子、窒素原子、硫黄原子、ハロゲン原子(フッ素原子、塩素原子等)等)を有していてもよい。
 XおよびXがとり得る電子吸引性基は、特に限定されないが、例えば、-C≡N、-COCH、-NO、および、-F、-Cl、-Br、-I等のハロゲン原子が挙げられる。電子吸引性基の中でも、-NOが好ましい。なお、XおよびXのうち一方のみが電子吸引性基の場合は、他方は特に限定されない。
In the general formula (1), R 1 , R 2 , X 1 and X 2 are each independently a hydrogen atom or a substituent. Examples of the substituent include halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphonyl group. , Phosphono group, phosphonate group, alkoxy group, amide group or organic group.
Here, the organic group is a group containing a carbon atom, for example, a group having 10 or less carbon atoms, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom). (A fluorine atom, a chlorine atom, etc.)).
The electron-withdrawing group that X 1 and X 2 can take is not particularly limited, and examples thereof include —C≡N, —COCH 3 , —NO 2 , and halogens such as —F, —Cl, —Br, and —I. Atom. Of the electron withdrawing groups, —NO 2 is preferred. When only one of X 1 and X 2 is an electron withdrawing group, the other is not particularly limited.
 Yがとり得る電子供与性基は、特に限定されないが、例えば、-CH、-C、-CH(CH、-C(CH、-C、-OH、-OCH、および、-OCが挙げられる。なかでも、-OCHが好ましい。 The electron-donating group that Y can take is not particularly limited. For example, —CH 3 , —C 2 H 5 , —CH (CH 3 ) 2 , —C (CH 3 ) 3 , —C 6 H 5 , — OH, -OCH 3, and include -OC 6 H 5. Of these, —OCH 3 is preferable.
 RおよびRがとり得る置換基は、特に限定されないが、例えば、電子供与性基が挙げられる。RおよびRは、それぞれ水素原子であることが好ましい。 Although the substituent which R < 1 > and R < 2 > can take is not specifically limited, For example, an electron-donating group is mentioned. R 1 and R 2 are each preferably a hydrogen atom.
 RおよびRがとり得る置換基は、特に限定されないが、例えば、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、シアノ基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基または有機基であり、同一であっても異なっていてもよい。RおよびRは、それぞれ水素原子であることが好ましい。
 なお、R、R、X、XおよびYは、環状構造を形成しないことが好ましい。
Substituents that R 3 and R 4 can take are not particularly limited. For example, halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, cyano groups, nitro groups, nitroso groups, sulfino groups, sulfo groups , Sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups or organic groups, which may be the same or different. R 3 and R 4 are each preferably a hydrogen atom.
Note that R 1 , R 2 , X 1 , X 2 and Y preferably do not form a cyclic structure.
 Bが示す塩基は、特に限定されないが、例えば、第1級アミン、第2級アミン、第3級アミン等のアミン(アミン化合物)、ピリジン等の含窒素環状化合物、ヒドラジン化合物、アミド化合物、水酸化四級アンモニウム塩等を使用することができる。また、例えば、国際公開番号WO2009/19979に開示されるアミン等の塩基を使用してもよい。塩基の中でも、第2級アミン、第3級アミン、含窒素環状化合物が好ましい。Bが示す塩基は、強塩基であることが好ましい。 Although the base which B shows is not specifically limited, For example, primary amines, secondary amines, amines such as tertiary amines (amine compounds), nitrogen-containing cyclic compounds such as pyridine, hydrazine compounds, amide compounds, water An oxide quaternary ammonium salt or the like can be used. In addition, for example, a base such as an amine disclosed in International Publication No. WO2009 / 19979 may be used. Among the bases, secondary amines, tertiary amines, and nitrogen-containing cyclic compounds are preferable. The base represented by B is preferably a strong base.
 塩基としては、例えば、下記に示すような、1,4-ジアザビシクロ[2.2.2]オクタン(DABCO)、N,N-ジメチル-4-アミノピリジン(DMAP)、1-アザビシクロ[2.2.2]オクタン(ABCO)、1,8-ビス(ジメチルアミノ)ナフタレン(DMAN)、ジアザビシクロウンデセン(DBU)、ジアザビシクロノネン(DBN)、1,1,3,3-テトラメチルグアニジン(TMG)、2-エチル-4-メチルイミダゾール(2E4MZ)、ピペリジン(PPD)、1-エチル-ピペリジン(EPPD)、ジブチルアミン(DBA)、1,5,7-トリアザビシクロ[4.4.0]デカ-5-エン(TBD)等が挙げられる。 Examples of the base include 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethyl-4-aminopyridine (DMAP), 1-azabicyclo [2.2, as shown below. .2] Octane (ABCO), 1,8-bis (dimethylamino) naphthalene (DMAN), diazabicycloundecene (DBU), diazabicyclononene (DBN), 1,1,3,3-tetramethylguanidine (TMG), 2-ethyl-4-methylimidazole (2E4MZ), piperidine (PPD), 1-ethyl-piperidine (EPPD), dibutylamine (DBA), 1,5,7-triazabicyclo [4.4. 0] Dec-5-ene (TBD) and the like.
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
 前記塩基は、pKaが8~20であることが好ましく、10~16であることがより好ましい。 The base preferably has a pKa of 8 to 20, more preferably 10 to 16.
 前記塩基は、DMAP、DMAN、DBU、TMG、2E4MZ、PPD、EPPD、DBAおよびTBDが好ましい。 The base is preferably DMAP, DMAN, DBU, TMG, 2E4MZ, PPD, EPPD, DBA and TBD.
 前記光塩基発生剤は、下記一般式(2)で表される光塩基発生剤であることが好ましい。 The photobase generator is preferably a photobase generator represented by the following general formula (2).
 式(2)中、X、X、YおよびBは、式(1)と同様である。 In formula (2), X 1 , X 2 , Y and B are the same as in formula (1).
 また、前記光塩基発生剤は、下記一般式(3)で表される光塩基発生剤であることがより好ましい。 The photobase generator is more preferably a photobase generator represented by the following general formula (3).
Figure JPOXMLDOC01-appb-I000014
 式(3)中、Bは式(1)と同様である。
Figure JPOXMLDOC01-appb-I000014
In Formula (3), B is the same as Formula (1).
 以下に、前記光塩基発生剤の具体例として、4-メトキシ-3-ニトロフェニル酢酸(MONPA)と種々の塩基で調整した光塩基発生剤を示すが、これらに限定されるものではない。 Hereinafter, specific examples of the photobase generator include photobase generators prepared with 4-methoxy-3-nitrophenylacetic acid (MONPA) and various bases, but are not limited thereto.
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000015
 前記光塩基発生剤は、1種を単独で用いてもよく、2種以上を併用してもよい。前記光塩基発生剤の配合量は、感光性樹脂組成物全量基準で3~50質量%であることが好ましく、10~30質量%であることがより好ましい。 The photobase generator may be used alone or in combination of two or more. The blending amount of the photobase generator is preferably 3 to 50% by mass, and more preferably 10 to 30% by mass based on the total amount of the photosensitive resin composition.
 本発明の感光性樹脂組成物は、本発明の効果を損なわない範囲で、前記光塩基発生剤以外の光塩基発生剤を含有してもよい。 The photosensitive resin composition of the present invention may contain a photobase generator other than the photobase generator as long as the effects of the present invention are not impaired.
(高分子前駆体)
 本発明の感光性樹脂組成物は、前記光塩基発生剤から発生する塩基を触媒として変性させる樹脂成分として、高分子前駆体を含有することができる。高分子前駆体としては、例えば、ポリイミド前駆体として、ポリアミック酸またはポリアミック酸エステルの繰り返し単位を有する高分子前駆体が挙げられる。
(Polymer precursor)
The photosensitive resin composition of the present invention can contain a polymer precursor as a resin component that is modified using a base generated from the photobase generator as a catalyst. Examples of the polymer precursor include a polymer precursor having a repeating unit of polyamic acid or polyamic acid ester as a polyimide precursor.
 前記ポリアミック酸またはポリアミック酸エステルの繰り返し単位を有する高分子前駆体は、下記一般式(4)で表わされることが好ましい。  The polymer precursor having a repeating unit of polyamic acid or polyamic acid ester is preferably represented by the following general formula (4).
Figure JPOXMLDOC01-appb-I000016
 式(4)中、Rは4価の有機基であり、Rは2価の有機基であり、R11が2価の有機基である。R11としては、例えば、フェノール基、アルキルフェノール基、(メタ)アクリレート基、環状アルキル基、環状アルケニル基、ヒドロキシアミド酸基、芳香族または脂肪族エステル基、アミド基、アミドイミド基、炭酸エステル基、シロキサン基、アルキレンオキサイド、ウレタン基、エポキシ基、オキセタニル基などを構成成分として含む基を挙げることができる。ここで、有機基とは、炭素原子を含む基である。
Figure JPOXMLDOC01-appb-I000016
In formula (4), R 7 is a tetravalent organic group, R 8 is a divalent organic group, and R 11 is a divalent organic group. Examples of R 11 include a phenol group, an alkylphenol group, a (meth) acrylate group, a cyclic alkyl group, a cyclic alkenyl group, a hydroxyamidic acid group, an aromatic or aliphatic ester group, an amide group, an amideimide group, a carbonate ester group, Examples thereof include a group containing a siloxane group, an alkylene oxide, a urethane group, an epoxy group, an oxetanyl group, or the like as a constituent component. Here, the organic group is a group containing a carbon atom.
 mは、1以上の整数であり、nは、0または1以上の整数である。ここで、高分子前駆体の好ましい数平均分子量は、1000~100万であり、より好ましくは5000~50万であり、さらにより好ましくは1万~20万である。 M is an integer of 1 or more, and n is 0 or an integer of 1 or more. Here, the preferred number average molecular weight of the polymer precursor is 1,000 to 1,000,000, more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000.
 式(4)中、RおよびRは用途に応じて、芳香族基、好ましくは炭素原子数6~32の芳香族基、または脂肪族基、好ましくは炭素原子数4~20の脂肪族基、から選ばれる。RおよびRは、高分子前駆体の製造において用いられる後述の酸二無水物、およびジアミンに含まれる置換基RおよびRであると好ましい。 In the formula (4), R 7 and R 8 are aromatic groups, preferably aromatic groups having 6 to 32 carbon atoms, or aliphatic groups, preferably aliphatic groups having 4 to 20 carbon atoms, depending on applications. Selected from the group. R 7 and R 8 are preferably the following acid dianhydrides used in the production of the polymer precursor and substituents R 7 and R 8 contained in the diamine.
 また、短波長光により感光性樹脂組成物をパターン形成する場合には、ポリマーの吸収特性の観点から、RおよびRとして脂肪族基を用いることが好ましい。また、例えば、RおよびRとしてフッ素を含有する基を用いる場合は、光吸収の低波長化または誘電特性を向上することができる。 Moreover, when patterning the photosensitive resin composition with short wavelength light, it is preferable to use an aliphatic group as R 7 and R 8 from the viewpoint of the absorption characteristics of the polymer. For example, when a group containing fluorine is used as R 7 and R 8 , the wavelength of light absorption can be reduced or the dielectric characteristics can be improved.
 本発明では、用途に応じて高分子前駆体の構造を選べるのが重要である。 In the present invention, it is important that the structure of the polymer precursor can be selected according to the application.
 なお、Rの4価は酸と結合するための価数のみを示しているが、Rは置換基を有していてもよい。同様に、Rの2価はアミンと結合するための価数のみを示しているが、他に更なる置換基を有していてもよい。 Incidentally, tetravalent R 7 shows only valence for bonding with the acid but, R 7 may have a substituent. Similarly, the divalent value of R 8 indicates only the valency for bonding to the amine, but may have other substituents.
 RおよびR10は、水素原子または1価の有機基またはケイ素を有する官能基である。 R 9 and R 10 are a hydrogen atom, a monovalent organic group, or a functional group having silicon.
 RおよびR10が1価の有機基である場合は、例えば、アルキル基、アルケニル基、アルキニル基、アリール基などを挙げることができる。RおよびR10が1価のケイ素を有する官能基である場合は、例えば、シロキサン基、シラン基、シラノール基などを挙げることができる。またRおよびR10の一部のみを水素または一価の有機基とすることも可能であり、これにより、溶解性を制御することができる。 When R 9 and R 10 are monovalent organic groups, examples thereof include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. When R 9 and R 10 are a functional group having monovalent silicon, examples thereof include a siloxane group, a silane group, and a silanol group. In addition, only a part of R 9 and R 10 can be hydrogen or a monovalent organic group, whereby the solubility can be controlled.
 高分子前駆体としては、RおよびR10が水素原子であるようなポリアミック酸が好適に用いられる。これにより、アルカリ現像性が良好となり、良好なパターンが得られる。 A polyamic acid in which R 9 and R 10 are hydrogen atoms is preferably used as the polymer precursor. Thereby, alkali developability becomes favorable and a favorable pattern is obtained.
(ポリアミック酸)
 ポリアミック酸は、従来公知の手法を適用することにより調製可能である。例えば、酸二無水物とジアミンを溶液中で混合するのみで調製できる。1段階の反応で合成することができ、容易かつ低コストで得られ、更なる修飾が不要であるため、好ましく使われている。高分子前駆体の合成方法は特に限定されないが、公知の手法が適用可能である。
(Polyamic acid)
The polyamic acid can be prepared by applying a conventionally known method. For example, it can be prepared simply by mixing acid dianhydride and diamine in a solution. It is preferably used because it can be synthesized by a one-step reaction, can be obtained easily and at low cost, and does not require further modification. The method for synthesizing the polymer precursor is not particularly limited, but a known method can be applied.
 本発明で用いることのできるテトラカルボン酸二無水物の例としては、下記一般式(5)で示されるものを挙げることができる。ただし、下記に示す具体例は一例であり、本発明の趣旨に反しない限り、公知のものを用いることができることは言うまでもない。 Examples of tetracarboxylic dianhydrides that can be used in the present invention include those represented by the following general formula (5). However, the specific examples shown below are merely examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.
Figure JPOXMLDOC01-appb-I000017
(式中のRは、上述したとおりである。) 
Figure JPOXMLDOC01-appb-I000017
(R 7 in the formula is as described above.)
 なお、本実施形態に係るポリアミック酸における繰り返し単位中のR基は、ポリアミック酸製造の原料として用いられるテトラカルボン酸二無水物のRに由来することが好ましい。 Incidentally, R 7 groups in the repeating units in the polyamic acid according to the present embodiment is preferably derived from the R 7 of the tetracarboxylic dianhydride used as a raw material for polyamic acid production.
 上記高分子前駆体の製造に適用可能な酸二無水物としては、例えば、1,3,3a,4,5,9b-ヘキサヒドロ-5(テトラヒドロ-2,5-ジオキソ-3-フラニル)ナフト[1,2-c]フラン-1,3-ジオン、エチレンテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、シクロブタンテトラカルボン酸二無水物、メチルシクロブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物などの脂肪族テトラカルボン酸二無水物;ピロメリット酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、2,2’,3,3’-ベンゾフェノンテトラカルボン酸二無水物、2,3’,3,4’-ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、2,2’,3,3’-ビフェニルテトラカルボン酸二無水物、2,3’,3,4’-ビフェニルテトラカルボン酸二無水物、2,2’,6,6’-ビフェニルテトラカルボン酸二無水物、2,2-ビス(3,4-ジカルボキシフェニル)プロパン二無水物、2,2-ビス(2,3-ジカルボキシフェニル)プロパン二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、ビス(3,4-ジカルボキシフェニル)スルホン二無水物、1,1-ビス(2,3-ジカルボキシフェニル)エタン二無水物、ビス(2,3-ジカルボキシフェニル)メタン二無水物、ビス(3,4-ジカルボキシフェニル)メタン二無水物、2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物、2,2-ビス(2,3-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物、1,3-ビス〔(3,4-ジカルボキシ)ベンゾイル〕ベンゼン二無水物、1,4-ビス〔(3,4-ジカルボキシ)ベンゾイル〕ベンゼン二無水物、2,2-ビス{4-〔4-(1,2-ジカルボキシ)フェノキシ〕フェニル}プロパン二無水物、2,2-ビス{4-〔3-(1,2-ジカルボキシ)フェノキシ〕フェニル}プロパン二無水物、ビス{4-〔4-(1,2-ジカルボキシ)フェノキシ〕フェニル}ケトン二無水物、ビス{4-〔3-(1,2-ジカルボキシ)フェノキシ〕フェニル}ケトン二無水物、4,4’-ビス〔4-(1,2-ジカルボキシ)フェノキシ〕ビフェニル二無水物、4,4’-ビス〔3-(1,2-ジカルボキシ)フェノキシ〕ビフェニル二無水物、ビス{4-〔4-(1,2-ジカルボキシ)フェノキシ〕フェニル}ケトン二無水物、ビス{4-〔3-(1,2-ジカルボキシ)フェノキシ〕フェニル}ケトン二無水物、ビス{4-〔4-(1,2-ジカルボキシ)フェノキシ〕フェニル}スルホン二無水物、ビス{4-〔3-(1,2-ジカルボキシ)フェノキシ〕フェニル}スルホン二無水物、ビス{4-〔4-(1,2-ジカルボキシ)フェノキシ〕フェニル}スルフィド二無水物、ビス{4-〔3-(1,2-ジカルボキシ)フェノキシ〕フェニル}スルフィド二無水物、2,2-ビス{4-〔4-(1,2-ジカルボキシ)フェノキシ〕フェニル}-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物、2,2-ビス{4-〔3-(1,2-ジカルボキシ)フェノキシ〕フェニル}-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物、1,1,1,3,3,3-ヘキサフルオロ-2,2-ビス(2,3-または3,4-ジカルボキシフェニル)プロパン二無水物、1,4,5,8-ナフタレンテトラカルボン酸二無水物、1,2,5,6-ナフタレンテトラカルボン酸二無水物、1,2,3,4-ベンゼンテトラカルボン酸二無水物、3,4,9,10-ぺリレンテトラカルボン酸二無水物、2,3,6,7-アントラセンテトラカルボン酸二無水物、1,2,7,8-フェナントレンテトラカルボン酸二無水物、ピリジンテトラカルボン酸二無水物、スルホニルジフタル酸無水物、m-ターフェニル-3,3’,4,4’-テトラカルボン酸二無水物、p-ターフェニル-3,3’,4,4’-テトラカルボン酸二無水物などの芳香族テトラカルボン酸二無水物等が挙げられる。 Examples of acid dianhydrides applicable to the production of the polymer precursor include 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [ 1,2-c] furan-1,3-dione, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides; pyromellitic dianhydrides, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydrides, 2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetraca Boronic acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6 '-Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2 , 3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3 3,3-hexafluoro Lopan dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4- Dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) Phenoxy] phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-di Carboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-di) Carboxy) phenoxy] biphenyl dianhydride, 4, 4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3 -(1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- ( 1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3 3-hexafluoropro Dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, Pyridinetetracarboxylic dianhydride, sulfo Rudiphthalic anhydride, m-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, etc. An aromatic tetracarboxylic dianhydride etc. are mentioned.
 これらは単独あるいは2種以上混合して用いられる。そして、特に好ましく用いられるテトラカルボン酸二無水物として1,3,3a,4,5,9b-ヘキサヒドロ-5(テトラヒドロ-2,5-ジオキソ-3-フラニル)ナフト[1,2-c]フラン-1,3-ジオン、ピロメリット酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、2,2’,6,6’-ビフェニルテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物が挙げられる。 These may be used alone or in combination of two or more. As a particularly preferred tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan -1,3-dione, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1, Examples include 1,1,3,3,3-hexafluoropropane dianhydride.
 併用する酸二無水物としてフッ素が導入された酸二無水物や、脂環骨格を有する酸二無水物を用いると、透明性をそれほど損なわずに溶解性や熱膨張率等の物性を調整することが可能である。また、ピロメリット酸無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、1,4,5,8-ナフタレンテトラカルボン酸二無水物などの剛直な酸二無水物を用いると、最終的に得られるポリイミドの線熱膨張係数が小さくなるが、透明性の向上を阻害する傾向があるので、共重合割合に注意しながら併用してもよい。 When acid dianhydride into which fluorine is introduced or acid dianhydride having an alicyclic skeleton is used as the acid dianhydride to be used in combination, the physical properties such as solubility and thermal expansion coefficient are adjusted without significantly impairing transparency. It is possible. Also, rigid acid dianhydrides such as pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copolymerization ratio.
 酸二無水物の複数のカルボキシル基は、単一の芳香環上に存在しても、複数の芳香環上に存在してもよく、例えば、下記式で表される酸二無水物を使用することができる。 A plurality of carboxyl groups of the acid dianhydride may be present on a single aromatic ring or a plurality of aromatic rings. For example, an acid dianhydride represented by the following formula is used. be able to.
Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000018
 本発明で用いることができるアミンは、下記一般式(6)で示されるジアミンが挙げられる。ただし、下記のものは一例であり、本発明の趣旨に反しない限り、公知のものを用いることができることは言うまでもない。
Figure JPOXMLDOC01-appb-I000019
(式中のRは、上述したとおりである。)
Examples of amines that can be used in the present invention include diamines represented by the following general formula (6). However, the following are examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.
Figure JPOXMLDOC01-appb-I000019
(R 8 in the formula is as described above.)
 R基が2価の芳香族基である場合のジアミンの例としては、パラフェニレンジアミン、3,3’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ジメチル-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、3,3’-ジクロロ-4,4’-ジアミノビフェニル、9,10-ビス(4-アミノフェニル)アントラセン、4,4’-ジアミノベンゾフェノン、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、4,4’-ジアミノジフェニルスルフォキシド、1,3-ビス(3-アミノフェノキシ)ベンゼン、ビス〔4-(4-アミノフェノキシ)フェニル〕スルホン、ビス〔4-(3-アミノフェノキシ)フェニル〕スルホン、4,4’-ビス(4-アミノフェノキシ)ビフェニル、4,4’-ビス(3-アミノフェノキシビフェニル、ビス〔4-(4-アミノフェノキシ)フェニル〕エーテル、1,1,1,3,3,3-ヘキサフルオロ-2,2-ビス(4-アミノフェニル)プロパン、1,1,1,3,3,3-ヘキサフルオロ-2,2-ビス〔4-(4-アミノフェノキシ)フェニル〕プロパン、1,1,1,3,3,3-ヘキサフルオロ-2,2-ビス(3-アミノ-4-メチルフェニル)プロパン、メタフェニレンジアミン、4,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルスルフィド、3,4’-ジアミノジフェニルエーテル、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼンを挙げることができる。 Examples of diamines when the R 8 group is a divalent aromatic group include paraphenylenediamine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4 ′. -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,4 '-Diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis (3-aminophenoxy) benzene, bis [4 -(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) biff Nyl, 4,4′-bis (3-aminophenoxybiphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,1,1,3,3,3-hexafluoro-2,2-bis ( 4-aminophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3 3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) propane, metaphenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether 1,4-bis (4-aminophenoxy) benzene and 1,3-bis (4-aminophenoxy) benzene.
 R基が2価の脂肪族基である場合のジアミンの例としては、1,1-メタキシリレンジアミン、1,3-プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、4,4-ジアミノヘプタメチレンジアミン、1,4-ジアミノシクロヘキサン、イソホロンジアミン、テトラヒドロジシクロペンタジエニレンジアミン、ヘキサヒドロ-4,7-メタノインダニレンジメチレンジアミン、トリシクロ[6.2.1.02,7]-ウンデシレンジメチルジアミン、4,4’-メチレンビス(シクロヘキシルアミン)、イソホロンジアミンを挙げることができる。 Examples of diamines when the R 8 group is a divalent aliphatic group include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, Octamethylenediamine, Nonamethylenediamine, 4,4-Diaminoheptamethylenediamine, 1,4-Diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentadienylenediamine, Hexahydro-4,7-methanoindanylenediethylenediamine And tricyclo [6.2.1.02,7] -undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine), and isophoronediamine.
 また、別の例としては、下記一般式(11)で示されるジアミノポリシロキサン等が挙げられる。 Another example is diaminopolysiloxane represented by the following general formula (11).
Figure JPOXMLDOC01-appb-I000020
Figure JPOXMLDOC01-appb-I000020
 ただし、式中、R28およびR29はそれぞれ独立して二価の炭化水素基を表し、R30およびR31は、それぞれ独立して一価の炭化水素基を表す。pは1以上、好ましくは1~10の整数である。 However, in the formula, R 28 and R 29 each independently represent a divalent hydrocarbon group, and R 30 and R 31 each independently represent a monovalent hydrocarbon group. p is 1 or more, preferably an integer of 1 to 10.
 具体的には、上記式(11)におけるR28およびR29としては、メチレン基、エチレン基、プロピレン基等の炭素数1~7のアルキレン基、フェニレン基等の炭素数6~18のアリーレン基などが挙げられ、R30およびR31としては、メチル基、エチル基等の炭素数1~7のアルキル基、フェニル基等の炭素数6~12のアリール基などが挙げられる。  Specifically, R 28 and R 29 in the formula (11) are an alkylene group having 1 to 7 carbon atoms such as a methylene group, an ethylene group or a propylene group, or an arylene group having 6 to 18 carbon atoms such as a phenylene group. Examples of R 30 and R 31 include an alkyl group having 1 to 7 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 12 carbon atoms such as a phenyl group.
 また、高分子前駆体としては、ポリアミック酸エステルも好適に用いることができる。ポリアミック酸エステルは、公知の方法により得ることができる。 Also, polyamic acid ester can be suitably used as the polymer precursor. The polyamic acid ester can be obtained by a known method.
 例えば、3,3’-ベンソフェノンテトラカルボン酸二無水物などの酸無水物とエタノールなどのアルコールを反応させハーフエステルとする。そのハーフエステルを塩化チオニルを用いてジエステルジ酸クロライドとする。そのジエステルジ酸クロライドを3,5-ジアミノ安息香酸などのジアミンと反応させることにより、ポリアミック酸のエステルを得ることができる。 For example, an acid anhydride such as 3,3'-benzophenone tetracarboxylic dianhydride and an alcohol such as ethanol are reacted to form a half ester. The half ester is converted to diester diacid chloride using thionyl chloride. An ester of polyamic acid can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.
 感光性樹脂組成物中、少なくとも一部にポリアミック酸、または、ポリアミック酸エステルの繰り返し単位を有する高分子前駆体としては、単一種類の材料を用いてもよいし、複数種類を混合物として用いてもよい。また、RおよびRの少なくとも何れか一方がそれぞれ複数の構造からなる、共重合体であってもよい。 In the photosensitive resin composition, as a polymer precursor having at least a part of a polyamic acid or a polyamic acid ester repeating unit, a single type of material may be used, or a plurality of types may be used as a mixture. Also good. Further, it may be a copolymer in which at least one of R 7 and R 8 has a plurality of structures.
 また、上記の酸無水物とアルコールとを反応させて得たハーフエステルに、ジイソシアン酸イソホロンなどのジイソシアネートと反応させることによって、ポリアミック酸エステルを得てもよい。尚、上記のジアミンを用いた合成方法よりも、ジイソシアネートを用いた合成方法の方が、簡便にポリアミック酸エステルを合成することができる。
 ポリアミック酸エステルを得るために用いることができるジイソシアネートとしては、下記一般式(7)で示されるジイソシアネートが挙げられる。ただし、下記のものは一例であり、本発明の趣旨に反しない限り、公知のものを用いることができる。
Moreover, you may obtain polyamic acid ester by making half-ester obtained by making said acid anhydride and alcohol react with diisocyanates, such as isophorone diisocyanate. In addition, the synthetic method using diisocyanate can synthesize | combine polyamic acid ester more simply than the synthetic method using said diamine.
Examples of the diisocyanate that can be used for obtaining the polyamic acid ester include diisocyanates represented by the following general formula (7). However, the following are examples, and known ones can be used as long as they do not contradict the gist of the present invention.
Figure JPOXMLDOC01-appb-I000021
(式中のRは、上述したとおりである。)
Figure JPOXMLDOC01-appb-I000021
(R 8 in the formula is as described above.)
 前記ジイソシアネートとしては、例えば、ジイソシアン酸イソホロン(ITI)、トルエンジイソシアネート(TDI)、4,4’-ジイソシアン酸メチレンジフェニル(MDI)、2,2-ビス(4-イソシアナトフェニル)ヘキサフルオロプロパン、ヘキサメチレンジイソシアネート(HMDI)等が挙げられる。 Examples of the diisocyanate include isophorone diisocyanate (ITI), toluene diisocyanate (TDI), methylene diphenyl 4,4′-diisocyanate (MDI), 2,2-bis (4-isocyanatophenyl) hexafluoropropane, hexa And methylene diisocyanate (HMDI).
 前記高分子前駆体は、下記一般式(4-1)で表される構造を有するポリアミック酸エステルであることが好ましい。
Figure JPOXMLDOC01-appb-I000022
(式(4-1)中、前記一般式(4)と同様に、Rは4価の有機基であり、Rは2価の有機基であり、R11は2価の有機基であり、mは1以上の整数であり、nは0または1以上の整数である。R9-1およびR10-1は、相互に同一でも異なってもよく、1価の有機基またはケイ素を有する官能基である。Rは、脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであることが好ましい。)
The polymer precursor is preferably a polyamic acid ester having a structure represented by the following general formula (4-1).
Figure JPOXMLDOC01-appb-I000022
(In the formula (4-1), as in the general formula (4), R 7 is a tetravalent organic group, R 8 is a divalent organic group, and R 11 is a divalent organic group. M is an integer of 1 or more, and n is 0 or an integer of 1 or more, and R 9-1 and R 10-1 may be the same or different from each other, and may be a monovalent organic group or silicon. R 8 is preferably any one of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group.)
 式(4-1)中、Rで表される4価の有機基は特に限定されず、用途に応じて選択すればよい。例えば、芳香族基、好ましくは炭素原子数6~32の芳香族基、または脂肪族基、好ましくは炭素原子数4~20の脂肪族基が挙げられる。Rは、前記高分子前駆体の製造において用いられる前記一般式(5)で表される酸二無水物に含まれる置換基Rであることが好ましい。 In formula (4-1), the tetravalent organic group represented by R 7 is not particularly limited, and may be selected according to the application. For example, an aromatic group, preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, preferably an aliphatic group having 4 to 20 carbon atoms. R 7 is preferably a substituent R 7 contained in the acid dianhydride represented by the general formula (5) used in the production of the polymer precursor.
 前記一般式(4-1)で表される構造を有するポリアミック酸エステルは、特に、解像性の観点から、Rは、芳香族環と脂肪族炭化水素環との縮合環を含む4価の有機基、芳香族基と脂環式炭化水素基とを含む4価の有機基、またはフッ素原子を含む4価の有機基であることが好ましい。 In the polyamic acid ester having the structure represented by the general formula (4-1), in particular, from the viewpoint of resolution, R 7 is a tetravalent containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring. The organic group is preferably a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a tetravalent organic group containing a fluorine atom.
 前記フッ素原子を含む4価の有機基は、芳香族基(好ましくはフェニル基、ナフタレン基、特にフェニル基)を有することが好ましく、トリフルオロメチル基と芳香族基を有することが好ましい。 The tetravalent organic group containing a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthalene group, particularly a phenyl group), and preferably has a trifluoromethyl group and an aromatic group.
 前記一般式(4-1)で表される構造を有するポリアミック酸エステルは、下記一般式(4-1-1)および(4-1-2)の少なくともいずれか一方で表される構造を有することが好ましい。
Figure JPOXMLDOC01-appb-I000023
(式(4-1-1)中、R、R9-1、R10-1、R11、mおよびnは式(4-1)と同様である。)
Figure JPOXMLDOC01-appb-I000024
(式(4-1-2)中、R、R9-1、R10-1、R11、mおよびnは式(4-1)と同様である。)
The polyamic acid ester having the structure represented by the general formula (4-1) has a structure represented by at least one of the following general formulas (4-1-1) and (4-1-2). It is preferable.
Figure JPOXMLDOC01-appb-I000023
(In the formula (4-1-1), R 8 , R 9-1 , R 10-1 , R 11 , m and n are the same as in the formula (4-1).)
Figure JPOXMLDOC01-appb-I000024
(In formula (4-1-2), R 8 , R 9-1 , R 10-1 , R 11 , m and n are the same as in formula (4-1).)
 式(4-1)中のRは、脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであることが好ましい。前記フェニレン基およびアルキレン基は、それぞれ式(4-1)においてRと結合する2つの窒素原子と直接に結合する。一方、前記脂環式骨格、および、前記アルキレン基で結合されたビスフェニレン骨格は、式(4-1)においてRと結合する2つの窒素原子と直接に結合してもよく、しなくともよい。Rは、前記高分子前駆体の製造において用いられる前記一般式(6)で表されるジアミンまたは前記一般式(7)で表されるジイソシアネートに含まれる置換基Rであることが好ましい。 R 8 in formula (4-1) is preferably any of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group. The phenylene group and the alkylene group are directly bonded to the two nitrogen atoms bonded to R 8 in the formula (4-1). On the other hand, the alicyclic skeleton and the bisphenylene skeleton bonded by the alkylene group may be directly bonded to the two nitrogen atoms bonded to R 8 in the formula (4-1) or not. Good. R 8 is preferably a substituent R 8 contained in the diamine represented by the general formula (6) or the diisocyanate represented by the general formula (7) used in the production of the polymer precursor.
 Rにおける前記脂環式骨格を有する基は、置換基を有していてもよく、縮合環を形成していてもよい。前記脂環式骨格を有する基は、下記一般式(8A)で表されることが好ましい。
Figure JPOXMLDOC01-appb-I000025
(式(8A)中、n1は0~10の整数を表し、R8A1は脂肪族基であり、好ましくは炭素数1~5のアルキレン基であり、より好ましくはメチレン基を表し、R8A2はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表す。)
The group having the alicyclic skeleton in R 8 may have a substituent and may form a condensed ring. The group having an alicyclic skeleton is preferably represented by the following general formula (8A).
Figure JPOXMLDOC01-appb-I000025
(In the formula (8A), n1 represents an integer of 0 to 10, R 8A1 represents an aliphatic group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, and R 8A2 represents Each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group.)
 Rにおける前記フェニレン基は、置換基を有していてもよく、縮合環を形成していてもよい。前記フェニレン基は、下記一般式(8B)で表されることが好ましい。
Figure JPOXMLDOC01-appb-I000026
(式(8B)中、n2は0~4の整数を表し、R8B1はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表す。)
The phenylene group for R 8 may have a substituent and may form a condensed ring. The phenylene group is preferably represented by the following general formula (8B).
Figure JPOXMLDOC01-appb-I000026
(In Formula (8B), n2 represents an integer of 0 to 4, and R 8B1 each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group.)
 Rにおける前記アルキレン基で結合されたビスフェニレン骨格を有する基は、置換基を有していてもよく、縮合環を形成していてもよい。前記アルキレン基で結合されたビスフェニレン骨格を有する基は、下記一般式(8C)で表されることが好ましい。
Figure JPOXMLDOC01-appb-I000027
(式(8C)中、n3およびn4はそれぞれ独立に0~4の整数を表し、R8C1およびR8C2はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表し、R8C3は炭素数1~5のアルキレン基を表す。)
The group having a bisphenylene skeleton bonded to the alkylene group in R 8 may have a substituent and may form a condensed ring. The group having a bisphenylene skeleton bonded with the alkylene group is preferably represented by the following general formula (8C).
Figure JPOXMLDOC01-appb-I000027
(In the formula (8C), n3 and n4 each independently represents an integer of 0 to 4, and R 8C1 and R 8C2 are each independently an aliphatic group or an aromatic group, preferably a methyl group, an ethyl group, etc. R 8C3 represents an alkylene group having 1 to 5 carbon atoms.)
 式(8C)中のR8C3のアルキレン基は、脂肪族基または芳香族基等の置換基を有していてもよい。 The alkylene group represented by R 8C3 in formula (8C) may have a substituent such as an aliphatic group or an aromatic group.
 Rにおける前記アルキレン基は、炭素数1~10のアルキレン基であることが好ましく、炭素数2~8のアルキレン基であることがより好ましい。なお、Rにおける前記アルキレン基は、脂肪族基または芳香族基等の置換基を有していてもよい。 The alkylene group for R 8 is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms. Incidentally, the alkylene group in R 8 may have a substituent such as an aliphatic group or an aromatic group.
 Rは、解像性に優れるため、脂環式骨格を有する基であることが好ましく、脂環式骨格を有し、芳香族骨格を有しない基であることがより好ましい。 R 8 is preferably a group having an alicyclic skeleton because of excellent resolution, and more preferably a group having an alicyclic skeleton and no aromatic skeleton.
 本発明において、式(4-1)中のR9-1およびR10-1は、それぞれ独立に1価の有機基またはケイ素を有する官能基である。R9-1およびR10-1における前記1価の有機基としては、例えば、アルキル基、アルケニル基、アルキニル基、アリール基等を挙げることができる。R9-1およびR10-1における前記1価のケイ素を有する官能基としては、例えば、シロキサン基、シラン基、シラノール基などを挙げることができる。 In the present invention, R 9-1 and R 10-1 in formula (4-1) are each independently a monovalent organic group or a functional group having silicon. Examples of the monovalent organic group in R 9-1 and R 10-1 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Examples of the functional group having monovalent silicon in R 9-1 and R 10-1 include a siloxane group, a silane group, and a silanol group.
 式(4-1)中のR9-1およびR10-1は、ポリアミック酸エステルの合成時における溶解性の観点からアルキル基であることが好ましい。アルキル基としては、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、ヘキシル基などが挙げられる。ここでアルキル基は、ブチル基、ペンチル基、または、ヘキシル基であることが好ましい。 R 9-1 and R 10-1 in the formula (4-1) are preferably alkyl groups from the viewpoint of solubility during the synthesis of the polyamic acid ester. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Here, the alkyl group is preferably a butyl group, a pentyl group, or a hexyl group.
 本発明において、式(4-1)中のR11は、2価の有機基であり、例えば、芳香族または脂肪族エステル基、アミド基、アミドイミド基、シロキサン基、エポキシ基、オキセタニル基等を少なくとも一部の構成として含む基を挙げることができる。 In the present invention, R 11 in the formula (4-1) is a divalent organic group such as an aromatic or aliphatic ester group, an amide group, an amidoimide group, a siloxane group, an epoxy group, or an oxetanyl group. A group included as at least a part of the structure can be given.
 以下に、本発明の感光性樹脂組成物に配合可能な他の成分を説明する。 Hereinafter, other components that can be blended in the photosensitive resin composition of the present invention will be described.
 本発明の感光性樹脂組成物に用いることができる溶媒は、光塩基発生剤、高分子前駆体および他の添加剤を溶解させるものであれば特に制限はない。一例としては、N,N’-ジメチルホルムアミド、N-メチルピロリドン、N-エチル-2-ピロリドン、N,N’-ジメチルアセトアミド、ジエチレングリコールジメチルエーテル、シクロペンタノン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、テトラメチル尿素、1,3-ジメチル-2-イミダゾリノン、N-シクロヘキシル-2-ピロリドン、ジメチルスルホキシド、ヘキサメチルホスホルアミド、ピリジン、γ-ブチロラクトン、ジエチレングリコールモノメチルエーテルを挙げることができる。これらは単独で用いても、2種以上を混合して用いてもかまわない。使用する溶媒の量は特に限定されないが、例えば、塗布膜厚や粘度に応じて、高分子前駆体100質量部に対し、50~9000質量部の範囲で用いればよい。 The solvent that can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve a photobase generator, a polymer precursor, and other additives. Examples include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Examples include butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited. For example, the solvent may be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the polymer precursor depending on the coating film thickness and viscosity.
 本発明の感光性樹脂組成物には、更に光感度を向上させるために増感剤を添加することもできる。増感剤としては、例えばミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジメチルアミノベンザル)-4-メチルシクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンズチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン等が挙げられ、感度の点で、4-(1-メチルエチル)-9H-チオキサンテン-9-オンなどのチオキサントン類を用いることが好ましい。これらは単独でまたは2~5種類の組み合わせで用いることができる。増感剤は、高分子前駆体100質量部に対し、0.1~10質量部を用いるのが好ましい。 A sensitizer can also be added to the photosensitive resin composition of the present invention in order to further improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal) cyclohexanone. 2,6-bis (4′-dimethylaminobenzal) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) Chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p- Dimethylaminophenylvinylene) benzothiazole, 2- (p-di Acetylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4′-dimethylaminobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7 -Diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3- Ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N′-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid Amyl, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benz And thiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like. 4- (1-Methylethyl)- It is preferable to use thioxanthones such as 9H-thioxanthen-9-one. These can be used alone or in combination of 2 to 5 kinds. The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer precursor.
 また、本発明の感光性樹脂組成物には、基材との接着性向上のため接着助剤を配合することもできる。接着助剤としては、本発明の趣旨に反しない限り公知のものを用いることができる。例えば、γ-アミノプロピルジメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、γ-グリシドキシプロピルメチルジメトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン、N-[3-(トリエトキシシリル)プロピル]フタルアミド酸、ベンゾフェノンテトラカルボン酸二無水物と(トリエトキシシリル)プロピルアミンの反応生成物等を挙げることができる。接着助剤の配合量は、高分子前駆体100質量部に対し、0.5~10質量部の範囲が好ましい。 In addition, an adhesion aid can be blended with the photosensitive resin composition of the present invention in order to improve the adhesion to the substrate. Any known adhesion assistant can be used as long as it is not contrary to the gist of the present invention. For example, γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, N- [3- ( And (triethoxysilyl) propyl] phthalamic acid, a reaction product of benzophenonetetracarboxylic dianhydride and (triethoxysilyl) propylamine. The blending amount of the adhesion assistant is preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer precursor.
 また、本発明の感光性樹脂組成物には、塩基増殖剤を添加してもよい。厚膜のパターンを形成する時、表面から下まで同じ程度の光塩基発生剤の分解率が求められる。この場合、感度を向上するため、塩基増殖剤の添加が好ましい。例えば、特開2012-237776号公報、特開2006-282657号公報などに開示された塩基増殖剤の使用が可能である。 In addition, a base proliferating agent may be added to the photosensitive resin composition of the present invention. When forming a thick film pattern, the decomposition rate of the same amount of photobase generator is required from the surface to the bottom. In this case, in order to improve sensitivity, the addition of a base proliferating agent is preferable. For example, the base proliferating agents disclosed in JP 2012-237776 A, JP 2006-282657 A, and the like can be used.
 なお、本発明の感光性樹脂組成物には、硬化後の膜特性を大きく損なわない範囲で、光によって酸を発生させる他の感光性成分を加えてもよい。本発明の感光性樹脂組成物にエチレン性不飽和結合を1つまたは2つ以上有する化合物を加える場合、光ラジカル発生剤を添加してもよい。 In addition, you may add to the photosensitive resin composition of this invention the other photosensitive component which generates an acid with light in the range which does not impair the film | membrane characteristic after hardening significantly. When adding a compound having one or more ethylenically unsaturated bonds to the photosensitive resin composition of the present invention, a photo radical generator may be added.
 本発明の感光性樹脂組成物に加工特性や各種機能性を付与するために、その他に様々な有機または無機の低分子または高分子化合物を配合してもよい。例えば、染料、界面活性剤、レベリング剤、可塑剤、微粒子等を用いることができる。微粒子には、ポリスチレン、ポリテトラフルオロエチレン等の有機微粒子、コロイダルシリカ、カーボン、層状珪酸塩等の無機微粒子等が含まれ、それらは多孔質や中空構造であってもよい。多孔質形状や中空構造を得るための具体的材料としては各種顔料、フィラー、および繊維等がある。 In order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various other organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers, fibers, and the like.
 本発明のドライフィルムは、キャリアフィルム(支持体)上に、本発明の感光性樹脂組成物を塗布、乾燥させることにより得られる樹脂層を有する。ドライフィルムの形成は、本発明の感光性樹脂組成物を上記有機溶剤で希釈して適切な粘度に調整した上で、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、スプレーコーター等でキャリアフィルム上に均一な厚さに塗布する。その後、塗布された感光性樹脂組成物を、通常、50~130℃の温度で1~30分間乾燥することで、樹脂層を形成することができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で、10~150μm、好ましくは20~60μmの範囲で適宜選択される。 The dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film (support). The dry film is formed by diluting the photosensitive resin composition of the present invention with the above-mentioned organic solvent and adjusting the viscosity to an appropriate viscosity, followed by comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer Apply a uniform thickness on a carrier film with a roll coater, gravure coater, spray coater, etc. Thereafter, the applied photosensitive resin composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 μm, preferably 20 to 60 μm.
 キャリアフィルムとしては、プラスチックフィルムが用いられ、ポリエチレンテレフタレート等のポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等のプラスチックフィルムを用いることが好ましい。キャリアフィルムの厚さについては特に制限はないが、一般に、10~150μmの範囲で適宜選択される。 As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 μm.
 キャリアフィルム上に本発明の感光性樹脂組成物からなる樹脂層を形成した後、膜の表面に塵が付着することを防ぐ等の目的で、さらに、膜の表面に、剥離可能なカバーフィルムを積層することが好ましい。剥離可能なカバーフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができる。カバーフィルムとしては、カバーフィルムを剥離するときに、樹脂層とキャリアフィルムとの接着力よりも小さいものであればよい。 After the resin layer made of the photosensitive resin composition of the present invention is formed on the carrier film, a peelable cover film is further formed on the film surface for the purpose of preventing dust from adhering to the film surface. It is preferable to laminate. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a cover film, what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.
 次に、本発明の感光性樹脂組成物を用いた硬化物としてのパターン膜の製造方法について、一例として、高分子前駆体としてポリイミド前駆体であるポリアミック酸エステルを配合した場合について説明する。 Next, as an example of a method for producing a patterned film as a cured product using the photosensitive resin composition of the present invention, a case where a polyamic acid ester that is a polyimide precursor is blended as a polymer precursor will be described.
 まず、ステップ1として感光性樹脂組成物を基材上に塗布し、乾燥することにより塗膜を得る。感光性樹脂組成物を基材上に塗布する方法としては、従来から感光性樹脂組成物の塗布に用いられていた方法、例えば、スピンコーター、バーコーター、ブレードコーター、カーテンコーター、スクリーン印刷機等で塗布する方法、スプレーコーターで噴霧塗布する方法、さらにはインクジェット法等を用いることができる。塗膜の乾燥方法としては、風乾、オーブンまたはホットプレートによる加熱乾燥、真空乾燥等の方法が用いられる。また、塗膜の乾燥は、感光性樹脂組成物中のポリアミック酸エステルのイミド化が起こらないような条件で行うことが望ましい。具体的には、自然乾燥、送風乾燥、あるいは加熱乾燥を、20~140℃で1分~1時間の条件で行うことができる。好ましくは、ホットプレート上で1~20分乾燥を行う。また、真空乾燥も可能であり、この場合は、室温で1分~1時間の条件で行うことができる。 First, as Step 1, a photosensitive resin composition is applied on a substrate and dried to obtain a coating film. As a method for coating the photosensitive resin composition on the substrate, methods conventionally used for coating the photosensitive resin composition, such as spin coater, bar coater, blade coater, curtain coater, screen printer, etc. The method of apply | coating, the method of spray-coating with a spray coater, Furthermore, the inkjet method etc. can be used. As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Moreover, it is desirable that the coating film be dried under conditions such that imidation of the polyamic acid ester in the photosensitive resin composition does not occur. Specifically, natural drying, blast drying, or heat drying can be performed at 20 to 140 ° C. for 1 minute to 1 hour. Preferably, drying is performed on a hot plate for 1 to 20 minutes. Vacuum drying is also possible, and in this case, it can be carried out at room temperature for 1 minute to 1 hour.
 基材に特に制限はなく、シリコンウェハー、配線基板、各種樹脂、金属、半導体装置のパッシベーション保護膜などに広く適用できる。 The base material is not particularly limited, and can be widely applied to silicon wafers, wiring boards, various resins, metals, and passivation protective films for semiconductor devices.
 また、低温でのイミド化が可能であるため、プリント配線板の基板等の高温処理に適さない部材、材料に広く適用可能であるのが特徴である。 Also, since imidization at low temperature is possible, it is characterized by being widely applicable to members and materials that are not suitable for high-temperature processing such as printed wiring board substrates.
 次に、ステップ2として上記塗膜を、パターンを有するフォトマスクを介して、あるいは、直接露光する。露光光線は、光塩基発生剤を活性化させ塩基を発生させることができる波長のものを用いる。上述したように、適宜増感剤を用いると、光感度を調製することができる。露光装置としては、コンタクトアライナー、ミラープロジェクション、ステッパー、レーザーダイレクト露光装置等を用いることができる。 Next, in step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light having a wavelength capable of activating the photobase generator to generate a base is used. As described above, the photosensitivity can be adjusted by appropriately using a sensitizer. As the exposure apparatus, a contact aligner, mirror projection, stepper, laser direct exposure apparatus, or the like can be used.
 続いて、ステップ3として塗膜中に発生した塩基により塗膜のイミド化を促進させるように加熱する。これにより、上記ステップ2において露光部に発生した塩基が触媒となって、ポリアミック酸エステルが部分的にイミド化する。加熱時間および加熱温度は、用いるポリアミック酸エステル、塗布膜厚、光塩基発生剤の種類によって適宜変更する。典型的には、10μm程度の塗布膜厚の場合、110~200℃で2~10分程度である。加熱温度が低すぎると、部分的イミド化を効率的に達成することができない。一方、加熱温度が高すぎると、未露光部のイミド化が進行して、露光部と未露光部との溶解性の差を小さくしてしまい、パターン形成に支障が生ずる懸念がある。 Subsequently, in step 3, heating is performed so as to promote imidization of the coating film by the base generated in the coating film. Thereby, the base generated in the exposed portion in Step 2 serves as a catalyst, and the polyamic acid ester is partially imidized. The heating time and heating temperature are appropriately changed depending on the polyamic acid ester used, the coating film thickness, and the type of photobase generator. Typically, in the case of a coating film thickness of about 10 μm, it is about 2 to 10 minutes at 110 to 200 ° C. If the heating temperature is too low, partial imidization cannot be achieved efficiently. On the other hand, if the heating temperature is too high, imidization of the unexposed area proceeds to reduce the difference in solubility between the exposed area and the unexposed area, which may cause a problem in pattern formation.
 次いで、ステップ4として塗膜を現像液で処理する。これにより、基材上にポリアミック酸エステルおよび部分的にイミド化したポリイミドからなるパターン膜を形成することができる。 Next, in step 4, the coating film is treated with a developer. Thereby, the pattern film which consists of a polyamic acid ester and the partially imidized polyimide can be formed on a base material.
 現像に用いる方法としては、従来知られているフォトレジストの現像方法、例えば回転スプレー法、パドル法、超音波処理を伴う浸せき法等の中から任意の方法を選択することができる。現像液としては、水酸化ナトリウム、炭酸ナトリウム、ケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ジエチルアミン、トリエチルアミン、トリエタノールアミン等の有機アミン類、テトラメチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等の四級アンモニウム塩類等の水溶液を挙げることができる。また、必要に応じて、これらにメタノール、エタノール、イソプロピルアルコール等の水溶性有機溶媒や界面活性剤を適当量添加水溶液として使用することができる。その後、必要に応じて塗膜をリンス液により洗浄してパターン膜を得る。リンス液としては、蒸留水、メタノール、エタノール、イソプロパノール等を単独または組み合わせて用いることができる。
 また、現像液としては、例えば、N-メチル-2-ピロリドン、N-アセチル-2-ピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、ジメチルスルホキシド、γ-ブチロラクトン、ヘキサメチルホスホルトリアミド、メタノール、エタノール、イソプロピルアルコール、メチルカルビトール、エチルカルビトール、トルエン、キシレン、乳酸エチル、ピルビン酸エチル、プロピレングリコールモノメチルエーテルアセテート、メチル-3-メトキシプロピオネート、エチル-3-エトキシプロピオネート、2-ヘプタノン、酢酸エチル、ジアセトンアルコールなど有機溶剤を使用してもよい。
As a method used for the development, an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution of quaternary ammonium salts such as Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant can be used in an appropriate amount as an aqueous solution. Thereafter, the coating film is washed with a rinse liquid as necessary to obtain a pattern film. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol or the like can be used alone or in combination.
Examples of the developer include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, hexamethylphosphoryl tri Amide, methanol, ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropio Organic solvents such as nate, 2-heptanone, ethyl acetate, diacetone alcohol may be used.
 その後、ステップ5としてパターン膜を加熱する。加熱温度は、ポリイミドのパターン膜を硬化可能なように適宜設定する。例えば、不活性ガス中で、150~300℃で5~120分程度の加熱を行う。加熱温度のより好ましい範囲は、150~250℃であり、さらに好ましい範囲は180~220℃である。加熱は、例えば、ホットプレート、オーブン、温度プログラムを設定できる昇温式オーブンを用いることにより行う。このときの雰囲気(気体)としては空気を用いてもよく、窒素、アルゴン等の不活性ガスを用いてもよい。 Thereafter, in step 5, the pattern film is heated. The heating temperature is appropriately set so that the polyimide pattern film can be cured. For example, heating is performed in an inert gas at 150 to 300 ° C. for about 5 to 120 minutes. A more preferable range of the heating temperature is 150 to 250 ° C, and a more preferable range is 180 to 220 ° C. The heating is performed by using, for example, a hot plate, an oven, or a temperature rising oven in which a temperature program can be set. At this time, the atmosphere (gas) may be air, or an inert gas such as nitrogen or argon.
 本発明の感光性樹脂組成物の用途は特に限定されず、例えば、印刷インキ、接着剤、充填剤、電子材料、光回路部品、成形材料、レジスト材料、建築材料、3次元造形、光学部材等、樹脂材料が用いられる公知の種々の分野・製品などが挙げられる。特にポリイミド膜の耐熱性、寸法安定性、絶縁性等の特性が有効とされる広範な分野・製品、例えば、塗料または印刷インキ、或いは、カラーフィルター、フレキシブルディスプレー用フィルム、半導体装置、電子部品、層間絶縁膜、ソルダーレジストなどの配線被覆膜、光回路、光回路部品、反射防止膜、ホログラム、光学部材または建築材料の形成材料として好適に用いられる。 The use of the photosensitive resin composition of the present invention is not particularly limited. For example, printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, optical member, etc. And various known fields and products in which resin materials are used. In particular, a wide range of fields and products in which the properties of polyimide film such as heat resistance, dimensional stability, and insulation are effective, such as paint or printing ink, color filters, flexible display films, semiconductor devices, electronic components, It is suitably used as a material for forming an interlayer insulating film, a wiring coating film such as a solder resist, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member or a building material.
 特に、高分子前駆体としてポリイミド前駆体を含有する場合、本発明の感光性樹脂組成物は、主にパターン形成材料(レジスト)として用いられ、それによって形成されたパターン膜は、ポリイミドからなる永久膜として耐熱性や絶縁性を付与する成分として機能し、例えば、カラーフィルター、フレキシブルディスプレー用フィルム、電子部品、半導体装置、層間絶縁膜、ソルダーレジストやカバーレイ膜などの配線被覆膜、ソルダーダム、光回路、光回路部品、反射防止膜、その他の光学部材または電子部材を形成するのに適している。 In particular, when a polyimide precursor is contained as a polymer precursor, the photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern film formed thereby is a permanent film made of polyimide. Functions as a component that imparts heat resistance and insulation as a film, such as color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films such as solder resists and coverlay films, solder dams, It is suitable for forming an optical circuit, an optical circuit component, an antireflection film, other optical members or electronic members.
 本発明において、前記塩基発生剤は、下記一般式(8)で表されるカルボン酸と、塩基とを混合して製造することができる。 
Figure JPOXMLDOC01-appb-I000028
In the present invention, the base generator can be produced by mixing a carboxylic acid represented by the following general formula (8) and a base.
Figure JPOXMLDOC01-appb-I000028
 前記カルボン酸は、下記一般式(9)で表されるカルボン酸であることがより好ましく、下記式(10)で表される4-メトキシ-3-ニトロフェニル酢酸(MONPA)であることがさらに好ましい。
Figure JPOXMLDOC01-appb-I000029
The carboxylic acid is more preferably a carboxylic acid represented by the following general formula (9), further 4-methoxy-3-nitrophenylacetic acid (MONPA) represented by the following formula (10). preferable.
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000030
 式(8)、(9)中、R~R、X、X、Yは、前記一般式(1)と同様である。 In the formulas (8) and (9), R 1 to R 4 , X 1 , X 2 and Y are the same as those in the general formula (1).
 前記塩基としては、前記一般式(1)において、Bが示す塩基を用いることができる。 As the base, a base represented by B in the general formula (1) can be used.
 前記カルボン酸と塩基との混合は、遮光してカルボン酸の溶液に塩基の溶液を滴下して行うことが好ましい。 The mixing of the carboxylic acid and the base is preferably carried out by dripping the base solution into the carboxylic acid solution in the dark.
 以下、本発明を、実施例を用いてより詳細に説明するが、本発明は下記実施例に限定されるものではない。なお、以下において「部」および「%」とあるのは、特に断りのない限り全て質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.
[カルボン酸の合成]
(参考合成例1:4-メトキシ-3-ニトロフェニル酢酸(MONPA)の合成)
 500ml二口ナスフラスコで、0℃で、濃硝酸(67質量%)30mlと、4-メトキシフェニル酢酸(MOPA)3.32g(20.0mmol)とを混合し、攪拌した(室温、6h)。得られた混合物を冷水に滴下し、吸引濾過を行った後、冷水で洗浄し、淡黄色の固体物として、4-メトキシ-3-ニトロフェニル酢酸(MONPA)を得た(収量:2.51g、収率:60%)。
[Synthesis of carboxylic acid]
(Reference Synthesis Example 1: Synthesis of 4-methoxy-3-nitrophenylacetic acid (MONPA))
In a 500 ml two-necked eggplant flask, 30 ml of concentrated nitric acid (67 mass%) and 3.32 g (20.0 mmol) of 4-methoxyphenylacetic acid (MOPA) were mixed and stirred (room temperature, 6 h). The obtained mixture was added dropwise to cold water, subjected to suction filtration, and then washed with cold water to obtain 4-methoxy-3-nitrophenylacetic acid (MONPA) as a pale yellow solid (yield: 2.51 g). Yield: 60%).
[光塩基発生剤の合成]
(実施例1-1:MOMPA-TBDの合成)
 50mlナスフラスコで、10mlの乾燥エタノールに溶解した上記で合成した4-メトキシ-3-ニトロフェニル酢酸(MONPA)0.300g(1.42mmol)と、10mlのドライエタノールに溶解した1,5,7-トリアザビシクロ[4.4.0]デカ-5-エン(TBD)0.198g(1.42mmol)とを混合し、室温で一晩攪拌した。得られた混合物を濃縮し、EtOH/EtOで再沈殿し、橙色の粘性液体として、MOMPA-TBDを得た(収量:0.289g、収率:58%)。H-NMR(300MHz、CDCl)のチャート図を図1に、また、ピークの解析結果を下記に示す。    
[Synthesis of photobase generator]
Example 1-1 Synthesis of MOMPA-TBD
In a 50 ml eggplant flask, 0.300 g (1.42 mmol) of 4-methoxy-3-nitrophenylacetic acid (MONPA) synthesized above dissolved in 10 ml of dry ethanol and 1,5,7 dissolved in 10 ml of dry ethanol -Triazabicyclo [4.4.0] dec-5-ene (TBD) (0.198 g, 1.42 mmol) was mixed and stirred overnight at room temperature. The resulting mixture was concentrated and reprecipitated with EtOH / Et 2 O to give MOMPA-TBD as an orange viscous liquid (yield: 0.289 g, yield: 58%). A chart of 1 H-NMR (300 MHz, CDCl 3 ) is shown in FIG. 1, and peak analysis results are shown below.
δ1.96 (quint, J = 5.9 Hz, 4H, -CH2-), 3.1-3.4 (m, 8H, -NCH2-), 3.53 (s, 2H, Bn-H), 3.92 (s, 3H, -OCH3), 7.00 (d, J = 8.6 Hz, 1H, Ar-H), 7.51 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.85(d, J = 2.2 Hz, 1H, Ar-H), 10.64 (br, 1.4H, NH). δ1.96 (quint, J = 5.9 Hz, 4H, -CH 2- ), 3.1-3.4 (m, 8H, -NCH 2- ), 3.53 (s, 2H, Bn-H), 3.92 (s, 3H, -OCH 3 ), 7.00 (d, J = 8.6 Hz, 1H, Ar-H), 7.51 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.85 (d, J = 2.2 Hz, 1H, Ar-H), 10.64 (br, 1.4H, NH).
(実施例1-2:MOMPA-DBUの合成)
 合成例1における1,5,7-トリアザビシクロ[4.4.0]デカ-5-エン(TBD)0.198g(1.42mmol)を、ジアザビシクロウンデセン(DBU)0.216g(1.42mmol)にかえた以外は合成例1と同じ方法で、橙色の粘性液体として、MOMPA-DBUを得た(収量:0.419g、収率:81%)。H-NMR(300MHz、CDCl)のチャート図を図2に、また、ピークの解析結果を下記に示す。
Example 1-2 Synthesis of MOMPA-DBU
0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) in Synthesis Example 1 was added to 0.216 g of diazabicycloundecene (DBU) ( MOMPA-DBU was obtained as an orange viscous liquid in the same manner as in Synthesis Example 1 except for changing to 1.42 mmol) (yield: 0.419 g, yield: 81%). A chart of 1 H-NMR (300 MHz, CDCl 3 ) is shown in FIG. 2, and peak analysis results are shown below.
δ1.6-1.8 (m, 6.7H, -CH2-), 1.99 (quint, J = 6.0 Hz, 2H, -CH2-), 2.7-2.9 (m, 2H,
-CH2-), 3.3-3.5 (m, 6H, -NCH2-), 3.56 (s, 2H, Bn-H), 3.92 (s, 3H, -OCH3), 6.99 (d, J = 8.6 Hz, 1H, Ar-H), 7.53 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.86 (d, J = 2.2 Hz, 1H, Ar-H).
δ1.6-1.8 (m, 6.7H, -CH 2- ), 1.99 (quint, J = 6.0 Hz, 2H, -CH 2- ), 2.7-2.9 (m, 2H,
-CH 2- ), 3.3-3.5 (m, 6H, -NCH 2- ), 3.56 (s, 2H, Bn-H), 3.92 (s, 3H, -OCH 3 ), 6.99 (d, J = 8.6 Hz , 1H, Ar-H), 7.53 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.86 (d, J = 2.2 Hz, 1H, Ar-H).
(実施例1-3:MOMPA-2E4MZの合成)
 合成例1における1,5,7-トリアザビシクロ[4.4.0]デカ-5-エン(TBD)0.198g(1.42mmol)を、2-エチル-4-メチルイミダゾール(2E4MZ)0.156g(1.42mmol)にかえた以外は合成例1と同じ方法で、橙色の粘性液体として、MOMPA-2E4MZを得た(収量:0.186g、収率:41%)。H-NMR(300MHz、CDCl)のチャート図を図3に、また、ピークの解析結果を下記に示す。
(Example 1-3: Synthesis of MOMPA-2E4MZ)
In Synthesis Example 1, 0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) was added to 2-ethyl-4-methylimidazole (2E4MZ) 0. MOMPA-2E4MZ was obtained as an orange viscous liquid in the same manner as in Synthesis Example 1 except that the amount was changed to .156 g (1.42 mmol) (yield: 0.186 g, yield: 41%). A chart of 1 H-NMR (300 MHz, CDCl 3 ) is shown in FIG. 3, and peak analysis results are shown below.
δ1.12 (t, J = 7.6 Hz, 6H, -CH2CH3), 2.15 (s, 3H, -CH3), 2.65 (q, J = 7.6 Hz, 2H, -CH2CH3), 3.61 (s, 2H, Bn-H), 3.93 (s, 3H, -OCH3), 6.56 (s, 1H, Im-H), 7.01 (d, J = 8.6 Hz, 1H, Ar-H), 7.48 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.82 (d, J = 2.2 Hz, 1H, Ar-H). δ1.12 (t, J = 7.6 Hz, 6H, -CH 2 CH 3 ), 2.15 (s, 3H, -CH 3 ), 2.65 (q, J = 7.6 Hz, 2H, -CH 2 CH 3 ), 3.61 (s, 2H, Bn-H), 3.93 (s, 3H, -OCH 3 ), 6.56 (s, 1H, Im-H), 7.01 (d, J = 8.6 Hz, 1H, Ar-H), 7.48 ( dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.82 (d, J = 2.2 Hz, 1H, Ar-H).
(実施例1-4:MOMPA-DBAの合成)
 合成例1における1,5,7-トリアザビシクロ[4.4.0]デカ-5-エン(TBD)0.198g(1.42mmol)を、ジブチルアミン(DBA)0.184g(1.42mmol)にかえた以外は合成例1と同じ方法で、橙色の固体物として、MOMPA-DBAを得た(収量:0.473g、収率:98%)。H-NMR(300MHz、CDCl)のチャート図を図4に、また、ピークの解析結果を下記に示す。
(Example 1-4: Synthesis of MOMPA-DBA)
0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) in Synthesis Example 1 and 0.184 g (1.42 mmol) of dibutylamine (DBA) ) MOMPA-DBA was obtained as an orange solid (yield: 0.473 g, yield: 98%) in the same manner as in Synthesis Example 1 except that The chart of 1 H-NMR (300 MHz, CDCl 3 ) is shown in FIG. 4, and the peak analysis results are shown below.
δ0.86 (t, J = 7.3 Hz, 6H, -CH3), 1.26 (sext, J = 7.3 Hz, 4H, -CH2-), 1.4-1.6 (m, 4H, -CH2-), 2.6-2.7 (m, 4H, -CH2-), 3.47 (s, 2H, Bn-H), 3.93 (s, 3H, -OCH3), 6.99 (d, J = 8.6 Hz, 1H, Ar-H), 7.44 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.81 (d, J = 2.2 Hz, 1H, Ar-H). δ0.86 (t, J = 7.3 Hz, 6H, -CH 3 ), 1.26 (sext, J = 7.3 Hz, 4H, -CH 2- ), 1.4-1.6 (m, 4H, -CH 2- ), 2.6 -2.7 (m, 4H, -CH 2- ), 3.47 (s, 2H, Bn-H), 3.93 (s, 3H, -OCH 3 ), 6.99 (d, J = 8.6 Hz, 1H, Ar-H) , 7.44 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.81 (d, J = 2.2 Hz, 1H, Ar-H).
(比較例1-1:特許第4830435号に記載の光塩基発生剤の合成)
 ケトプロフェン5.09g(20 mmol)と1,4-ジアザビシクロ[2.2.2]オクタン1.12g(10 mmol)をフラスコへ入れ、50℃で加熱し、完全にケトプロフェンと1,4-ジアザビシクロ[2.2.2]オクタンが溶解するまでシクロヘキサンを徐々に投入した。その後、冷却すると白色の沈殿を得た。45℃で2時の減圧乾燥を行って、下記に示す光塩基発生剤を得た。
Figure JPOXMLDOC01-appb-I000031
(Comparative Example 1-1: Synthesis of photobase generator described in Japanese Patent No. 4830435)
Ketoprofen (5.09 g, 20 mmol) and 1,4-diazabicyclo [2.2.2] octane (1.12 g, 10 mmol) were placed in a flask and heated at 50 ° C. to completely dissolve ketoprofen and 1,4-diazabicyclo [ 2.2.2] Cyclohexane was slowly added until octane was dissolved. After cooling, a white precipitate was obtained. The photobase generator shown below was obtained by drying under reduced pressure at 45 ° C. for 2 hours.
Figure JPOXMLDOC01-appb-I000031
[光塩基発生剤のモル吸光係数の測定]
 上記で合成した各光塩基発生剤について、島津製作所社製MultiSpec-1500を用いてUV-visスペクトルを測定し、i線(365nm)におけるモル吸光係数を測定した。溶液セルは石英製で光路長1cmのものを用いた。尚、モル吸光係数は、溶液の吸光度を吸収層の厚さと溶質のモル濃度で割った値である。結果を表1に示す。
[Measurement of molar extinction coefficient of photobase generator]
About each photobase generator synthesized above, UV-vis spectrum was measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the molar extinction coefficient at i-line (365 nm) was measured. A solution cell made of quartz and having an optical path length of 1 cm was used. The molar extinction coefficient is a value obtained by dividing the absorbance of the solution by the thickness of the absorbing layer and the molar concentration of the solute. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
 前記一般式(1)を満たす実施例1-1~1-4の光塩基発生剤は、i線におけるモル吸光係数が高いことがわかる。 It can be seen that the photobase generators of Examples 1-1 to 1-4 satisfying the general formula (1) have a high molar extinction coefficient at i-line.
[光塩基発生剤の耐熱性の評価]
 実施例1-1の光塩基発生剤(MONPA-TBD)を、マック・サイエンス社製TG-DTA2000Sを用いて、TG-DTA測定し(昇温速度5℃/min)、200℃付近まで安定であることを確認した。
[Evaluation of heat resistance of photobase generator]
The photobase generator (MONPA-TBD) of Example 1-1 was measured using a TG-DTA2000S manufactured by Mac Science Co., Ltd. (TG-DTA measurement (temperature increase rate 5 ° C./min)) and stable up to about 200 ° C. I confirmed that there was.
[ポリアミック酸エステルの合成]
(合成例1:ポリアミック酸エステルA-1の合成)
 酸二無水物として6FDA(4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物)5gに乾燥tert-ブチルアルコール約25gを加えて還流した。還流開始後約30分ほぼ透明な液が得られた。更に、約5時間還流し、冷却し、ポアーサイズ0.7μmのフィルタで濾過し不純物を除いた。減圧乾燥してtert-ブチルアルコールを完全に除去し、白い結晶として、表1に記載する酸無水物のハーフエステルを得た。
 容量100mlの三口フラスコに、表1に記載する酸無水物のハーフエステル5mmolと無水3-メチル-1-フェニル-2-ホスホレン1-オキシド0.0125mmolを投入した後、窒素を流しながら、10mlの脱水スルホランで溶解させた。ジイソシアネートとして無水ITI(ジイソシアン酸イソホロン)5mmolを5ml脱水スルホランで溶解させ、フラスコに約5分間で滴下した。混合溶液を200℃、3時間で反応させ、MeOH 500mlで沈殿した。沈殿を含めた溶液を濾過し、乾燥を行って、高分子前駆体ポリマーを得た。得られたポリマーをDMAc(N,N-ジメチルアセトアミド)に溶解し、MeOHで再沈殿した。濾過、乾燥を行って、脱水DMAcを溶媒として15質量%のポリアミック酸エステルA-1溶液を作製した。
[Synthesis of polyamic acid ester]
(Synthesis Example 1: Synthesis of polyamic acid ester A-1)
About 25 g of dry tert-butyl alcohol was added to 5 g of 6FDA (4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride) as an acid dianhydride and refluxed. An almost transparent liquid was obtained for about 30 minutes after the start of reflux. Further, the mixture was refluxed for about 5 hours, cooled, and filtered through a filter having a pore size of 0.7 μm to remove impurities. By drying under reduced pressure, tert-butyl alcohol was completely removed to obtain acid anhydride half esters as shown in Table 1 as white crystals.
A 100 ml three-necked flask was charged with 5 mmol of the acid anhydride half ester described in Table 1 and 0.0125 mmol of anhydrous 3-methyl-1-phenyl-2-phospholene 1-oxide, and then 10 ml of nitrogen was allowed to flow. Dissolved with dehydrated sulfolane. As the diisocyanate, 5 mmol of anhydrous ITI (isophorone diisocyanate) was dissolved in 5 ml of dehydrated sulfolane and added dropwise to the flask in about 5 minutes. The mixed solution was reacted at 200 ° C. for 3 hours and precipitated with 500 ml of MeOH. The solution including the precipitate was filtered and dried to obtain a polymer precursor polymer. The obtained polymer was dissolved in DMAc (N, N-dimethylacetamide) and reprecipitated with MeOH. Filtration and drying were performed to prepare a 15% by mass polyamic acid ester A-1 solution using dehydrated DMAc as a solvent.
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
(合成例2:ポリアミック酸エステルA-2の合成)
 酸二無水物として、6FDAをTDA(1,3,3a,4,5,9b-ヘキサヒドロ-5(テトラヒドロ-2,5-ジオキソ-3-フラニル)ナフト[1,2-c]フラン-1,3-ジオン)に変更した以外は、合成例1と同様にしてポリアミック酸エステルA-2溶液を作製した。
Figure JPOXMLDOC01-appb-T000034
(Synthesis Example 2: Synthesis of polyamic acid ester A-2)
As acid dianhydride, 6FDA is converted to TDA (1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1, A polyamic acid ester A-2 solution was prepared in the same manner as in Synthesis Example 1 except that the compound was changed to 3-dione).
Figure JPOXMLDOC01-appb-T000034
(合成例3:ポリアミック酸エステルA-3の合成)
 3,3’,4,4’‐ジフェニルエーテルテトラカルボン酸二無水物(ODPA)7.75gと4,4’‐ジアミノジフェニルエーテル(DDE)4.86gとをN‐メチルピロリドン(NMP)30gに溶解し、60℃で4時間、その後室温下で一晩攪拌し、ポリアミド酸を得た。そこに水冷下で無水トリフルオロ酢酸を9.45g加え、室温で3時間攪拌し、エタノール1.73gを加えた。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリアミック酸エステルA-3の溶液を作製した。ポリアミック酸エステルA-3の数平均分子量は27000であった。
(Synthesis Example 3: Synthesis of polyamic acid ester A-3)
3.75 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.86 g of 4,4′-diaminodiphenyl ether (DDE) were dissolved in 30 g of N-methylpyrrolidone (NMP). The mixture was stirred at 60 ° C. for 4 hours and then at room temperature overnight to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added thereto under water cooling, and the mixture was stirred at room temperature for 3 hours, and 1.73 g of ethanol was added. The reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to prepare a solution of polyamic acid ester A-3. The number average molecular weight of the polyamic acid ester A-3 was 27000.
(実施例2-1)
 下記表に記載の配合比(質量比)で、上記で得られたポリアミック酸エステルの溶液に対して、光塩基発生剤を配合し、溶解させて、実施例および比較例の感光性樹脂組成物を得た。尚、表中のポリアミック酸エステルの配合量は、固形分量を示す。
Example 2-1
Photobase generators are blended and dissolved in the polyamic acid ester solution obtained above at the blending ratio (mass ratio) described in the following table, and the photosensitive resin compositions of Examples and Comparative Examples are used. Got. In addition, the compounding quantity of the polyamic acid ester in a table | surface shows solid content.
 4インチのシリコンウエハー上に下記表中の実施例2-1の感光性樹脂組成物をスピンコートによって塗布し、80℃のホットプレート上で20分間加熱して、厚さ10μmの感光性樹脂組成物膜を形成した。この膜にi線フィルタを装着した高圧水銀灯露光装置によりマスクパターンを通して0から1000mJ/cmの範囲の光量で露光を行った。露光後、140℃のホットプレート上で10分加熱し、次に、テトラメチルアンモニウムヒドロキシド2.38%水溶液と2-プロパノールを重量比1:1で混合した現像液に90秒間浸漬し、さらに20秒間水洗することでパターン現像を行った。 The photosensitive resin composition of Example 2-1 in the following table was applied on a 4-inch silicon wafer by spin coating, and heated on a hot plate at 80 ° C. for 20 minutes to form a photosensitive resin composition having a thickness of 10 μm. A material film was formed. The film was exposed with a light amount in the range of 0 to 1000 mJ / cm 2 through a mask pattern by a high pressure mercury lamp exposure apparatus equipped with an i-line filter. After the exposure, it was heated on a hot plate at 140 ° C. for 10 minutes, and then immersed in a developer mixed with a tetramethylammonium hydroxide 2.38% aqueous solution and 2-propanol at a weight ratio of 1: 1 for 90 seconds. Pattern development was performed by washing with water for 20 seconds.
 その結果、露光量150mJ/cm2 以上の光照射することでパターンが形成されていることが確認できた。 As a result, it was confirmed that a pattern was formed by irradiating light with an exposure amount of 150 mJ / cm 2 or more.
(実施例2-2~2-9、比較例2-1~2-3)
 実施例2-1と同様の手順により、下記表に記載の配合比(質量比)および露光量で現像試験を実施し、パターン形成されている露光量を確認した。
(Examples 2-2 to 2-9, Comparative Examples 2-1 to 2-3)
In the same procedure as in Example 2-1, a development test was carried out with the blending ratio (mass ratio) and exposure amount shown in the following table, and the exposure amount in which a pattern was formed was confirmed.
Figure JPOXMLDOC01-appb-T000035
*1:1000mJ/cmでもパターン形成できなかった。
Figure JPOXMLDOC01-appb-T000035
* 1: A pattern could not be formed even at 1000 mJ / cm 2 .
 前記一般式(1)を満たす光塩基発生剤を含有する実施例の感光性樹脂組成物は、感度に優れ、低温の硬化条件にもかかわらず、パターン形成性に優れることがわかる。 It can be seen that the photosensitive resin compositions of the examples containing the photobase generator satisfying the general formula (1) are excellent in sensitivity and excellent in pattern formability despite low-temperature curing conditions.

Claims (15)

  1.  下記一般式(1)で表されるカルボン酸と塩基のイオン型の光塩基発生剤を含有することを特徴とする感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-I000001
    (式(1)中、R~R、XおよびXは、それぞれ独立して、水素原子または置換基であり、XおよびXの少なくとも一方は電子吸引性基であり、Yは電子供与性基であり、Bは塩基を示す。)
    A photosensitive resin composition comprising an ionic photobase generator of a carboxylic acid and a base represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-I000001
    (In the formula (1), R 1 to R 4 , X 1 and X 2 are each independently a hydrogen atom or a substituent, and at least one of X 1 and X 2 is an electron-withdrawing group; Is an electron donating group, and B is a base.)
  2.  前記光塩基発生剤のモル吸光係数が、300L・mol-1・cm-1以上であることを特徴とする請求項1記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the photoabsorber has a molar extinction coefficient of 300 L · mol −1 · cm −1 or more.
  3.  前記一般式(1)において、電子吸引性基が、-C≡N、-COCH、-NO、-F、-Cl、-Br、および、-Iからなる群から選択されることを特徴とする請求項1記載の感光性樹脂組成物。 In the general formula (1), the electron-withdrawing group is selected from the group consisting of —C≡N, —COCH 3 , —NO 2 , —F, —Cl, —Br, and —I. The photosensitive resin composition according to claim 1.
  4.  前記一般式(1)において、電子供与性基が、-CH、-C、-CH(CH、-C(CH、-C、-OH、-OCH、および、-OCからなる群から選択されることを特徴とする請求項1記載の感光性樹脂組成物。 In the general formula (1), the electron-donating group is —CH 3 , —C 2 H 5 , —CH (CH 3 ) 2 , —C (CH 3 ) 3 , —C 6 H 5 , —OH, — 2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is selected from the group consisting of OCH 3 and —OC 6 H 5 .
  5.  さらに、高分子前駆体を含有することを特徴とする請求項1記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, further comprising a polymer precursor.
  6.  前記高分子前駆体が、ポリアミック酸、および、ポリアミック酸エステルの少なくとも何れか一方であることを特徴とする請求項5記載の感光性樹脂組成物。 6. The photosensitive resin composition according to claim 5, wherein the polymer precursor is at least one of polyamic acid and polyamic acid ester.
  7.  前記高分子前駆体が、下記一般式(4-1)で表される構造を有するポリアミック酸エステルであることを特徴とする請求項5記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-I000002
    (式(4-1)中、Rは4価の有機基であり、Rは脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、R9-1およびR10-1は、相互に同一でも異なってもよく、1価の有機基またはケイ素を有する官能基であり、R11は2価の有機基であり、mは1以上の整数であり、nは0または1以上の整数である。)
    6. The photosensitive resin composition according to claim 5, wherein the polymer precursor is a polyamic acid ester having a structure represented by the following general formula (4-1).
    Figure JPOXMLDOC01-appb-I000002
    (In formula (4-1), R 7 is a tetravalent organic group, R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene. R 9-1 and R 10-1 may be the same or different from each other, and may be a monovalent organic group or a functional group having silicon, and R 11 may be a divalent organic group. M is an integer of 1 or more, and n is 0 or an integer of 1 or more.)
  8.  前記一般式(4-1)中のRが、芳香族環と脂肪族炭化水素環との縮合環を含む4価の有機基、芳香族基と脂環式炭化水素基とを含む4価の有機基、またはフッ素原子を含む4価の有機基であることを特徴とする請求項7記載の感光性樹脂組成物。 R 7 in the general formula (4-1) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, or a tetravalent group containing an aromatic group and an alicyclic hydrocarbon group. The photosensitive resin composition according to claim 7, wherein the organic resin group is a tetravalent organic group containing a fluorine atom.
  9.  前記高分子前駆体が、下記一般式(4-1-1)および(4-1-2)の少なくともいずれか一方で表される構造を有するポリアミック酸エステルであることを特徴とする請求項5記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-I000003
    (式(4-1-1)中、Rは脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、R9-1およびR10-1は、相互に同一でも異なってもよく、1価の有機基またはケイ素を有する官能基であり、R11は2価の有機基であり、mは1以上の整数であり、nは0または1以上の整数である。)
    Figure JPOXMLDOC01-appb-I000004
    (式(4-1-2)中、Rは脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、R9-1およびR10-1は、相互に同一でも異なってもよく、1価の有機基またはケイ素を有する官能基であり、R11は2価の有機基であり、mは1以上の整数であり、nは0または1以上の整数である。)
    6. The polymer precursor is a polyamic acid ester having a structure represented by at least one of the following general formulas (4-1-1) and (4-1-2): The photosensitive resin composition as described.
    Figure JPOXMLDOC01-appb-I000003
    (In the formula (4-1-1), R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R 9 -1 and R 10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R 11 is a divalent organic group, and m is an integer of 1 or more. And n is 0 or an integer of 1 or more.)
    Figure JPOXMLDOC01-appb-I000004
    (In the formula (4-1-2), R 8 is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R 9 -1 and R 10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R 11 is a divalent organic group, and m is an integer of 1 or more. And n is 0 or an integer of 1 or more.)
  10.  請求項1記載の感光性樹脂組成物を、フィルムに塗布、乾燥して得られる樹脂層を有することを特徴とするドライフィルム。 A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 1 to a film and drying the film.
  11.  請求項1~9のいずれか1項記載の感光性樹脂組成物または請求項10記載のドライフィルムの樹脂層を、硬化して得られることを特徴とする硬化物。 A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 9 or the resin layer of the dry film according to claim 10.
  12.  請求項11記載の硬化物を有することを特徴とするプリント配線板。 A printed wiring board comprising the cured product according to claim 11.
  13.  下記一般式(1)で表されるカルボン酸と塩基のイオン型であることを特徴とする光塩基発生剤。
    Figure JPOXMLDOC01-appb-I000005
    (式(1)中、R~R、XおよびXは、それぞれ独立して、水素原子または置換基であり、XおよびXの少なくとも一方は電子吸引性基であり、Yは電子供与性基であり、R~Rは、それぞれ独立して、水素原子または置換基であり、Bは塩基を示す。)
    A photobase generator characterized by being an ionic type of a carboxylic acid and a base represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-I000005
    (In the formula (1), R 1 to R 4 , X 1 and X 2 are each independently a hydrogen atom or a substituent, and at least one of X 1 and X 2 is an electron-withdrawing group; Is an electron donating group, R 1 to R 4 each independently represents a hydrogen atom or a substituent, and B represents a base.)
  14.  前記一般式(1)において、電子吸引性基が、-C≡N、-COCH、-NO、-F、-Cl、-Br、および、-Iからなる群から選択されることを特徴とする請求項13記載の光塩基発生剤。 In the general formula (1), the electron-withdrawing group is selected from the group consisting of —C≡N, —COCH 3 , —NO 2 , —F, —Cl, —Br, and —I. The photobase generator according to claim 13.
  15.  前記一般式(1)において、電子供与性基が、-CH、-C、-CH(CH、-C(CH、-C、-OH、-OCH、および、-OCからなる群から選択されることを特徴とする請求項13または14記載の光塩基発生剤。 In the general formula (1), the electron-donating group is —CH 3 , —C 2 H 5 , —CH (CH 3 ) 2 , —C (CH 3 ) 3 , —C 6 H 5 , —OH, — The photobase generator according to claim 13 or 14, wherein the photobase generator is selected from the group consisting of OCH 3 and -OC 6 H 5 .
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