WO2017141734A1 - 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 - Google Patents

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 Download PDF

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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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English (en)
French (fr)
Japanese (ja)
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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 KR1020187026536A priority Critical patent/KR102679410B1/ko
Priority to JP2018500038A priority patent/JP6767470B2/ja
Priority to CN201780011878.7A priority patent/CN108700805B/zh
Publication of WO2017141734A1 publication Critical patent/WO2017141734A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/56—Compounds 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic 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
    • C07D233/56—Heterocyclic 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
    • C07D233/58—Heterocyclic 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic 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
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying 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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JP5321188B2 (ja) * 2008-03-31 2013-10-23 大日本印刷株式会社 感光性樹脂組成物、物品、及びパターン形成方法
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JP2007101685A (ja) * 2005-09-30 2007-04-19 Dainippon Printing Co Ltd 感光性樹脂組成物及び物品
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JP7269721B2 (ja) 2018-12-12 2023-05-09 東京応化工業株式会社 感エネルギー性樹脂組成物、硬化物及び硬化物の製造方法

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