[go: up one dir, main page]

WO2018003725A1 - Composition de résine photosensible négative, film durci, procédé de production de film durci, dispositif semi-conducteur, procédé de production de stratifié, procédé de production de dispositif semi-conducteur et précurseur de polyimide - Google Patents

Composition de résine photosensible négative, film durci, procédé de production de film durci, dispositif semi-conducteur, procédé de production de stratifié, procédé de production de dispositif semi-conducteur et précurseur de polyimide Download PDF

Info

Publication number
WO2018003725A1
WO2018003725A1 PCT/JP2017/023341 JP2017023341W WO2018003725A1 WO 2018003725 A1 WO2018003725 A1 WO 2018003725A1 JP 2017023341 W JP2017023341 W JP 2017023341W WO 2018003725 A1 WO2018003725 A1 WO 2018003725A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
resin composition
photosensitive resin
negative photosensitive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/023341
Other languages
English (en)
Japanese (ja)
Inventor
健太 吉田
悠 岩井
渋谷　明規
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to KR1020187036825A priority Critical patent/KR102187513B1/ko
Priority to JP2018525148A priority patent/JP6837063B2/ja
Publication of WO2018003725A1 publication Critical patent/WO2018003725A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a negative photosensitive resin composition, a cured film, a method for producing a cured film, a semiconductor device, a method for producing a laminate, a method for producing a semiconductor device, and a polyimide precursor.
  • Thermosetting resins that are cured by cyclization are used for insulating layers of semiconductor devices and the like because they are excellent in heat resistance and insulation. 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.
  • Patent Document 1 discloses (A) a substituent having a repeating unit represented by the general formula (1) in the main chain and a photopolymerizable carbon-carbon double bond at both molecular ends.
  • a polyimide precursor having an actinic functional group having a structure modified with an aminobenzene or a trimellitic acid derivative (B) a photo-assisting agent having a photopolymerizable functional group, and (C) N-aryl
  • a resin composition containing a photopolymerization initiator containing an ⁇ -amino acid and a thioxanthone, wherein the content of the photopolymerization initiator is 7 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor Part of the photosensitive resin composition is described.
  • R 1 is a tetravalent organic group
  • R 2 is a divalent organic group.
  • Patent Document 1 Since Patent Document 1 has a polyamic acid structure, it is susceptible to hydrolysis by water. Therefore, the stability over time is low, and furthermore, the synthesized resin cannot be purified in an aqueous system, so that it is difficult to apply it in semiconductor applications that require high quality.
  • an object of the present invention is to provide a negative photosensitive resin composition excellent in resolution. Moreover, it is providing the cured film using said negative photosensitive resin composition, the manufacturing method of a cured film, a semiconductor device, the manufacturing method of a laminated body, the manufacturing method of a semiconductor device, and a polyimide precursor.
  • the present inventors can improve the resolution by providing a polymerizable group at the end of the polyimide precursor and setting the weight average molecular weight of the polyimide precursor to 50000 or less.
  • the present invention has been completed. Accordingly, the present invention provides the following.
  • ⁇ 1> includes a polyimide precursor, a photopolymerization initiator, and a solvent,
  • the polyimide precursor has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50000 or less, and is a negative photosensitive.
  • Resin composition In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and R 1 and R 2 are each independently a non-polymerizable organic group; (A) l -L 1- * (2) In the formula (2), A represents a polymerizable group, L 1 represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site with another site. ⁇ 2> The negative photosensitive resin composition according to ⁇ 1>, wherein l in formula (2) is an integer of 2 to 5.
  • ⁇ 6> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polyimide precursor has a weight average molecular weight of 5000 or more.
  • ⁇ 7> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a polyfunctional radical polymerizable monomer.
  • ⁇ 8> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a thermal base generator.
  • ⁇ 9> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the photopolymerization initiator is at least one selected from an oxime compound and a metallocene compound.
  • ⁇ 10> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 11> A cured film obtained by curing the negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 12> The cured film according to ⁇ 11>, wherein the film thickness is 1 to 30 ⁇ m.
  • ⁇ 13> a photosensitive resin composition layer forming step in which the negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10> is applied to a substrate to form a layer; An exposure step of exposing the negative photosensitive resin composition layer; A development processing step of performing development processing on the exposed photosensitive resin composition layer; The manufacturing method of the cured film which has this.
  • ⁇ 15> A semiconductor device having the cured film according to ⁇ 11> or ⁇ 12>.
  • ⁇ 16> A method for producing a laminate including the method for producing a cured film according to ⁇ 13> or ⁇ 14>.
  • ⁇ 17> A method for producing a semiconductor device, comprising the method for producing a cured film according to ⁇ 13> or ⁇ 14>.
  • X represents a divalent organic group
  • Y represents a tetravalent organic group
  • R 1 and R 2 are each independently a non-polymerizable organic group;
  • A represents a polymerizable group
  • L 1 represents a single bond or an l + 1 valent organic group
  • l represents an integer of 1 to 10
  • * represents a bonding site with another site.
  • a negative photosensitive resin composition excellent in resolution.
  • a cured film, a cured film manufacturing method, a semiconductor device, a laminate manufacturing method, a semiconductor device manufacturing method, and a polyimide precursor using the negative photosensitive resin composition.
  • the description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group 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).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • the light used for exposure generally includes active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • 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) acryl” represents both “acryl” and “methacryl”
  • (Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
  • solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC) measurement unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220 (manufactured by Tosoh Corporation), and guard columns TSK guard column Super AW-H and TSK Super AWM-H (Tosoh Corporation) ))).
  • the eluent was measured using N-methyl-2-pyrrolidone (NMP) unless otherwise stated.
  • NMP N-methyl-2-pyrrolidone
  • RI differential refractive index
  • the negative photosensitive resin composition of the present invention includes a polyimide precursor, a photopolymerization initiator, and a solvent. It has a structure represented by Formula (2) mentioned later at least at one terminal, and has a weight average molecular weight of 50000 or less.
  • the composition of this invention can be set as the negative photosensitive resin composition excellent in resolution. It is assumed that the mechanism for obtaining such an effect is as follows. According to the study by the present inventors, it was found that the glass transition temperature (Tg) can be improved by providing a polymerizable group at the terminal of the polyimide precursor. So far, polyimide precursors have generally been provided with a polymerizable group in the side chain because the polymerizable group can be introduced at a high density. However, it has been found that when a polymerizable group is added to the side chain of the polyimide precursor, the polymerizable group of the side chain may be detached during the cyclization of the polyimide precursor.
  • Tg glass transition temperature
  • the resolution during development was inferior. This was thought to be due to the relatively small amount of polymerizable groups relative to the polyimide precursor. Therefore, by setting the weight average molecular weight of the polyimide precursor to 50000 or less, the amount of the polymerizable group relative to the polyimide precursor can be relatively increased, and as a result, the resolution has been successfully improved. is there. Furthermore, according to the present invention, it is possible to improve the resolution while maintaining a high Tg of the cured film of the negative photosensitive resin composition.
  • R 1 and R 2 in the formula (1) are non-polymerizable groups having 1 to 4 carbon atoms, whereby the rate of remaining film after thermosetting can be improved. That is, when polyimide is cyclized, the R 1 and R 2 portions of the formula (1) are easily detached, and the film is reduced when it is detached.
  • the R 1 and R 2 portions of the formula (1) are non-polymerizable groups having 1 to 4 carbon atoms, so that even when these groups are eliminated by cyclization, the film can be more effectively reduced. Can be suppressed. That is, the remaining film ratio after thermosetting can be maintained higher.
  • the lower limit value of the glass transition temperature measured by the method described in Examples described later is preferably 226 ° C or higher, more preferably 228 ° C or higher, and 230 ° C or higher. Is more preferable. If the glass transition temperature is equal to or higher than the above value, an improvement in reliability in a high temperature process such as a vapor deposition process for forming a metal wiring or a bonding process between electrodes can be expected.
  • the upper limit value of the glass transition temperature is not particularly defined, but for example, the desired performance is sufficiently exhibited even at 350 ° C. or lower.
  • the exposed film residual film ratio is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more.
  • the exposed portion residual film ratio is a value defined as follows. The details of the measurement method can be referred to the description of Examples described later.
  • Exposed part residual film ratio (%) [film thickness after development of exposed part / film thickness of unexposed part before development] ⁇ 100
  • the residual film ratio after thermosetting is preferably 70% or more, more preferably 80% or more, and further preferably 85% or more.
  • the composition of the present invention has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50,000 or less. Containing.
  • This polyimide precursor is also the polyimide precursor of the present invention.
  • X represents a divalent organic group
  • Y represents a tetravalent organic group
  • R 1 and R 2 are each independently a non-polymerizable organic group
  • A represents a polymerizable group
  • L 1 represents a single bond or an l + 1 valent organic group
  • l represents an integer of 1 to 10
  • * represents a bonding site with another site.
  • Examples of the divalent organic group represented by X in the formula (1) include a linear or branched aliphatic group, a group containing a cyclic aliphatic group, and an aromatic group.
  • a branched aliphatic group, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and includes an aromatic group having 6 to 20 carbon atoms. Groups are more preferred.
  • a particularly preferred embodiment includes a group 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 group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group.
  • L is preferably 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.
  • the divalent organic group represented by X in the formula (1) is preferably a group derived from 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.
  • the divalent organic group represented by X is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms.
  • a diamine containing a group or a group consisting of a combination thereof is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred.
  • the following aromatic groups are mentioned as an example of an aromatic group.
  • A represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S—. , —S ( ⁇ O) 2 —, —NHCO—, and a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, It is more preferably a group selected from —O—, —C ( ⁇ O) —, —S—, —SO 2 —, —CH 2 —, —O—, —S—, —SO 2 —, More preferably, it is a divalent group selected from the group consisting of —C (CF 3 ) 2 — and —C (CH 3 ) 2 —.
  • 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; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether
  • 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 two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is 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 (above trade names, manufactured by HUNTSMAN), 1- (2- (2- (2- (2- Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like, but is not limited thereto. .
  • x, y, and z are average values.
  • the divalent organic group represented by X in the formula (1) is also 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 the 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 or a trifluoromethyl group. It is.
  • 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 formula (61), R 18 and R 19 are each independently a fluorine atom or a trifluoromethyl group.
  • Examples of the diamine compound that gives the structure of formula (51) or (61) include 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diamino.
  • Biphenyl 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 112 represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO.
  • -, - NHCO- is preferably a group selected from these combinations, a single bond, an alkylene group which ⁇ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - CO- More preferably a group selected from -S- and -SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2- , -O-, -CO More preferred is a divalent group selected from the group consisting of —, —S— and —SO 2 —.
  • tetravalent organic group represented by Y in Formula (1) examples include a tetracarboxylic acid residue remaining after the removal of the acid dianhydride 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 a compound represented by the following formula (O).
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetra Carboxylic 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′-oxydi
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
  • At least one of X and Y in the formula (1) has a hydroxyl group.
  • the non-polymerizable organic group represented by R 1 and R 2 in the formula (1) is preferably a group not containing a carbon-carbon unsaturated double bond.
  • a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are preferable.
  • the aromatic group include an aryl group and an aralkyl group.
  • the non-polymerizable organic group represented by R 1 and R 2 is more preferably a non-polymerizable organic group having 1 to 4 carbon atoms, and is a linear or branched alkyl group having 1 to 4 carbon atoms. Is more preferable.
  • non-polymerizable organic group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group.
  • Group, sec-butyl group and tert-butyl group are preferable, methyl group and ethyl group are more preferable, and methyl group is more preferable.
  • the polyimide precursor of the present invention has a structure represented by the formula (2) at least at one end.
  • A represents a polymerizable group
  • L 1 represents a single bond or an l + 1 valent organic group
  • l represents an integer of 1 to 10
  • * represents a bonding site with another site.
  • the polymerizable group represented by A in the formula (2) is preferably a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a group represented by the following formula (A-1), and a group represented by the formula (A-2).
  • * represents a bonding site with L 1 and equation (2).
  • R 3 represents a hydrogen atom or a methyl group
  • Z represents an oxygen atom or NH.
  • L 1 represents a single bond or an l + 1 valent organic group, preferably an l + 1 valent organic group.
  • the l + 1 valent organic group is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. Groups. Specific examples of the l + 1 valent organic group include the following structural units or a group formed by combining two or more of the following structural units (which may form a ring structure).
  • l represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and further preferably an integer of 2 to 5. According to this aspect, the remaining film ratio after development in the exposed portion can be increased.
  • the structure represented by Formula (2) is preferably a structure represented by Formula (3) or Formula (4), and more preferably a structure represented by Formula (3). According to this aspect, the remaining film ratio after development in the exposed portion can be increased.
  • R 3 represents a hydrogen atom or a methyl group
  • Z represents an oxygen atom or NH
  • L 2 represents a single bond or an m + 1 valent organic group
  • m represents an integer of 1 to 10.
  • * Indicates a binding site with another site.
  • L 3 represents a single bond or an n + 1 valent organic group
  • n represents an integer of 1 to 10
  • * represents a bonding site with another site.
  • the m + 1 valent organic group represented by L 2 in Formula (3) and the n + 1 valent organic group represented by L 3 in Formula (4) are the groups described for the l + 1 valent organic group represented by L 1 in Formula (2).
  • the preferable range is also the same.
  • m represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and further preferably an integer of 2 to 5. According to this aspect, the remaining film ratio in the exposed portion can be increased.
  • n represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and further preferably an integer of 2 to 5. According to this aspect, the remaining film ratio in the exposed portion can be increased.
  • the polyimide precursor of the present invention has a fluorine atom in the repeating unit.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.
  • the polyimide precursor of the present invention may further contain a repeating unit containing an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate.
  • a repeating unit containing an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate.
  • the diamine component for introducing an aliphatic group having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • the repeating unit represented by the formula (1) may be one type or two or more types. Moreover, the polyimide precursor may contain the structural isomer of the repeating unit represented by Formula (1). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit represented by the formula (1).
  • the polyimide precursor of the present invention preferably contains 50 mol% or more of the repeating units represented by the formula (1), more preferably 70 mol% or more, more preferably 90 mol% or more of all repeating units. More preferably.
  • the weight average molecular weight (Mw) of the polyimide precursor is 50000 or less, preferably 40000 or less, and more preferably 35000 or less.
  • the lower limit is preferably more than 2000, more preferably 5000 or more, further preferably 6000 or more, and further preferably 7000 or more. If the weight average molecular weight of a polyimide precursor is 50000 or less, it is excellent in developability. Moreover, if the weight average molecular weight of a polyimide precursor is 5000 or more, the mechanical strength of the obtained cured film is favorable.
  • the degree of dispersion (Mw / Mn) 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 content of the polyimide precursor in the composition of the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and further preferably 70 to 96% by mass of the total solid content of the composition of the present invention.
  • the composition of the present invention has a repeating unit represented by the formula (1), and has a structure represented by “(A) 1 -L 1- *” at least at one end;
  • the content of the polyimide precursor having a weight average molecular weight of 50000 or less is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and further 70 to 96% by mass based on the total solid content of the composition of the present invention. preferable.
  • the carboxyl group is esterified. Can be manufactured.
  • the reaction product is further reacted with a compound having a polymerizable group. it can.
  • the molar ratio of tetracarboxylic dianhydride or derivative thereof to the above alcohol is 0.9 to 1.1: 2.1 to 1.
  • the molar ratio of tetracarboxylic dianhydride or derivative thereof to diamine is 0.8 to 1.2: 1.2 to 0. .8 is preferable, and 1.001 to 1.2: 0.999 to 0.8 is more preferable.
  • the reaction temperature of the above reaction is preferably ⁇ 20 to 60 ° C.
  • the reaction time is preferably 30 minutes to 10 hours.
  • the molecular weight of the alcohol to be reacted with tetracarboxylic dianhydride is preferably 30 to 150, more preferably 30 to 80, and further preferably 30 to 65.
  • the alcohol to be reacted with tetracarboxylic dianhydride is preferably an alcohol having 1 to 8 carbon atoms, more preferably an alcohol having 1 to 4 carbon atoms, still more preferably an alcohol having 1 to 3 carbon atoms, and an alcohol having 1 or 2 carbon atoms.
  • Alcohol is more preferable, and alcohol having 1 carbon (methanol) is even more preferable.
  • Specific examples of the alcohol include methanol, ethanol, propanol, and n-butanol, and methanol is particularly preferable.
  • the compound having a polymerizable group is preferably a compound having 1 to 10 polymerizable groups, more preferably a compound having 2 to 8 polymerizable groups, and still more preferably a compound having 2 to 5 polymerizable groups.
  • a group containing a carbon-carbon unsaturated double bond is preferable.
  • a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styryl group, a group represented by the above formula (A-1) and a group represented by the above formula (A-2) Is mentioned.
  • the molecular weight of the compound having a polymerizable group is preferably from 100 to 2000, more preferably from 100 to 1500, and further preferably from 100 to 1000. If the molecular weight of the compound having a polymerizable group is within the above range, specific examples of the compound in which a polyimide precursor excellent in resolution can be easily obtained include pentaerythritol trimethyl when an acid dianhydride is excessively used.
  • EO ethylene oxide
  • 2-isocyanatoethyl (meth) acrylate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate are exemplified.
  • 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.
  • one end of the main chain of the precursor is sealed with an end-capping agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound in order to further improve storage stability. You may stop. Of these, it is more preferable to use a monoamine.
  • 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
  • a step of depositing a solid may be included. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction solution in a poor solvent such as water or alcohol. Then, a polyimide precursor can be dried and a powdery polyimide precursor can be obtained.
  • the composition of the present invention contains a photopolymerization initiator.
  • the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferred.
  • the composition of the present invention contains a photo radical polymerization initiator
  • the composition of the present invention is applied to a substrate such as a semiconductor wafer to form a negative photosensitive resin composition layer, and then irradiated with light. Curing due to radicals occurs, and the solubility in the light irradiation part can be reduced. For this reason, for example, by exposing a negative photosensitive resin composition layer through a photomask having a pattern for masking only the electrode portion, it is possible to easily produce regions having different solubility according to the electrode pattern. There are advantages.
  • a photoinitiator having photosensitivity to light in the ultraviolet region to the visible region is 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. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
  • ketone compounds include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kaya Cure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • 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 the 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 exposure latitude can be improved more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a thermal base generator.
  • 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.
  • Preferable oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-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.
  • IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, light described in JP2012-14052A) A polymerization initiator 2) is also preferably used.
  • 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.
  • an oxime compound having a fluorine atom examples 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. And the compound (C-3) described in paragraph 0101 of JP-A No. 164471.
  • oxime compounds having a specific substituent as disclosed in JP-A-2007-267979 there are oxime compounds having a thioaryl group as 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, triaryls from the viewpoint of exposure sensitivity.
  • Selected from the group consisting of imidazole 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. are preferred.
  • More preferred photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is particularly preferred.
  • Photopolymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), and the like.
  • 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 the group represented by 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.
  • R 55 is the alkyl
  • the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 30% by mass with respect to the total solid content of the composition of the present invention. 10% by mass.
  • the photoinitiator may contain only 1 type and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total is preferably in the above range.
  • the composition of the present invention contains a solvent.
  • a known solvent can be arbitrarily used as the solvent.
  • the solvent is preferably an organic solvent.
  • Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • 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 oxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.
  • alkyl oxyacetates for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl al
  • 3-alkyloxypropionic acid alkyl esters for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropionate)) Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
  • 2-alkyloxypropionic acid alkyl esters for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
  • aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
  • Suitable examples of the sulfoxides include dimethyl sulfoxide.
  • Preferable examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
  • the solvent is preferably in the form of a mixture of two or more from the viewpoint of improving the properties of 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 concentration of the composition of the present invention is 5 to 80% by mass, more preferably 5 to 70% by mass, and more preferably 10 to 60% by mass from the viewpoint of applicability. % Is particularly preferred.
  • the solvent content may be adjusted depending on the desired thickness and coating method. For example, if the coating method is spin coating or slit coating, the content of the solvent having a solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, and more preferably 1.0% by mass to 25% by mass.
  • a photosensitive resin composition layer having a desired thickness can be uniformly formed by adjusting the amount of solvent by the coating method.
  • the solvent may contain only 1 type and may contain 2 or more types. When two or more solvents are contained, the total is preferably in the above range.
  • the composition of the present invention preferably contains a polyfunctional radically polymerizable monomer (hereinafter also referred to as a polymerizable monomer). By setting it as such a structure, the cured film excellent in heat resistance can be formed.
  • a polyfunctional radically polymerizable monomer hereinafter also referred to as a polymerizable monomer.
  • a compound having a radical polymerizable group can be used as the polymerizable monomer.
  • the radical polymerizable group include groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acryloyl group, and a (meth) allyl group.
  • the radical polymerizable group is preferably a (meth) acryloyl group.
  • the polymerizable monomer preferably has two or more radical polymerizable groups, more preferably three or more.
  • the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.
  • the composition of the present invention preferably contains at least one bifunctional or higher polymerizable monomer containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher polymerizable monomer. Is more preferable. Further, it may be a mixture of a bifunctional polymerizable monomer and a trifunctional or higher functional polymerizable monomer.
  • the number of functional groups of the polymerizable monomer means the number of radical polymerizable groups in one molecule.
  • the polymerizable monomer examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof are esters of saturated carboxylic acids and polyhydric alcohol compounds
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
  • the polymerizable monomer is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure.
  • Examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490. it can. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970.
  • polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid can also be mentioned.
  • preferable polymerizable monomers include groups having a fluorene ring and an ethylenically unsaturated bond described in JP2010-160418A, JP2010-129825A, Japanese Patent No. 4364216, and the like. It is also possible to use a compound having two or more or a cardo resin. Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid compounds. Also, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.
  • polymerizable monomers represented by the following formulas (MO-1) to (MO-5) can also be suitably used.
  • T is an oxyalkylene group
  • the terminal on the carbon atom side is bonded to R.
  • n is an integer from 0 to 14, and m is an integer from 0 to 8.
  • a plurality of R and T present in the molecule may be the same or different.
  • the compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-267979 can be used. .
  • dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (As commercial products, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are bonded via ethylene glycol and prop
  • Examples of commercially available polymerizable monomers include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains, DPCA-60, a 6-functional acrylate having 6 pentyleneoxy chains, TPA-330, a 3-functional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 manufactured by Nippon Kayaku Co., Ltd.
  • NK ester M-40G (Manufactured by Sanyo Kokusaku Pulp), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku ( UA-306H, UA-306T, UA-306I, AH-600 T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (NOF Co., Ltd.), and the like.
  • Polymerizable monomers include urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used as polymerizable monomers. You can also.
  • the polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
  • the polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. More preferred is a polymerizable monomer.
  • the aliphatic polyhydroxy compound is pentaerythritol and / or diester. It is a compound that is pentaerythritol.
  • examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the polymerizable monomer having an acid group one kind may be used alone, or two or more kinds may be mixed and used.
  • a preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.
  • the content of the polymerizable monomer is preferably 1 to 50% by mass with respect to the total solid content of the composition of the present invention from the viewpoint of good polymerizability and heat resistance.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 30% by mass or less.
  • As the polymerizable monomer one kind may be used alone, or two or more kinds may be mixed and used.
  • the mass ratio of the polyimide precursor to the polymerizable monomer is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90/10 to 50 / 50 is most preferred. If the mass ratio of a polyimide precursor and a polymerizable monomer is in the above range, a cured film that is superior in polymerizability and heat resistance can be formed.
  • a monofunctional polymerizable monomer can be preferably used from the viewpoint of warpage suppression by controlling the elastic modulus of the cured film.
  • Monofunctional polymerizable monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
  • N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Goods and the like are preferably used.
  • the monofunctional polymerizable monomer a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • composition of this invention can further contain other polymerizable compounds other than the polyimide precursor and polymerizable monomer mentioned above.
  • Other polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
  • R 4 represents a t-valent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by —OR 6 or —OCO—R 7.
  • R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 7 represents an organic group having 1 to 10 carbon atoms.
  • the content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. More preferably, it is 10 to 35 parts by mass. Further, the compound represented by the following formula (AM4) is contained in the total amount of other polymerizable compounds in an amount of 10 to 90% by mass, and the compound represented by the following formula (AM5) is contained in an amount of 10 to 90% by mass. Is also preferable.
  • R 4 represents a divalent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by —OR 6 or —OCO—R 7
  • R 6 represents a hydrogen atom or a carbon atom.
  • R 7 represents an organic group having 1 to 10 carbon atoms.
  • R 4 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by —OR 6 or —OCO—R 7.
  • R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 7 represents an organic group having 1 to 10 carbon atoms.
  • the occurrence of cracks can be more effectively suppressed when the composition of the present invention is applied to an uneven substrate. Moreover, it is excellent in pattern workability and can form the cured film which has high heat resistance from which 5% mass reduction
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
  • Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • Epoxy compound compound having an epoxy group
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and warping of the composition.
  • the epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed. Moreover, the film
  • the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
  • epoxy compound examples include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane.
  • Epicron (registered trademark) 850-S Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( )), EP-4003S, EP-4000S (trade name, manufactured by
  • an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance.
  • Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
  • the content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. If the content of the epoxy compound is 5 parts by mass or more, warpage of the obtained cured film can be further suppressed, and if it is 50 parts by mass or less, pattern filling caused by reflow during curing can be further suppressed.
  • oxetane compound compound having oxetanyl group
  • examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester.
  • Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Two or more kinds may be mixed.
  • the content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.
  • a benzoxazine compound (compound having a benzoxazolyl group))
  • a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal contraction is further reduced to suppress warpage.
  • benzoxazine compound examples include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzoxazine. Compounds. These may be used alone or in combination of two or more.
  • the content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.
  • the composition of the present invention preferably further contains a metal discoloration inhibitor.
  • a metal discoloration prevention agent it can suppress effectively that the metal ion derived from a metal layer (metal wiring) moves into a negative photosensitive resin composition layer.
  • the metal discoloration 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 , 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 phenols Compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
  • triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.
  • an ion trapping agent that traps anions such as halogen ions can be used.
  • Examples of other metal discoloration inhibitors include rust preventives described in paragraph 0094 of JP2013-15701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711A, and JP2011-59656A. And the compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A, and the like.
  • metal discoloration inhibitor examples include the following compounds.
  • the content of the metal discoloration inhibitor is preferably 0.01 to 5.0% by mass relative to the total solid content of the composition of the present invention. 05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is more preferable. Only one type of metal discoloration inhibitor may be used, or two or more types may be used. When two or more metal discoloration inhibitors are used, the total is preferably within the above range.
  • the composition of the present invention preferably contains a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, 4,4′-thiobis (3-methyl).
  • a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication WO2015 / 125469 can also be used. Further, the following compounds can be used (Me is a methyl group).
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition of the present invention. 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 composition of the present invention preferably contains a thermal base generator.
  • the type of the thermal base generator is not particularly defined, but 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 kind.
  • pKa1 represents the logarithm ( ⁇ Log 10 Ka) of the reciprocal of the dissociation constant (Ka) of the first proton of the acid, and will be described in detail later.
  • the base generated from these compounds can promote the cyclization reaction of the polyimide precursor and the like. Can be carried out at low temperatures. In addition, even if these compounds coexist with a polyimide precursor that is cured by cyclization with a base, since the cyclization of the polyimide precursor hardly proceeds unless heated, a composition having excellent storage stability can be obtained. Can be prepared.
  • the solution obtained by stirring means a compound having a value measured at 20 ° C. of less than 7 using a pH (power of hydrogen) meter.
  • 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 composition having excellent stability can be prepared.
  • the base generation temperature of the acidic compound (A1) and ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor or the like can be lowered.
  • 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, cyclization temperature of a polyimide precursor, a polybenzoxazole precursor, etc. can be made lower.
  • the base generated by the thermal base generator preferably has a boiling point of 80 ° C. or higher, more preferably 100 ° C. or higher, and further 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 an ammonium salt and a compound represented by the formula (101) or (102) described later.
  • 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 in Formula (101) and Formula (102) 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 in 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, a polyimide precursor or the like can be cyclized at a low temperature, and the stability of the 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 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 carboxyl groups, and more preferably a divalent carboxylic acid anion.
  • the stability, curability and developability of the 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 composition can be further improved.
  • pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and the determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafliger Ed .: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R. M.). al; Oxford, 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 in which Hammett's substituent constant ⁇ m exhibits a positive value.
  • ⁇ m is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642.
  • the electron withdrawing group in this embodiment 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 is preferably 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 hydroxyl group or a carboxyl group, and Ar represents an aromatic group Represents.
  • the carboxylate anion is preferably represented by the following formula (XA).
  • Formula (XA) In the formula (XA), L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, —NR X —, and a combination thereof, and R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
  • carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
  • thermal base generator examples include the following compounds.
  • the content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solid content of the composition of the present invention.
  • 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 further 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 composition of this invention contains the metal adhesive improvement agent for improving the adhesiveness with the metal material used for an electrode, wiring, etc.
  • metal adhesion improvers include silane coupling agents.
  • silane coupling agent examples include compounds described in paragraphs 0062 to 0073 of JP-A No. 2014-191002, compounds described in paragraphs 0063 to 0071 of international publication WO 2011 / 080992A1, and JP-A No. 2014-191252. Examples thereof include compounds described in paragraphs 0060 to 0061, compounds described in paragraphs 0045 to 0052 of JP 2014-41264 A, and compounds described in paragraph 0055 of international publication WO 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound for a silane coupling agent. In the following formula, Et represents an ethyl group.
  • the content of the metal adhesion improving agent 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. Adhesiveness between the cured film and the metal layer after the curing process becomes good by setting it to 0.1 parts by mass or more, and heat resistance and mechanical properties of the cured film after the curing process are good by setting it to 30 parts by mass or less. Become. 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 the present invention is various additives, for example, a photobase generator, a thermal polymerization initiator, a thermal acid generator, a sensitizing dye, a chain transfer, as necessary, as long as the effects of the present invention are not impaired.
  • An agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the composition.
  • the composition of the present invention may contain a photobase generator.
  • a photobase generator is a compound that generates a base upon exposure and does not exhibit activity under normal conditions of room temperature and normal pressure. However, when an electromagnetic wave is irradiated and heated as an external stimulus, a base (basic substance) is generated. If it is a compound which generate
  • the content of the photobase generator is not particularly limited as long as a desired resin pattern can be formed, and can be a general content.
  • the photobase generator is preferably in the range of 0.01 parts by weight to less than 30 parts by weight with respect to 100 parts by weight of the polyimide precursor, and is in the range of 0.05 parts by weight to 25 parts by weight. Is more preferable, and is more preferably in the range of 0.1 to 20 parts by mass. Only one photobase generator may be used, or two or more photobase generators may be used. When there are two or more photobase generators, the total is preferably in the above range.
  • a known compound can be used as a photobase generator.
  • M.M. 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. 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.
  • 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 an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound can be mentioned.
  • the photobase generator carbamate derivatives, amide derivatives, imide derivatives, ⁇ -cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives, and the like can also be used. Further, the photobase generator having a cinnamic acid amide structure described in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. WO2009 / 123122, and Japanese Patent Application Laid-Open No. 2006-189591 and Japanese Patent Application Laid-Open No. 2008-247747.
  • a photobase generator having a carbamate structure, or a photobase generator having an oxime structure or a carbamoyloxime structure described in JP2007-249013A and JP2008-003581A can also be used.
  • Other 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 thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compound described in paragraph 0052 of WO2010 / 064631.
  • 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 a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved.
  • Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
  • the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, based on the total solid content of the composition of the present invention, 0.1 to 30% by mass is more preferable, and 0.1-20% 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, more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polyimide precursor. 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.
  • the composition of the present invention may contain a thermal acid generator.
  • the thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the cured film.
  • Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.
  • 0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable.
  • the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less from the viewpoint of electrical insulation of the cured film.
  • 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 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 a base 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 base generator, the thermal radical polymerization initiator, and the photopolymerization initiator are decomposed by causing a chemical change to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
  • the content of the sensitizing dye is preferably 0.01 to 20% by mass, and preferably 0.1 to 15% by mass with respect to the total solid content of the composition of the present invention. Is more preferable, and 0.5 to 10% by mass is even more preferable.
  • 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 generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated.
  • 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 content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the composition of the present invention, and 1 to 10 parts by mass. Part is more preferable, and 1 to 5 parts by mass is more preferable. 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.
  • surfactant Various kinds of surfactants may be added to the composition of the present invention from the viewpoint of further improving applicability.
  • the surfactant various types of surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
  • the following surfactants are also preferable.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0%, based on the total solid content of the composition of the present invention. 0.005 to 1.0 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.
  • the composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in the process of drying after coating. May be.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide
  • 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 of the present invention. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
  • 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 properties.
  • the metal content of the composition of the present invention is preferably less than 5 ppm by weight (parts per million), 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 of the present invention.
  • the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like, and distillation may be performed under a condition in which 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 size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • 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.
  • circulation filtration may be used.
  • you may pressurize and filter.
  • the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • the adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • 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.
  • a laminate may be obtained by laminating two or more cured films of the present invention.
  • Such a laminate preferably has a metal layer between the cured films.
  • Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
  • Fields to which the cured film 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 electronic photoresists, galvanic resists, galvanic resists, etching resists, solder top resists, and the like.
  • 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 using the composition of the present invention.
  • the negative photosensitive resin composition of the present invention is applied to a substrate to form a layer, a negative photosensitive resin composition layer forming step, an exposure step of exposing the negative photosensitive resin composition layer, And a development process for the exposed negative photosensitive resin composition layer.
  • the production method of the present invention may include a step of heating the developed negative 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 method for producing a laminate of the present invention includes the method for producing a cured film of the present invention.
  • a negative photosensitive resin composition layer forming step, an exposure step, and a development processing step are performed again. It is preferable to carry out again in the above order.
  • the negative 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 the cured film of the present invention.
  • a semiconductor device including the cured film of the present invention.
  • an embodiment of a semiconductor device using the composition of the present invention as an interlayer insulating film for a rewiring layer will be described.
  • 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 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.
  • the plurality of semiconductor elements 101a to 101d are each 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 flip-chip connection of semiconductor elements 101b to 101d having through electrodes 102b to 102d are 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 adjacent through electrode 102c 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.
  • 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 laminated body 101 is laminated 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 of 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 of the present invention can be widely used in various applications using polyimide.
  • polyimide is resistant to heat
  • the cured film in the present invention is used for plastic substrates and interlayer insulation films for liquid crystal displays, organic EL displays, electronic paper and other display devices, automotive parts, heat resistant paints, coating agents, and films. Can also be suitably used.
  • the polyimide precursor of this invention can also be used for a positive photosensitive resin composition.
  • ODPA 4,4′-oxydiphthalic dianhydride
  • the structure of the obtained polyimide precursor (P-1) was confirmed by 1 H-NMR (nuclear magnetic resonance spectrum) (DMSO (dimethyl sulfoxide) -d6 solution). 10.6 to 10.3 ppm (m, 2H), 8.2 to 6.7 ppm (m, 14 H), 6.4 to 6.2 ppm (m, 1 H), 6.2 to 6.0 ppm (m, 1 H) ), 6.0 to 5.8 ppm (m, 0.9H), 4.4 to 4.0 ppm (m, 3H), 3.9 to 3.6 ppm (s, 6H).
  • DMSO dimethyl sulfoxide
  • the weight average molecular weight of the obtained P-1 was 50,000.
  • the measurement conditions are as follows. Column: 1 TSK guardcolumn Super AW-H (4.6 mm ID. ⁇ 35 mm) 1 TSK Super AWM-H (6.0 mm ID.
  • the obtained mixed solution was diluted with NMP, and the weight average molecular weight measured by GPC was 50,000.
  • the polyimide precursor was precipitated in a mixed solvent of 3 liters of water and 3 liters of acetone. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again.
  • the obtained polyimide precursor was dried at room temperature under reduced pressure for 2 days.
  • the obtained solid was dissolved in NMP, and the weight average molecular weight measured by GPC was 20000. It was thought that it decomposed in the purification process.
  • ODPA Tokyo Chemical Industry BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, Tokyo Chemical Industry ODA: Tokyo Chemical Industry Benzidine (4,4′-diaminobiphenyl): Tokyo Chemical Industry Manufactured by Ethanol: Wako Pure Chemical Industries, Ltd. n-Butanol: Wako Pure Chemical Industries, Ltd. n-Octanol: Wako Pure Chemical Industries, Ltd.
  • DPHA Nippon Kayaku
  • KAYARAD DPHA M-305 Pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd.
  • Aronix M-305 701 Glycerol dimethacrylate, Shin-Nakamura Chemical Co., Ltd.
  • Hydroxyethyl acrylate Wako Pure Chemical Industries, Ltd.
  • M-215 Isocyanuric acid ethylene oxide (EO) modified diacrylate, manufactured by Toagosei Co., Ltd., Aronix M-215 Karenz BEI: 1,1- (bisacryloyloxymethyl) ethyl isocyanate, manufactured by Showa Denko Karenz MOI: 2-isocyanatoethyl methacrylate, manufactured by Showa Denko 4-Aminostyrene: manufactured by Tokyo Chemical Industry
  • the negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 ⁇ m, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating.
  • a negative photosensitive resin composition layer was formed by applying in layers.
  • the obtained silicon wafer to which the negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform negative photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer. Obtained.
  • the negative photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
  • Exposed part residual film ratio (%) [film thickness after development of exposed part / film thickness of unexposed part before development] ⁇ 100 5: 90% or more 4: 70% or more and less than 90% 3: 50% or more and less than 70% 2: 30% or more and less than 50% 1: less than 30% Evaluation of 3 or more is practically preferable.
  • the negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 ⁇ m, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating.
  • a negative photosensitive resin composition layer was formed by applying in layers.
  • the silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform negative photosensitive resin composition layer having a thickness of 15 ⁇ m was formed on the silicon wafer. did. This was developed with cyclopentanone for 60 seconds, and the unexposed portion residual film ratio was determined from the change in film thickness before and after development.
  • Unexposed area remaining film ratio (%) [(film thickness after development of unexposed area) / film thickness before development of unexposed area] ⁇ 100 5: Less than 5% 4: 5% or more but less than 20% 3: 20% or more but less than 50% 2: 50% or more but less than 90% 1: 90% or more Evaluation of 3 or more is practically preferable.
  • the negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 ⁇ m, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating.
  • a negative photosensitive resin composition layer was formed by applying in layers.
  • the silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform negative photosensitive resin composition layer having a thickness of 15 ⁇ m was formed on the silicon wafer. did.
  • the negative photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed negative photosensitive resin composition layer (resin layer) was heated at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and was maintained for 3 hours after reaching 230 ° C., and the remaining film ratio after heating was determined from the change in film thickness before and after heating.
  • Residual film ratio after thermosetting (%) [film thickness after thermosetting / film thickness before thermosetting] ⁇ 100 5: 85% or more 4: 80% or more and less than 85% 3: 70% or more and less than 80% 2: 60% or more and less than 70% 1: less than 60% Evaluation of 2 or more is practically preferable.
  • the negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 ⁇ m, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating.
  • a negative photosensitive resin composition layer was formed by applying in layers.
  • the obtained silicon wafer to which the negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform negative photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer. Obtained.
  • the negative photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed negative photosensitive resin composition layer (resin layer) was heated at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and was maintained for 3 hours after reaching 230 ° C.
  • the cured resin layer was immersed in a 4.9% by mass hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film.
  • the obtained resin film was set in a viscoelasticity measuring device (Rhegel E4000, manufactured by UBM Co., Ltd.), and the temperature was increased from 0 ° C. to 350 ° C. at a frequency of 1 Hz and a temperature increase rate of 10 ° C./min. , Tg (° C.) was determined from the peak temperature of tan ⁇ .
  • Example 1 ⁇ Other Examples and Comparative Examples>
  • one or more of the polyimide precursor, photopolymerization initiator, radical polymerizable monomer, polymerization inhibitor, metal discoloration inhibitor, silane coupling agent, and solvent are changed as shown in Table 4 or Table 5.
  • some examples were blended with a thermal base generator, and others were performed in the same manner.
  • G-1 the following compound
  • G-2 the following compound
  • G-3 the following compound
  • G-4 the following compound
  • DMSO dimethyl sulfoxide
  • GBL ⁇ -butyrolactone
  • NMP N-methyl-2-pyrrolidone ethyl lactate
  • the Tg was high and the resolution was excellent.
  • the glass transition temperature was 230 ° C. or higher, which was 5 ° C. higher than those of Comparative Examples 1 and 2.
  • An increase in Tg of 5 ° C. can be said to be a very remarkable effect from the viewpoint of improving reliability in a high-temperature process such as a vapor deposition process for forming a metal wiring or a bonding process between electrodes.
  • R 1 and R 2 of formula (1) an organic group of a non-polymerizable group having 1 to 4 carbon atoms
  • Example 100 Manufacture of laminated body 1>
  • the photosensitive resin composition of Example 3 was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m, and then a photosensitive resin composition layer was formed on a silicon wafer by spin coating.
  • the obtained silicon wafer to which the photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was Development was performed with cyclopentanone for 60 seconds to form a 10 ⁇ m diameter hole.
  • the temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours.
  • After cooling to room temperature again using the same type of photosensitive resin composition as the photosensitive resin composition on the surface of the resin layer, filtration of the photosensitive resin composition in the same manner as described above, 3 of the patterned film was performed.
  • the procedure up to the time heating was performed again to form a laminate 1 having two resin layers.
  • Example 3 The photosensitive resin composition of Example 3 was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m, and then a photosensitive resin composition layer was formed on a silicon wafer by spin coating. The obtained silicon wafer to which the photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to cyclopenta
  • a hole having a diameter of 10 ⁇ m was formed by developing for 60 seconds in a non-process.
  • the temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours.
  • a 2 ⁇ m thick copper thin film (metal layer) was applied to a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion.
  • the photosensitive resin composition of Example 3 was filtered in the same manner as described above, and then the patterned film was used for 3 hours. The procedure up to the heating was performed again to produce a laminate 3 composed of resin layer / metal layer / resin layer.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention concerne une composition de résine photosensible négative ayant une excellente résolution. L'invention concerne également un film durci utilisant la composition de résine photosensible négative, un procédé de production d'un film durci, un dispositif semi-conducteur, un procédé de production d'un stratifié, un procédé de production d'un dispositif semi-conducteur et un précurseur de polyimide. La composition photosensible négative contient un précurseur de polyimide, un initiateur de photopolymérisation et un solvant. Le précurseur de polyimide possède une unité récurrente représentée par la formule (1), a une structure représentée par « (A)l-L1-* » sur au moins l'une des bornes, et un poids moléculaire moyen en poids ne dépassant pas 50 000. Dans la formule (1), X représente un groupe organique divalent, Y représente un groupe organique tétravalent, et R1 et R2 représentent chacun indépendamment des groupes organiques non polymérisables. Dans la structure susmentionnée, A représente un groupe polymérisable, L1 représente une liaison simple ou un groupe organique de valence l+1, l représente un nombre entier de 1 à 10, et * représente un site de liaison avec un autre site.
PCT/JP2017/023341 2016-06-29 2017-06-26 Composition de résine photosensible négative, film durci, procédé de production de film durci, dispositif semi-conducteur, procédé de production de stratifié, procédé de production de dispositif semi-conducteur et précurseur de polyimide Ceased WO2018003725A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020187036825A KR102187513B1 (ko) 2016-06-29 2017-06-26 네거티브형 감광성 수지 조성물, 경화막, 경화막의 제조 방법, 반도체 디바이스, 적층체의 제조 방법, 반도체 디바이스의 제조 방법 및 폴리이미드 전구체
JP2018525148A JP6837063B2 (ja) 2016-06-29 2017-06-26 ネガ型感光性樹脂組成物、硬化膜、硬化膜の製造方法、半導体デバイス、積層体の製造方法、半導体デバイスの製造方法およびポリイミド前駆体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-129366 2016-06-29
JP2016129366 2016-06-29

Publications (1)

Publication Number Publication Date
WO2018003725A1 true WO2018003725A1 (fr) 2018-01-04

Family

ID=60787309

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/023341 Ceased WO2018003725A1 (fr) 2016-06-29 2017-06-26 Composition de résine photosensible négative, film durci, procédé de production de film durci, dispositif semi-conducteur, procédé de production de stratifié, procédé de production de dispositif semi-conducteur et précurseur de polyimide

Country Status (4)

Country Link
JP (1) JP6837063B2 (fr)
KR (1) KR102187513B1 (fr)
TW (1) TWI728137B (fr)
WO (1) WO2018003725A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020246349A1 (fr) 2019-06-03 2020-12-10 三菱瓦斯化学株式会社 Composition de résine photosensible et film durci à base de celle-ci
WO2021059917A1 (fr) * 2019-09-25 2021-04-01 富士フイルム株式会社 Film organique et son procédé de fabrication, composition, stratifié et dispositif à semi-conducteur
WO2021198793A1 (fr) * 2020-03-31 2021-10-07 Kaneka Corporation Résines hybrides thermoplastiques-thermodurcissables, procédés, et leurs utilisations
US20220145009A1 (en) * 2019-07-30 2022-05-12 Fujifilm Corporation Coloring resin composition, film, color filter, solid-state imaging element, and image display device
WO2022203071A1 (fr) * 2021-03-26 2022-09-29 リンテック株式会社 Composition de résine durcissable et couche de résine durcie l'utilisant
WO2023276517A1 (fr) * 2021-07-02 2023-01-05 東レ株式会社 Composition de résine, produit durci, procédé de production de produit durci, composant électronique, dispositif d'affichage et dispositif à semi-conducteur
CN116234845A (zh) * 2020-09-29 2023-06-06 富士胶片株式会社 固化物的制造方法、层叠体的制造方法及半导体器件的制造方法
KR20230136738A (ko) * 2022-03-18 2023-09-26 닛산 가가쿠 가부시키가이샤 절연막 형성용 감광성 수지 조성물
JP2024147742A (ja) * 2018-07-20 2024-10-16 エルジー・ケム・リミテッド ポリイミド樹脂およびこれを含むネガティブ型感光性樹脂組成物
US12410280B2 (en) 2020-04-15 2025-09-09 Kaneka Corporation Synthesis, purification, and properties of ring-opened benzoxazine thermoplastic

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI808143B (zh) * 2018-03-29 2023-07-11 日商富士軟片股份有限公司 感光性樹脂組成物、硬化膜、積層體及它們的製造方法、半導體器件及用於該等之熱鹼產生劑
CN110515269B (zh) 2018-05-22 2022-12-20 臻鼎科技股份有限公司 感光树脂组合物及其制备方法、高分子膜及覆铜板
TWI668515B (zh) * 2018-05-22 2019-08-11 臻鼎科技股份有限公司 感光樹脂組合物及其製備方法、高分子膜及覆銅板
WO2021002395A1 (fr) * 2019-07-02 2021-01-07 富士フイルム株式会社 Composition durcissable de type négatif, film durci, corps stratifié, procédé de production de film durci et dispositif à semi-conducteurs

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000281671A (ja) * 1998-10-30 2000-10-10 Hitachi Chemical Dupont Microsystems Ltd テトラカルボン酸二無水物、その誘導体及び製造法、ポリイミド前駆体、ポリイミド、樹脂組成物、感光性樹脂組成物、レリーフパターンの製造法、並びに電子部品
JP2003167337A (ja) * 2001-12-04 2003-06-13 Hitachi Chemical Dupont Microsystems Ltd 多層配線構造の製造方法
JP2004124054A (ja) * 2002-06-07 2004-04-22 Toray Ind Inc 耐熱性樹脂前駆体組成物
WO2012165448A1 (fr) * 2011-06-01 2012-12-06 日本ゼオン株式会社 Composition de résine et substrat d'élément semi-conducteur
WO2015199219A1 (fr) * 2014-06-27 2015-12-30 富士フイルム株式会社 Générateur de base thermique, composition de résine thermodurcissable, film durci, procédé de fabrication de film durci, et dispositif semi-conducteur

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006193691A (ja) * 2005-01-17 2006-07-27 Nippon Kayaku Co Ltd 感光性ポリアミド酸及びこれを含有する感光性組成物
JP2007056196A (ja) * 2005-08-26 2007-03-08 Tokyo Institute Of Technology ポリイミド前駆体組成物、ポリイミド膜の製造方法及び半導体装置
JP4826415B2 (ja) * 2005-10-12 2011-11-30 東レ株式会社 感光性樹脂組成物
JP4923656B2 (ja) * 2006-03-22 2012-04-25 日立化成デュポンマイクロシステムズ株式会社 ネガ型感光性樹脂組成物、パターンの製造方法及び電子部品
JP5076390B2 (ja) * 2006-07-31 2012-11-21 日立化成デュポンマイクロシステムズ株式会社 ネガ型感光性樹脂組成物、パターン硬化膜の製造方法および電子部品
JP4840014B2 (ja) * 2006-07-31 2011-12-21 日立化成デュポンマイクロシステムズ株式会社 ポジ型感光性樹脂組成物、パターン硬化膜の製造方法および電子部品
JP5021337B2 (ja) * 2007-02-28 2012-09-05 旭化成イーマテリアルズ株式会社 熱塩基発生剤を含有する樹脂組成物
JP5942348B2 (ja) * 2011-07-04 2016-06-29 Jnc株式会社 熱硬化性インクジェット用インクおよびその用途
JP2013076845A (ja) 2011-09-30 2013-04-25 Nippon Zeon Co Ltd 感光性樹脂組成物
WO2015064280A1 (fr) * 2013-10-30 2015-05-07 太陽インキ製造株式会社 Composition de résine thermodurcissable photosensible et carte imprimée flexible
JP6300491B2 (ja) * 2013-11-08 2018-03-28 オリンパス株式会社 固体撮像装置および撮像装置
JP6278817B2 (ja) * 2014-04-24 2018-02-14 Ｊｆｅケミカル株式会社 ポリアミド酸組成物およびポリイミド組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000281671A (ja) * 1998-10-30 2000-10-10 Hitachi Chemical Dupont Microsystems Ltd テトラカルボン酸二無水物、その誘導体及び製造法、ポリイミド前駆体、ポリイミド、樹脂組成物、感光性樹脂組成物、レリーフパターンの製造法、並びに電子部品
JP2003167337A (ja) * 2001-12-04 2003-06-13 Hitachi Chemical Dupont Microsystems Ltd 多層配線構造の製造方法
JP2004124054A (ja) * 2002-06-07 2004-04-22 Toray Ind Inc 耐熱性樹脂前駆体組成物
WO2012165448A1 (fr) * 2011-06-01 2012-12-06 日本ゼオン株式会社 Composition de résine et substrat d'élément semi-conducteur
WO2015199219A1 (fr) * 2014-06-27 2015-12-30 富士フイルム株式会社 Générateur de base thermique, composition de résine thermodurcissable, film durci, procédé de fabrication de film durci, et dispositif semi-conducteur

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024147742A (ja) * 2018-07-20 2024-10-16 エルジー・ケム・リミテッド ポリイミド樹脂およびこれを含むネガティブ型感光性樹脂組成物
WO2020246349A1 (fr) 2019-06-03 2020-12-10 三菱瓦斯化学株式会社 Composition de résine photosensible et film durci à base de celle-ci
KR20220016450A (ko) 2019-06-03 2022-02-09 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 감광성 수지 조성물 및 그의 경화막
US20220145009A1 (en) * 2019-07-30 2022-05-12 Fujifilm Corporation Coloring resin composition, film, color filter, solid-state imaging element, and image display device
US12391801B2 (en) * 2019-07-30 2025-08-19 Fujifilm Corporation Coloring resin composition, film, color filter, solid-state imaging element, and image display device
JP2023041680A (ja) * 2019-09-25 2023-03-24 富士フイルム株式会社 有機膜及びその製造方法、組成物、積層体、及び、半導体デバイス
CN114402256A (zh) * 2019-09-25 2022-04-26 富士胶片株式会社 有机膜及其制造方法、组合物、层叠体及半导体器件
WO2021059917A1 (fr) * 2019-09-25 2021-04-01 富士フイルム株式会社 Film organique et son procédé de fabrication, composition, stratifié et dispositif à semi-conducteur
JPWO2021059917A1 (fr) * 2019-09-25 2021-04-01
JP7204937B2 (ja) 2019-09-25 2023-01-16 富士フイルム株式会社 有機膜及びその製造方法、組成物、積層体、及び、半導体デバイス
JP7478806B2 (ja) 2019-09-25 2024-05-07 富士フイルム株式会社 有機膜及びその製造方法、組成物、積層体、及び、半導体デバイス
JP7447303B2 (ja) 2020-03-31 2024-03-11 株式会社カネカ 熱可塑性－熱硬化性ハイブリッド樹脂、方法、およびその使用
JP2023519259A (ja) * 2020-03-31 2023-05-10 株式会社カネカ 熱可塑性－熱硬化性ハイブリッド樹脂、方法、およびその使用
WO2021198793A1 (fr) * 2020-03-31 2021-10-07 Kaneka Corporation Résines hybrides thermoplastiques-thermodurcissables, procédés, et leurs utilisations
US12410280B2 (en) 2020-04-15 2025-09-09 Kaneka Corporation Synthesis, purification, and properties of ring-opened benzoxazine thermoplastic
CN116234845A (zh) * 2020-09-29 2023-06-06 富士胶片株式会社 固化物的制造方法、层叠体的制造方法及半导体器件的制造方法
WO2022203071A1 (fr) * 2021-03-26 2022-09-29 リンテック株式会社 Composition de résine durcissable et couche de résine durcie l'utilisant
WO2023276517A1 (fr) * 2021-07-02 2023-01-05 東レ株式会社 Composition de résine, produit durci, procédé de production de produit durci, composant électronique, dispositif d'affichage et dispositif à semi-conducteur
KR20230136738A (ko) * 2022-03-18 2023-09-26 닛산 가가쿠 가부시키가이샤 절연막 형성용 감광성 수지 조성물
KR102628683B1 (ko) 2022-03-18 2024-01-25 닛산 가가쿠 가부시키가이샤 절연막 형성용 감광성 수지 조성물

Also Published As

Publication number Publication date
JP6837063B2 (ja) 2021-03-03
TW201807497A (zh) 2018-03-01
JPWO2018003725A1 (ja) 2019-05-16
KR102187513B1 (ko) 2020-12-07
KR20190010614A (ko) 2019-01-30
TWI728137B (zh) 2021-05-21

Similar Documents

Publication Publication Date Title
JP6837063B2 (ja) ネガ型感光性樹脂組成物、硬化膜、硬化膜の製造方法、半導体デバイス、積層体の製造方法、半導体デバイスの製造方法およびポリイミド前駆体
JP6782298B2 (ja) 樹脂組成物およびその応用
JP6813602B2 (ja) 感光性樹脂組成物、複素環含有ポリマー前駆体、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス
JP6808831B2 (ja) 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイスおよび化合物
JP6704048B2 (ja) ネガ型感光性樹脂組成物、硬化膜、硬化膜の製造方法、半導体デバイス、積層体の製造方法、半導体デバイスの製造方法およびポリイミド前駆体
JP6808829B2 (ja) 感光性樹脂組成物、ポリマー前駆体、硬化膜、積層体、硬化膜の製造方法および半導体デバイス
JP6751159B2 (ja) 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法および半導体デバイス
WO2018025738A1 (fr) Composition de résine photosensible, film durci, stratifié, procédé de fabrication de film durci, procédé de fabrication de stratifié et dispositif à semi-conducteur
JP7008732B2 (ja) 感光性樹脂組成物、樹脂、硬化膜、積層体、硬化膜の製造方法、半導体デバイス
JP7254194B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、樹脂、及び、樹脂の製造方法
WO2020066416A1 (fr) Composition de résine photosensible, film durci, stratifié, procédé de production de film durci, et dispositif à semi-conducteurs
JP7065120B2 (ja) 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法、半導体デバイス
WO2021002383A1 (fr) Composition de résine durcissable, procédé de production de composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur
JP7277572B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
WO2020054226A1 (fr) Composition de résine photosensible, film durci, stratifié, procédé de production de film durci, et dispositif à semi-conducteur
WO2021039782A1 (fr) Composition de résine durcissable, film durci, produit stratifié, procédé de production de film durci, dispositif semi-conducteur et procédé de production de résine
WO2020170997A1 (fr) Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et générateur de base thermique
WO2020066975A1 (fr) Composition de résine, film durci, stratifié, procédé de production de film durci et dispositif à semi-conducteur
WO2019189111A1 (fr) Composition de résine photosensible, film durci, stratifié, procédé de fabrication de ceux-ci, dispositif à semi-conducteur et générateur de base thermique utilisés dans ceux-ci
WO2019189327A1 (fr) Composition de résine photosensible, film durci, stratifié et application de ceux-ci
WO2020066244A1 (fr) Composition de résine photosensible, film durci, produit stratifié, procédé de production de film durci, dispositif à semi-conducteur et générateur de base thermique
JPWO2019013241A1 (ja) 熱硬化性樹脂組成物、およびその硬化膜、積層体、半導体デバイス、ならびにそれらの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17820081

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018525148

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187036825

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17820081

Country of ref document: EP

Kind code of ref document: A1