WO2017131037A1 - Composition de résine photosensible, film durci, stratifié, procédé de fabrication de film durci, procédé de fabrication de stratifié et dispositif semi-conducteur - Google Patents

Composition de résine photosensible, film durci, stratifié, procédé de fabrication de film durci, procédé de fabrication de stratifié et dispositif semi-conducteur Download PDF

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Publication number
WO2017131037A1
WO2017131037A1 PCT/JP2017/002563 JP2017002563W WO2017131037A1 WO 2017131037 A1 WO2017131037 A1 WO 2017131037A1 JP 2017002563 W JP2017002563 W JP 2017002563W WO 2017131037 A1 WO2017131037 A1 WO 2017131037A1
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Prior art keywords
group
resin composition
photosensitive resin
formula
cured film
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English (en)
Japanese (ja)
Inventor
悠 岩井
健志 川端
渋谷　明規
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2017564312A priority Critical patent/JP6712607B2/ja
Priority to KR1020187021308A priority patent/KR102104806B1/ko
Publication of WO2017131037A1 publication Critical patent/WO2017131037A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/0387—Polyamides or polyimides
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/84—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring

Definitions

  • the present invention relates to a photosensitive resin composition, a cured film using the same, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device.
  • the present invention relates to a photosensitive resin composition used for an interlayer insulating film for a rewiring layer of a semiconductor device.
  • Thermosetting resins that are cured by cyclization are excellent in heat resistance and insulation, and are therefore used in insulating layers of semiconductor devices. Moreover, since polyimide resin has low solubility in a solvent, it is used in the state of a precursor (polyimide precursor) before cyclization reaction, applied to a substrate, etc., and then heated to cyclize the polyimide precursor. A cured film is also formed.
  • a precursor polyimide precursor
  • a cured film is also formed.
  • B a photopolymerizable compound having a urethane bond and an ethylenically unsaturated group in the molecule.
  • a photosensitive resin composition for an interlayer insulating film of a semiconductor element, comprising a compound and (C) a photopolymerization initiator is disclosed.
  • the present invention aims to solve such problems, and is a photosensitive resin composition excellent in adhesiveness, and a cured film, a laminate, a method for producing a cured film using the same, and a laminate
  • An object is to provide a manufacturing method and a semiconductor device.
  • ⁇ 1> includes a polyimide precursor, at least one resin of polyimide, and at least one urethane (meth) acrylate,
  • the urethane (meth) acrylate has, in one molecule, at least one of a partial structure represented by the formula (A) and a partial structure represented by the formula (B), 4 to 15 (meth) acrylate groups,
  • * in the formula is a connecting hand.
  • the urethane (meth) acrylate has a partial structure represented by the formula (A), 4 to 15 (meth) acrylate groups, and a urethane structure in one molecule.
  • Photosensitive resin composition ⁇ 3> The photosensitive resin composition according to ⁇ 1> or ⁇ 2>, wherein the resin is a polyimide precursor.
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.
  • ⁇ 5> The photosensitive resin composition according to ⁇ 4>, wherein in formula (2), at least one of R 113 and R 114 contains a radical polymerizable group.
  • R 111 in the above formula (2) is the following formula (51) or formula (61);
  • R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group, a fluoromethyl group, A difluoromethyl group or a trifluoromethyl group;
  • Formula (61) In formula (61), R 18 and R 19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.
  • ⁇ 9> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a migration inhibitor.
  • ⁇ 10> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9>, further comprising a polymerization inhibitor.
  • ⁇ 11> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a radical photopolymerization initiator.
  • ⁇ 12> The photosensitive resin composition according to ⁇ 11>, wherein the radical photopolymerization initiator is an oxime compound.
  • ⁇ 13> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 12>, which is used for an interlayer insulating film for a rewiring layer.
  • ⁇ 14> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> A laminate having two or more cured films according to ⁇ 14>.
  • ⁇ 16> The laminate according to ⁇ 15>, having a metal layer between the cured films.
  • ⁇ 17> A method for producing a cured film, comprising using the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 18> a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer; An exposure step of exposing the photosensitive resin composition layer; The method for producing a cured film according to ⁇ 17>, further comprising a step of developing the exposed photosensitive resin composition layer.
  • ⁇ 19> The method for producing a cured film according to ⁇ 18>, wherein the development treatment is a negative development treatment.
  • ⁇ 21> The method for producing a cured film according to any one of ⁇ 17> to ⁇ 20>, wherein the cured film has a thickness of 1 to 30 ⁇ m.
  • the present invention it is possible to provide a photosensitive resin composition excellent in adhesiveness, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device using the same.
  • the description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • active light means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means actinic rays or radiation.
  • exposure in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acrylate represents both and / or “acrylate” and “methacrylate”
  • (meth) allyl means both “allyl” and “methallyl”
  • (Meth) acryl” represents either “acryl” and “methacryl” or any one
  • “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • solid content concentration is the mass percentage of the mass of the other component except a solvent with respect to the gross mass of a composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values by gel permeation chromatography (GPC measurement) unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the eluent is measured using THF (tetrahydrofuran).
  • detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.
  • the photosensitive resin composition of the present invention includes a polyimide precursor, at least one resin of polyimide, and at least one urethane (meth) acrylate, and the urethane (meth) acrylate is in one molecule. And at least one of the partial structure represented by the formula (A) and the partial structure represented by the formula (B), 4 to 15 (meth) acrylate groups, and a urethane structure.
  • * in the formula is a connecting hand.
  • the photosensitive resin composition excellent in heat resistance is obtained by having at least one of the partial structure represented by Formula (A) and the partial structure represented by Formula (B). Furthermore, the photosensitive resin composition excellent in exposure latitude can be obtained by increasing the compatibility of the polyimide precursor and the like with urethane (meth) acrylate.
  • the photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is referred to as a polyimide precursor and at least one resin of polyimide (hereinafter referred to as “polyimide precursor or the like”). And at least a polyimide precursor.
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in Formula (2) are preferably an oxygen atom or NH, and more preferably an oxygen atom.
  • R 111 in Formula (2) represents a divalent organic group.
  • the divalent organic group include a straight chain or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic group, a straight chain or branched aliphatic group having 2 to 20 carbon atoms, a carbon number A group consisting of a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms or a combination thereof is preferred, and a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferred.
  • R 111 is preferably derived from a diamine.
  • the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine.
  • One type of diamine may be used, or two or more types may be used.
  • a linear or branched aliphatic group having 2 to 20 carbon atoms a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof.
  • a diamine containing is preferable, and a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aromatic group.
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- and p-phenylenediamine, diaminotoluene, 4,4′- And 3,3′-diaminobiphenyl, 4,4′-diaminodiphenyl
  • diamines (DA-1) to (DA-18) shown below are also preferable.
  • a diamine having at least two alkylene glycol units in the main chain is also a preferred example.
  • Preferred is a diamine containing at least two ethylene glycol chains or propylene glycol chains in one molecule, more preferably a diamine containing no aromatic ring.
  • Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark).
  • EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like. It is not limited to.
  • x, y, and z are average values.
  • R 111 from the viewpoint of flexibility of the cured film obtained, it is preferably represented by -Ar-L-Ar-.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , —SO 2 — or —NHCO—, and a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO 2 —.
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance.
  • a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
  • Formula (51) In formula (51), R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group, a fluoromethyl group, It is preferably a difluoromethyl group or a trifluoromethyl group, and at least one is preferably a fluorine atom, a methyl group, or a trifluoromethyl group.
  • Examples of the monovalent organic group represented by R 10 to R 17 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
  • Formula (61) In the formula (61), R 18 and R 19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group, and at least one is a fluorine atom, a methyl group or a trifluoromethyl group. Preferably there is.
  • Examples of the diamine compound that gives the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′- Bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
  • R 115 in the formula (2) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
  • R 112 represents a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO 2 —.
  • R 115 include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used.
  • the tetracarboxylic dianhydride is preferably represented by the following formula (0).
  • a preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′ , 4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 4,4′-PM
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
  • R 111 and R 115 has an OH group. More specifically, examples of R 111 include a residue of a bisaminophenol derivative.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 preferably contains a radical polymerizable group, and both contain a radical polymerizable group.
  • the radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.
  • R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a polyoxyalkylene group having 4 to 30 carbon atoms.
  • suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group.
  • R 200 is a methyl group and R 201 is an ethylene group.
  • R 201 is an ethylene group.
  • a substituent that improves the solubility of the developer is preferably used.
  • the monovalent organic group includes an aromatic group having 1, 2, or 3, preferably one acidic group bonded to carbon constituting the aryl group, and And aralkyl groups.
  • Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
  • the acidic group is preferably an OH group.
  • R 113 or R 114 is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
  • R 113 or R 114 is preferably a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
  • the alkyl group preferably has 1 to 30 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • linear or branched alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the polycyclic alkyl group include an adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. Is mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable.
  • aromatic group examples include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene.
  • the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Also good. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
  • the polyimide precursor preferably has a fluorine atom in the structural unit.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
  • an aliphatic group having a siloxane structure may be copolymerized for the purpose of improving the adhesion to the substrate.
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
  • the repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors and the like used in the present invention is preferably a precursor having a repeating unit represented by the formula (2-A). By adopting such a structure, it becomes possible to further widen the width of the exposure latitude.
  • a 1 and A 2 each represent an oxygen atom
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently represent It represents a hydrogen atom or a monovalent organic group
  • at least one of R 113 and R 114 is a group containing a polymerizable group, and is preferably a polymerizable group.
  • a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and the preferred ranges are also the same. is there.
  • R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
  • the repeating structural unit represented by the formula (2) contained in the polyimide precursor may be one type or two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (2) may be included.
  • the polyimide precursor may also contain other types of repeating structural units in addition to the repeating unit of the above formula (2).
  • a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating unit represented by the formula (2).
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
  • the dispersion degree of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more.
  • the upper limit of the degree of dispersion of the polyimide precursor is not particularly defined, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, and still more preferably 3.2 or less, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is even more preferable.
  • the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but is preferably a polymer compound having a polymerizable group. Although there is no limitation in particular, it is preferable that it is a compound represented by following formula (4), and it is more preferable that it is a compound which has a polymeric group.
  • Formula (4) In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group.
  • the polymerizable group may be located in at least one of R 131 and R 132 , and has a polymerizable group at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be.
  • R 133 is a polymerizable group, and other groups are as defined in the formula (4).
  • Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, the other is an organic group, and the other groups are as defined in Formula (4).
  • a polymerizable group is synonymous with the polymerizable group described in the polymerizable group which said polyimide precursor etc. have.
  • R 131 represents a divalent organic group. Examples of the divalent organic group include those similar to R 111 in formula (2), and the preferred range is also the same. As the R 131, include diamine residues remaining after removal of the amino groups of the diamine. Examples of the diamine include aliphatic, cycloaliphatic or aromatic diamines. As a specific example, an example of R 111 in the formula (2) of the polyimide precursor can be given.
  • R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferred is a diamine residue containing at least two ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine residue containing no aromatic ring.
  • Examples of diamines containing two or more ethylene glycol chains and / or propylene glycol chains in one molecule include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine ( (Registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, Jeffermin (registered trademark) EDR-176, D-200, D-400, D-2000, D -4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-amino) Propoxy) propan-2-yl) oxy) propan-2-amine, 1- (2- (2- (2-aminopropoxy) Ethoxy) propoxy) the like-2-amine include, but are not limited to.
  • R 132 represents a tetravalent organic group.
  • the tetravalent organic group include those similar to R 115 in formula (2), and the preferred range is also the same.
  • four bonds of a tetravalent organic group exemplified as R 115 are bonded to four —C ( ⁇ O) — moieties in the above formula (4) to form a condensed ring.
  • R 132 is the following organic group, a structure represented by PI-C, which is employed in the examples of the present application, is formed.
  • R 132 also includes a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. Specific examples include those exemplified R 115 in formula (2) of the polyimide precursor. From the viewpoint of the strength of the cured film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
  • R 131 and R 132 has an OH group. More specifically, as R 131 , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Preferred examples include bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and (DA-1) to (DA-18) above. As R 132 , the above (DAA-1) to (DAA-5) can be mentioned as preferred examples.
  • an aliphatic group having a siloxane structure may be copolymerized for the purpose of improving the adhesion to the substrate.
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
  • the end of the main chain of the polyimide may be sealed with a terminal blocking agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound.
  • a terminal blocking agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound.
  • a monoamine e.g., aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
  • -Aminonaphthalene 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2, -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carbo Ci-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-amino
  • the polyimide preferably has an imidization ratio of 85% or more, more preferably 90% or more.
  • the imidization ratio is 85% or more, film shrinkage due to ring closure that occurs when imidization is performed by heating is reduced, and generation of warpage can be suppressed.
  • Polyimide In addition to all the repeating structural units of the formula based on one R 131 or R 132 (4), represented by the above formula comprising two or more different types of R 131 or R 132 (4) Repeating units may be included.
  • the polyimide may also contain other types of repeating structural units in addition to the repeating unit of the above formula (4).
  • polyimide can be prepared by reacting tetracarboxylic dianhydride with a diamine compound (partially replaced with a monoamine end-capping agent) at low temperature, or tetracarboxylic dianhydride (partially acid at low temperature).
  • Examples of commercially available polyimide products include Durimide (registered trademark) 284, manufactured by FUJIFILM Corporation, Matrimide 5218, and manufactured by HUNTSMAN.
  • the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000.
  • the weight average molecular weight is more preferably 20,000 or more.
  • the weight average molecular weight of at least 1 type of polyimide is the said range.
  • the composition of this invention may contain only 1 type in a polyimide precursor and a polyimide, and may contain 2 or more types. Also, two or more types of polyimide precursors may be included, which are the same type of resin and have different structures.
  • the content of the polyimide precursor and the like in the composition of the present invention is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, and further preferably 40 to 75% by mass. 50 to 70% by mass is particularly preferable.
  • the component which the composition of this invention may contain is demonstrated. It goes without saying that the present invention may contain components other than these, and these components are not essential.
  • a polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
  • an organic solvent is preferably used for the reaction.
  • One or more organic solvents may be used.
  • the organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
  • Polyimide may be produced by synthesizing a polyimide precursor and then cyclized by heating, or may be synthesized directly.
  • ⁇ End sealant In the production method of the polyimide precursor or the like, it is preferable to seal with a terminal sealing agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound in order to further improve storage stability. Of these, it is more preferable to use a monoamine.
  • a terminal sealing agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound in order to further improve storage stability.
  • a monoamine Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
  • -Aminonaphthalene 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2, -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carbo Ci-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-amino
  • Solid precipitation When manufacturing a polyimide precursor etc., the process of depositing a solid may be included. Specifically, solid precipitation can be achieved by precipitating a polyimide precursor or the like in the reaction solution in water and dissolving the polyimide precursor or the like such as tetrahydrofuran in a soluble solvent. Then, a polyimide precursor etc. can be dried and a powdery polyimide precursor etc. can be obtained.
  • the photosensitive resin composition of the present invention contains at least one urethane (meth) acrylate.
  • the urethane (meth) acrylate used in the present invention has at least one of the partial structure represented by the formula (A) and the partial structure represented by the formula (B) and 4 to 15 (meth) per molecule. It has an acrylate group and a urethane structure. However, * in the formula is a connecting hand.
  • the urethane (meth) acrylate preferably includes at least a partial structure represented by the formula (A).
  • the urethane (meth) acrylate in the present invention is a partial structure selected from the partial structure represented by the formula (A) and the partial structure represented by the formula (B) (hereinafter simply referred to as “partial structure”) in one molecule. It is preferable to have one.
  • the number of (meth) acrylate groups contained in the urethane (meth) acrylate is more preferably 5 to 15 and even more preferably 6 to 15 in one molecule. By setting it as such a range, it exists in the tendency which adhesiveness improves more effectively.
  • the (meth) acrylate group contained in the urethane (meth) acrylate is preferably an acrylate group. By adopting such a configuration, the exposure latitude tends to be more effectively improved.
  • the (meth) acrylate group contained in the urethane (meth) acrylate is a (meth) acryloyloxy group.
  • urethane (meth) acrylate having one partial structure represented by the formula (A), 4 to 15 (meth) acrylate groups, and one or more urethane structures in one molecule.
  • the urethane (meth) acrylate used in the present invention preferably has 2 to 8 urethane bonds, more preferably 3 to 6 in one molecule. By setting it as such a range, it exists in the tendency for adhesiveness to be exhibited more effectively.
  • the number of atoms connecting the partial structure and the (meth) acrylate group closest to the partial structure is preferably 4 to 15, more preferably 9 to 13.
  • the number of atoms connecting the partial structure and the (meth) acrylate group closest to the partial structure refers to the shortest number of atoms connecting the partial structure and the (meth) acrylate group. In this case, the number is 12.
  • the group connecting the partial structure and the (meth) acrylate group may be a combination of groups selected from —CH 2 —, —N (H) —, —O—, and —C ( ⁇ O) —. preferable.
  • the group connecting the partial structure and the (meth) acryloxy group is composed of a combination of —CH 2 — and a urethane bond.
  • the molecular weight of the urethane (meth) acrylate in the present invention is preferably 500 to 5000, and more preferably 800 to 3000. By setting it as such a range, the number of the functional groups per mass increases and the effect of this invention is exhibited more effectively.
  • the composition of the present invention preferably contains 5 to 50 parts by mass, more preferably 10 to 30 parts by mass of the urethane (meth) acrylate, based on the polyimide precursor or the like (resin). By setting it as such a range, the cured film which was more excellent in heat resistance and adhesiveness is obtained.
  • the urethane (meth) acrylate may contain only one type or two or more types. When 2 or more types are included, the total amount is preferably within the above range.
  • composition of this invention contains the said polyimide precursor etc. and urethane (meth) acrylate, according to a use etc., another component can be mix
  • the composition of the present invention preferably contains at least one of a migration inhibitor, a polymerization inhibitor, and a radical photopolymerization initiator.
  • the photosensitive resin composition of the present invention is preferably used as a negative photosensitive resin composition.
  • the photosensitive resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition.
  • the migration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenol compounds , Salicy
  • an ion trapping agent that captures anions such as halogen ions can also be used.
  • an ion trap agent A conventionally well-known thing can be used.
  • hydrotalcite represented by the following composition formula or hydrated bismuth oxide represented by the following composition formula is preferable.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, and 0.05 to 2.0% by mass with respect to the total solid content of the composition. More preferred is 0.1 to 1.0% by mass. Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.
  • the photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
  • a polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N -Phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol
  • a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication 2015/125469 can also be used.
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition. Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
  • the photosensitive resin composition of the present invention preferably contains a radical photopolymerization initiator (hereinafter sometimes simply referred to as “photopolymerization initiator”).
  • photopolymerization initiator By including a photoradical polymerization initiator, the composition is applied to a semiconductor wafer or the like to form a composition layer, and then irradiation with light causes curing due to the generated radicals, thereby improving the solubility in the light irradiation part. Can be reduced. For this reason, there exists an advantage that the area
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. Specifically, for example, using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent, It is preferable to measure at a concentration of 0.01 g / L.
  • halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group
  • Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo series
  • examples thereof include compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like.
  • halogenated hydrocarbon compounds having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US patents Examples thereof include compounds described in the specification of No. 42122976.
  • Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) 1,3,4-oxadiazole, 2-trichloromethyl-5-
  • ketone compound examples include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kayacure DETX manufactured by Nippon Kayaku is also suitably used as a commercial product.
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 in which an absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
  • the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • IRGACURE-819 and IRGACURE-TPO which are commercially available products can be used.
  • the metallocene compound include IRGACURE-784 (manufactured by BASF).
  • More preferred examples of the photopolymerization initiator include oxime compounds.
  • the oxime compound By using the oxime compound, the exposure latitude can be improved more effectively.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • Preferred oxime compounds include, for example, the following compounds, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane- 3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2 -Ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
  • Examples of oxime compounds include J.M. C. S. Perkin II (1979) p. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162.
  • IRGACURE OX-01 manufactured by BASF
  • IRGACURE OXE-02 manufactured by BASF
  • N-1919 manufactured by ADEKA
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arkles NCI-831 and Adeka Arkles NCI-930 made by ADEKA
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arkles NCI-831 and Adeka Arkles NCI-930 made by ADEKA
  • DFI-091 manufactured by Daitokemix Co., Ltd.
  • JP-A-2009-221114 which have an absorption maximum at 405 nm and have good sensitivity to a g-ray light source, may be used.
  • the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used.
  • cyclic oxime compounds in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
  • a compound described in JP-A-2009-242469 which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.
  • an oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013.
  • Specific examples include the following compounds.
  • the most preferred oxime compound includes an oxime compound having a specific substituent described in JP-A-2007-2699779, an oxime compound having a thioaryl group disclosed in JP-A-2009-191061, and the like.
  • Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazoles from the viewpoint of exposure sensitivity. Selected from the group consisting of dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Compounds are preferred.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, ⁇ -aminoketones.
  • Most preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, and most preferred are oxime compounds.
  • Photopolymerization initiators include N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), etc.
  • Aromatic ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc.
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkylbenzoin
  • benzyl derivatives such as benzyldimethyl ketal.
  • a compound represented by the following formula (I) can also be used.
  • R 50 represents an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, and R 51 is a group represented by the formula (II) or the same as R 50
  • Each of R 52 to R 54 is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or halogen.
  • the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the total solid content of the composition. More preferably, the content is 0.1 to 10% by mass. Only one type of photopolymerization initiator may be used, or two or more types may be used. When there are two or more photopolymerization initiators, the total is preferably in the above range.
  • the composition of the present invention may contain a polymerizable compound other than the urethane (meth) acrylate.
  • the other polymerizable compound is a compound having a polymerizable group, and a known compound that can be crosslinked by a radical, an acid, a base, or the like can be used.
  • the polymerizable group include the polymerizable groups described in the above-mentioned polyimide precursor and the like.
  • the compound having an ethylenically unsaturated bond used in the present invention is more preferably a compound containing two or more ethylenically unsaturated groups.
  • the polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer or a mixture thereof and a multimer thereof.
  • a monomer type polymerizable compound (hereinafter also referred to as a polymerizable monomer) is a compound different from a polymer compound.
  • the polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably it is.
  • the molecular weight of the polymerizable monomer is usually 100 or more.
  • the oligomer type polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded.
  • the weight average molecular weight of the oligomer type polymerizable compound is preferably 2000 to 20000, more preferably 2000 to 15000, and most preferably 2000 to 10,000.
  • the number of functional groups of the polymerizable compound in the present invention means the number of polymerizable groups in one molecule.
  • the polymerizable compound preferably contains at least one bifunctional or higher functional polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher functional polymerizable compound. More preferred.
  • the polymeric compound in this invention contains at least 1 sort (s) of polymeric compounds more than trifunctional from the point that a three-dimensional crosslinked structure can be formed and heat resistance can be improved.
  • a mixture of a bifunctional or lower polymerizable compound and a trifunctional or higher functional polymerizable compound may be used.
  • polymerizable compounds include compounds having an ethylenically unsaturated bond, compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group, epoxy compounds (compounds having an epoxy group), oxetane compounds (compounds having an oxetanyl group) ) And benzoxazine compounds (compounds having a benzoxazolyl group).
  • epoxy compounds compounds having an epoxy group
  • oxetane compounds compounds having an oxetanyl group
  • benzoxazine compounds compounds having a benzoxazolyl group.
  • composition of this invention can also be set as the structure which does not contain other polymeric compound substantially.
  • “Substantially free” means 5% by mass or less, preferably 1% by mass or less, of the amount of the predetermined urethane (meth) acrylate contained in the composition of the present invention.
  • the composition of the present invention may contain a thermal base generator.
  • the type of the thermal base generator is not particularly defined, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of the above.
  • pKa1 represents a logarithmic representation ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
  • the cyclization reaction of a polyimide precursor can be performed at low temperature, and it can be set as the composition excellent in stability. Moreover, since the base is not generated unless heated, the thermal base generator can suppress cyclization of the polyimide precursor during storage even if it coexists with the polyimide precursor, and is excellent in storage stability.
  • the thermal base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. including. Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can accelerate the cyclization reaction of the polyimide precursor, thereby cyclizing the polyimide precursor. Can be performed at low temperatures.
  • the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C.
  • the upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 165 ° C. or lower.
  • the lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is unlikely to be generated during storage, so that a polyimide precursor composition having excellent stability can be prepared.
  • the cyclization temperature of the polyimide precursor can be reduced.
  • the base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
  • the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be lowered more.
  • the base generated by the thermal base generator preferably has a boiling point of 80 ° C. or higher, preferably 100 ° C. or higher, and most preferably 140 ° C. or higher.
  • the molecular weight of the generated base is preferably 80 to 2000.
  • the lower limit is more preferably 100 or more.
  • the upper limit is more preferably 500 or less.
  • the molecular weight value is a theoretical value obtained from the structural formula.
  • the acidic compound (A1) preferably contains one or more selected from ammonium salts.
  • the ammonium salt (A2) is preferably an acidic compound.
  • the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated.
  • the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion.
  • the anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable.
  • numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
  • the anion outside the molecule of the cation moiety is also referred to as a counter anion.
  • R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group.
  • R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 5 and R 7 may be bonded to form a ring.
  • the ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).
  • R 101 represents an n-valent organic group
  • R 1 and R 7 have the same meanings as R 1 and R 7 in the formula (101) or formula (102).
  • Ar 101 and Ar 102 each independently represent an aryl group
  • n represents an integer of 1 or more
  • m represents an integer of 0 to 5.
  • the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation.
  • the upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the lower limit is preferably 0.5 or more, and more preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and further, the stability of the polyimide precursor composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the polyimide precursor composition is good.
  • the kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
  • the thermal base generator which can improve more stability, sclerosis
  • the stability, curability and developability of the polyimide precursor composition can be further improved by using an anion of a divalent carboxylic acid.
  • the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less.
  • pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the stability of the polyimide precursor composition can be further improved.
  • pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and the determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Hafliger, O., Hafliger, O., Hafliger, O. Compilation: Braude, EA, Nachod, FC, Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RM C. ord; , Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
  • the carboxylate anion is preferably represented by the following formula (X1).
  • EWG represents an electron withdrawing group.
  • the electron withdrawing group means a group having a positive Hammett's substituent constant ⁇ m.
  • ⁇ m is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) P.I. 631-642.
  • the electron withdrawing group of this invention is not limited to the substituent described in the said literature.
  • Me represents a methyl group
  • Ac represents an acetyl group
  • Ph represents a phenyl group.
  • EWG preferably represents a group represented by the following formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, or a carboxy group, and Ar represents an aromatic group.
  • the carboxylate anion is preferably represented by the following formula (X).
  • L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR X — and a combination thereof, and R X represents a hydrogen atom, An alkyl group, an alkenyl group or an aryl group is represented.
  • carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
  • the content of the thermal base generator in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
  • 1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.
  • the negative photosensitive resin composition of the present invention may contain a photobase generator.
  • a photobase generator generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure.
  • the base (basic substance) is generated. ) Is not particularly limited as long as it generates. Since the base generated by the exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably used in the negative type.
  • the content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be a general content.
  • the photobase generator is preferably in the range of 0.01 parts by weight or more and less than 30 parts by weight with respect to 100 parts by weight of the resin, more preferably in the range of 0.05 parts by weight to 25 parts by weight. Preferably, it is in the range of 0.1 to 20 parts by mass.
  • photobase generators can be used.
  • Shirai, and M.M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D.C. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym. Sci.
  • transition metal compound complexes those having a structure such as an ammonium salt, and those formed by salt formation of an amidine moiety with a carboxylic acid
  • An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound.
  • the photobase generator that can be used in the present invention is not particularly limited and known ones can be used.
  • carbamate derivatives, amide derivatives, imide derivatives, ⁇ -cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives examples thereof include oxime derivatives.
  • the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
  • the generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalytic action for the dehydration condensation reaction or the like in the imidization of the polyimide precursor is strong, and the catalytic effect in the dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. That is, since the catalytic effect of the generated basic substance is great, the apparent sensitivity as a negative photosensitive resin composition is improved. From the viewpoint of the catalytic effect, an amidine and an aliphatic amine are preferable.
  • the photobase generator is preferably a photobase generator that does not contain salt in the structure, and preferably has no charge on the nitrogen atom of the base moiety generated in the photobase generator.
  • the photobase generator it is preferable that the generated base is latentized using a covalent bond, and the base generation mechanism is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is broken. It is preferable that a base is generated.
  • the photobase generator contains no salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved.
  • the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
  • the generated base is latentized using a covalent bond as described above, and the generated base has an amide bond, carbamate bond, or oxime bond. It is preferably latentized by using.
  • the photobase generator according to the present invention include photobase generators having a cinnamic acid amide structure as disclosed in JP2009-80452A and WO2009 / 123122, and JP2006- No.
  • photobase generators having a carbamate structure, an oxime structure as disclosed in JP-A 2007-249013 and JP-A 2008-003581 examples include photobase generators having a carbamoyloxime structure, but are not limited thereto, and other known photobase generator structures can be used.
  • photobase generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019, and the compound described in paragraph 0052 of WO2010 / 064631.
  • the composition of the present invention may contain a thermal acid generator.
  • Thermal acid generator generates acid by heating, promotes cyclization of polyimide precursor, etc., and further improves the mechanical properties of the cured film, as well as compounds having hydroxymethyl, alkoxymethyl or acyloxymethyl groups, epoxy There is an effect of promoting the crosslinking reaction of at least one compound selected from a compound, an oxetane compound and a benzoxazine compound.
  • the thermal decomposition starting temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 250 ° C. or less.
  • no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (curing: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select one that generates an acid, since a decrease in sensitivity during development can be suppressed.
  • the acid generated from the thermal acid generator is preferably a strong acid.
  • arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid
  • alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid
  • trifluoromethanesulfone haloalkyl sulfonic acids such as acids are preferred.
  • Examples of such a thermal acid generator include those described in paragraph 0055 of JP2013-072935A.
  • those that generate an alkylsulfonic acid having 1 to 4 carbon atoms or a haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid ( 4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonate (4-((methoxycarbonyl ) Oxy) phenyl) methylsulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesul
  • JP2013-167742A is also preferable as the thermal acid generator.
  • the content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor or the like.
  • the content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor or the like.
  • 0.01 part by mass or more By containing 0.01 part by mass or more, the cyclization of the crosslinking reaction and the polyimide precursor is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved.
  • 20 mass parts or less are preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are more preferable.
  • One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the composition of the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator).
  • a thermal radical polymerization initiator a known thermal radical polymerization initiator can be used.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound.
  • the thermal radical polymerization initiator By adding a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor or the like is advanced.
  • a polyimide precursor etc. contain an ethylenically unsaturated bond, since polymerization reaction of a polyimide precursor etc.
  • Thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable.
  • the thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C. Specifically, compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be mentioned. In a commercial item, perbutyl Z and park mill D (made by NOF Corporation) can be used conveniently.
  • the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass with respect to the total solid content of the composition. 0.1 to 20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, and preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.
  • a corrosion inhibitor is added for the purpose of preventing the outflow of ions from the metal wiring.
  • the compound include a rust inhibitor described in paragraph 0094 of JP2013-15701A, and paragraph 0073 of JP2009-283711A.
  • a rust inhibitor described in paragraph 0094 of JP2013-15701A
  • paragraph 0073 of JP2009-283711A examples of the compound.
  • compounds described in paragraph 0052 of JP2011-59656A, compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, and the like can be used.
  • a compound having a triazole ring or a compound having a tetrazole ring can be preferably used.
  • the amount of the corrosion inhibitor is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the polyimide precursor or the like.
  • the corrosion inhibitor may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the composition of this invention contains the metal adhesive improvement agent for improving the adhesiveness with the metal material used for an electrode, wiring, etc.
  • the metal adhesion improver include sulfide compounds described in paragraphs 0046 to 0049 of JP2014-186186A and paragraphs 0032 to 0043 of JP2013-072935A.
  • the metal adhesion improver also include the following compounds.
  • the compounding amount of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor and the like.
  • membrane and metal after thermosetting becomes favorable, and the heat resistance of the film
  • Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
  • the composition of this invention contains the silane coupling agent at the point which can improve adhesiveness with a board
  • the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP2014-191002, compounds described in paragraphs 0063 to 0071 of international publication WO2011 / 080992A1, and JP2014-191252A.
  • the amount of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor and the like. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed. Only one type of silane coupling agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the composition of the present invention may contain a sensitizing dye.
  • a sensitizing dye absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizing dye in an electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur.
  • the amine generator, the thermal radical polymerization initiator, and the photopolymerization initiator are decomposed by causing a chemical change to generate radicals, acids, or bases.
  • preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the range of 300 nm to 450 nm.
  • polynuclear aromatics eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene
  • xanthenes eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • thioxanthones (For example, 2,4-diethylthioxanthone)
  • cyanines for example thiacarbocyanine, oxacarbocyanine
  • merocyanines for example merocyanine, carbomerocyanine
  • thiazines for example thionine, methylene blue, toluidine blue
  • acridines Eg, acridine orange, chloroflavin, acriflavine
  • combination with polynuclear aromatics for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes, and styrylbenzenes is preferable from the viewpoint of starting efficiency, and has an anthracene skeleton. More preferably, the compound is used. Particularly preferred specific compounds include 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene.
  • the content of the sensitizing dye is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 15% by mass, based on the total solid content of the composition. More preferably, it is 5 to 10% by mass.
  • a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
  • the composition of the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684.
  • As the chain transfer agent for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals.
  • thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • 2-mercaptobenzimidazoles for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • the preferred content of the chain transfer agent is preferably 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight, with respect to 100 parts by weight of the total solid content of the composition. Particularly preferred is 1 to 5 parts by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.
  • Various surfactants may be added to the composition of the present invention from the viewpoint of further improving coatability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • a fluorosurfactant liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved.
  • the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coated surface The coating property of is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content of the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and also has good solvent solubility.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
  • the following compounds are also exemplified as the fluorosurfactant used in the present invention.
  • the weight average molecular weight of the above compound is, for example, 14,000.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 , Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like.
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid.
  • Polyflow No. which is a system (co) polymer. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0%, based on the total solid content of the composition. % By mass. Only one surfactant may be used, or two or more surfactants may be used. When there are two or more surfactants, the total is preferably in the above range.
  • a higher fatty acid derivative such as behenic acid or behenamide is added to the composition of the present invention so that it is unevenly distributed on the surface of the composition during the drying process after coating. May be.
  • the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the composition. Only one type of higher fatty acid derivative or the like may be used. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
  • the composition of the present invention may contain an adhesion promoter.
  • adhesion promoter By including an adhesion promoter, adhesion can be further improved.
  • a preferred example of the adhesion promoter is a compound represented by the following formula (42).
  • Formula (42) (In Formula (42), R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom or a monovalent organic group.)
  • Another preferred example of the adhesion promoter is a compound represented by the following formula (43).
  • R 9 and R 10 are each independently an alkyl group having 1 to 5 carbon atoms, if R 9 there are a plurality or different and they are the same, R 10 is more If present, they may be the same or different, q is an integer from 1 to 10, and r is an integer from 0 to 3.
  • Specific examples of the adhesion promoter include aluminum chelate A (w) (trade name) (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum trisacetylacetonate), aluminum chelate D (trade name) (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum bisethyl) Acetoacetate monoacetylacetonate), TC-401 (trade name) (manufactured by Matsumoto Fine Chemical Co., titanium tetraacetylacetonate), ZC-150 (trade name) (manufactured by Matsumoto Fine Chemical Co., zirconium tetraacetylacetonate
  • the blending amount of the adhesion promoter when blended, is preferably 0.01 to 50% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass based on the total solid content of the composition. .
  • the adhesion promoter may contain only one type or two or more types. When 2 or more types are included, the total amount is preferably within the above range.
  • ⁇ Solvent> When laminating the composition of the present invention by coating, it is preferable to blend a solvent. Any known solvent can be used without limitation as long as the composition can be formed into a layer. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, and ⁇ -caprolactone , ⁇ -valerolactone, alkyl oxyacetate alkyl (eg, methyl oxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate
  • the solvent is preferably in the form of a mixture of two or more types from the viewpoint of improving the coated surface.
  • a mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent is preferably such that the total solid content of the composition is 5 to 80% by mass, more preferably 5 to 70% by mass, from the viewpoint of applicability. 10 to 60% by mass is particularly preferable.
  • One type of solvent may be sufficient and 2 or more types may be sufficient as it.
  • the total is preferably in the above range.
  • the contents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide are based on the total mass of the composition from the viewpoint of film strength. It is preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.5% by weight, and particularly preferably less than 0.1% by weight.
  • the composition of the present invention is within the range that does not impair the effects of the present invention, and various additives as necessary, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation.
  • An agent or the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the composition.
  • the water content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface.
  • the metal content of the composition of the present invention is preferably less than 5 ppm by weight, more preferably less than 1 ppm by weight, and particularly preferably less than 0.5 ppm by weight from the viewpoint of insulation.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the composition, and filter filtration is performed on the raw material constituting the composition. Examples thereof include a method of performing distillation under a condition in which the inside of the apparatus is lined with polytetrafluoroethylene or the like and contamination is suppressed as much as possible.
  • the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
  • a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, Especially less than 0.5 mass ppm is preferable.
  • the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.
  • the composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited, and can be performed by a conventionally known method.
  • the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • you may pressurize and filter and the pressure to pressurize is 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed by an adsorbent, or a combination of filter filtration and adsorbent may be used.
  • adsorbent known adsorbents can be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • the container for the composition used in the present invention a conventionally known container can be used.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and the 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the cured film of the present invention is formed by curing the composition of the present invention.
  • the thickness of the cured film of the present invention can be, for example, 1 ⁇ m or more, and can be 5 ⁇ m or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.
  • the laminated body of this invention has 2 or more layers of the cured film of this invention.
  • Such a laminate preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring whose details will be described later.
  • Fields to which the cured film or laminate of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like. Particularly, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
  • the cured film in the present invention can also be used for a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist).
  • the cured film of the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, the use for etching molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.
  • the method for producing a cured film of the present invention includes the use of the composition of the present invention, and preferably a photosensitive resin composition layer forming step in which the photosensitive resin composition is applied to a substrate to form a layer, and photosensitive An exposure step of exposing the photosensitive resin composition layer, and a step of developing the exposed photosensitive resin composition layer.
  • the production method of the present invention is particularly excellent when performing negative development processing.
  • the production method of the present invention may include a step of heating the developed photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the development processing step. Since the cured film of the present invention has excellent heat resistance, good performance can be maintained even when heated at 150 to 500 ° C.
  • the photosensitive resin composition layer forming step, the exposure step, and the development processing step are performed again. Including performing again in order.
  • the photosensitive resin composition layer forming step, the exposure step, and the development processing step are preferably performed 2 to 5 times in the above order (that is, 3 to 6 times in total).
  • a laminated body can be obtained by laminating a cured film.
  • the present invention also discloses a semiconductor device including at least one of the cured film and the laminate of the present invention.
  • a semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
  • the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described.
  • the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.
  • Each of the plurality of semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate.
  • the uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
  • the semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.
  • the stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected. That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto by a metal bump 103b such as a solder bump.
  • connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. ing.
  • An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.
  • the stacked body 101 is stacked on the wiring board 120.
  • the wiring substrate 120 for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used.
  • the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).
  • a surface electrode 120 a is provided on one surface of the wiring board 120.
  • An insulating layer 115 in which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected via the rewiring layer 105. It is connected.
  • the insulating layer 115 is formed using the composition in the present invention. That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump.
  • the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
  • An underfill layer 110 a is formed between the insulating layer 115 and the stacked body 101.
  • an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.
  • the cured film in the present invention can be widely used in various applications using polyimide.
  • polyimide is resistant to heat
  • the cured film and the like in the present invention can be suitably used for transparent plastic substrates, display parts such as liquid crystal displays and electronic paper, automobile parts, heat resistant paints, coating agents, and films.
  • reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 ml N-methylpyrrolidone were added.
  • the reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at ⁇ 10 ⁇ 4 ° C. During the addition of SOCl 2 the viscosity increased. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
  • the mixture was further stirred at 75 ° C. for 2 hours under a nitrogen atmosphere.
  • the polymer was precipitated in 5 liters of water and stirred for 15 minutes at a speed of 5000 rpm.
  • the acrylic resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Subsequently, the obtained acrylic resin was dried at 45 ° C. under reduced pressure for 3 days.
  • Examples and Comparative Examples> The following components were mixed to prepare a photosensitive resin composition coating solution as a uniform solution.
  • the photosensitive resin composition obtained above was filtered under pressure through a filter having a pore width of 0.8 ⁇ m.
  • composition of photosensitive resin composition >> (A) Resin: part by mass described in Table 1 (B) urethane (meth) acrylate or its comparative compound: part by mass described in Table 1 (C) photoradical polymerization initiator: part by mass described in Table 1 (D ) Polymerization inhibitor: parts by mass described in Table 1 (other components): in the Examples and Comparative Examples, the following amounts were added: Tetrazole (migration inhibitor): 0.100 parts by mass N-methyl-2- Pyrrolidone (solvent): 60.0 parts by mass
  • Resin A-1 to A-5 and RA-1 are polyimide precursors or comparative resins synthesized in the above synthesis examples.
  • A-6 is Matrimide 5218 (made by HUNTSMAN, polyimide).
  • RA-2 is polymethyl methacrylate (Mw: 15,000, manufactured by Aldrich).
  • C Photoradical polymerization initiator
  • C-1 Oxime-based photoradical polymerization initiator
  • IRGACURE OXE-01 manufactured by BASF
  • C-2 Aminoacetophenone photoradical polymerization initiator
  • IRGACURE-369 manufactured by BASF
  • C-3 Metallocene compound-based photoradical polymerization initiator
  • IRGACURE-784 manufactured by BASF
  • Polymerization inhibitor D-1 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • D-2 p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Each photosensitive resin composition was applied by spinning on a silicon wafer.
  • the silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform polymer layer having a thickness described in Table 1 on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). The exposure is performed with i-line, using a line and space photomask in 1 ⁇ m increments from 5 ⁇ m to 25 ⁇ m at each exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ / cm 2 at a wavelength of 365 nm. , Exposure was performed.
  • the exposed photosensitive resin composition layer was negatively developed with cyclopentanone for 60 seconds.
  • the change in the line width is small with respect to the change in exposure energy, it indicates that the exposure latitude is wide, which is a preferable result.
  • the measurement limit is 5 ⁇ m.
  • B Over 8 ⁇ m to 10 ⁇ m or less
  • C Over 10 ⁇ m to 15 ⁇ m or less
  • D Over 15 ⁇ m to 20 ⁇ m or less
  • E Over 20 ⁇ m.
  • F A pattern having a line width with sharp edges could not be obtained.
  • a photosensitive resin composition was applied to the surface of a silicon wafer by spinning on the silicon wafer.
  • the silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform polymer layer having a thickness described in Table 1 on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure was performed with i-line, and exposure was performed with an exposure energy of 400 mJ / cm 2 at a wavelength of 365 nm. The exposed photosensitive resin composition layer is heated at 250 ° C.
  • Each photosensitive resin composition was applied by spinning on a silicon wafer.
  • the silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a photosensitive resin composition layer having a uniform thickness described in Table 1 on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 400 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer was exposed to cyclopentanone for 60 seconds.
  • a copper plating process was performed, and a metal layer (copper thin film) having a thickness of 5 ⁇ m was formed on the surface of the photosensitive resin composition layer by vapor deposition to form a laminate 1.
  • a metal layer copper thin film having a thickness of 5 ⁇ m was formed on the surface of the photosensitive resin composition layer by vapor deposition to form a laminate 1.
  • the application of the photosensitive resin composition, exposure, development, and heating at 250 ° C. were repeated to obtain a laminate 2.
  • peeling occurrences refers to the number of peelings confirmed by confirming a sample having a width of 5 mm with an optical microscope. If peeling does not occur, it means that the film has excellent adhesiveness, which is a preferable result.
  • the numerical value of exposure latitude in the above table indicates exposure energy (unit: mJ / cm 2 ).
  • a photosensitive resin composition in which the blending amount of (B) urethane (meth) acrylate in Example 1 was 9.6% by mass with respect to (A) resin, and the amount of (B) urethane (meth) acrylate was increased and the solvent was reduced The thing was produced and the photosensitive resin composition layer was formed. Similarly, it was confirmed that a good photosensitive resin composition layer was obtained.
  • Example 100 The photosensitive resin composition of Example 1 was subjected to pressure filtration through a filter having a pore width of 1.0 ⁇ m, and then spin-coated (3500 rpm, 30 seconds) on the surface of the resin substrate on which the copper thin layer was formed. Applied. The photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (Nikon NSR1505i6). The exposure was performed through a mask at an exposure amount of 200 mJ / cm 2 at a wavelength of 365 nm.

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Abstract

L'invention concerne une composition de résine photosensible ayant une propriété d'adhérence supérieure, un film durci l'utilisant, un stratifié, un procédé de fabrication de film durci, un procédé de fabrication de stratifié et un dispositif semi-conducteur. La composition de résine comprend un précurseur de polyimide, au moins un type de résine de polyimide, et au moins un type de (méth)acrylate d'uréthane. Le (méth)acrylate d'uréthane a une structure de fraction représentée par la formule (A) et/ou une structure de fraction représentée par la formule (B), 4 à 15 groupes (méth)acrylate, et une structure d'uréthane. Il est à noter que le symbole * des formules représente un bras de liaison.
PCT/JP2017/002563 2016-01-29 2017-01-25 Composition de résine photosensible, film durci, stratifié, procédé de fabrication de film durci, procédé de fabrication de stratifié et dispositif semi-conducteur Ceased WO2017131037A1 (fr)

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KR1020187021308A KR102104806B1 (ko) 2016-01-29 2017-01-25 감광성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법, 적층체의 제조 방법, 및 반도체 디바이스

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JP2021120699A (ja) * 2020-01-30 2021-08-19 旭化成株式会社 ネガ型感光性樹脂組成物、並びにこれを用いたポリイミド及び硬化レリーフパターンの製造方法
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KR20230043166A (ko) 2020-08-26 2023-03-30 후지필름 가부시키가이샤 경화성 수지 조성물, 경화물, 적층체, 경화물의 제조 방법, 및, 반도체 디바이스
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JP7592393B2 (ja) * 2019-04-09 2024-12-02 旭化成株式会社 ネガ型感光性樹脂組成物、ポリイミドの製造方法および硬化レリーフパターンの製造方法
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KR20220108029A (ko) * 2019-11-29 2022-08-02 에이치디 마이크로시스템즈 가부시키가이샤 수지 조성물, 경화물의 제조 방법, 경화물, 커버 코트층, 표면 보호막 및 전자 부품
TWI869552B (zh) * 2020-02-28 2025-01-11 日商富士軟片股份有限公司 硬化性樹脂組成物、硬化膜、積層體、硬化膜之製造方法及半導體器件
TWI899243B (zh) * 2020-06-05 2025-10-01 日商富士軟片股份有限公司 樹脂組成物及其製造方法以及圖案形成用組成物的製造方法
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KR102875352B1 (ko) * 2021-02-17 2025-10-27 후지필름 가부시키가이샤 영구막의 제조 방법, 적층체의 제조 방법, 및, 반도체 디바이스의 제조 방법

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