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WO2011059089A1 - Précurseur de polyimide et composition de résine photosensible contenant le précurseur de polyimide - Google Patents

Précurseur de polyimide et composition de résine photosensible contenant le précurseur de polyimide Download PDF

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Publication number
WO2011059089A1
WO2011059089A1 PCT/JP2010/070306 JP2010070306W WO2011059089A1 WO 2011059089 A1 WO2011059089 A1 WO 2011059089A1 JP 2010070306 W JP2010070306 W JP 2010070306W WO 2011059089 A1 WO2011059089 A1 WO 2011059089A1
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WIPO (PCT)
Prior art keywords
film
resin composition
polyimide precursor
photosensitive resin
mass
Prior art date
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PCT/JP2010/070306
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English (en)
Japanese (ja)
Inventor
長武 山崎
建樹 清水
有久　慎司
明宏 加藤
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Asahi Kasei Corp
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Asahi Kasei E Materials Corp
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Priority to JP2011540575A priority Critical patent/JP5758300B2/ja
Priority to KR1020127009908A priority patent/KR101392539B1/ko
Priority to CN201080049271.6A priority patent/CN102597061B/zh
Publication of WO2011059089A1 publication Critical patent/WO2011059089A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08L79/085—Unsaturated 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a polyimide precursor in which an aliphatic diamine having an alkyl ether structure is selectively introduced into a polyimide structure, and a photosensitive resin including the polyimide precursor, each having a polyamic acid structure and a polyimide structure as repeating structural units.
  • the present invention relates to a composition, a photosensitive film using the photosensitive resin composition, a flexible printed board obtained using the photosensitive film, and a laminate thereof.
  • FPC flexible printed circuit board
  • FCCL Flexible Copper Clad Laminate
  • Developed photosensitive coverlays are energetically developed for fine processing by lithography for miniaturization and thinning of FPC.
  • a photosensitive cover lay using a polyimide precursor is expected as an excellent cover lay from the viewpoint of bending resistance derived from polyimide, heat resistance, and electrical insulation.
  • the conventional screen printing has problems such as a solvent removal process and double-sided processing, such as two processes, and a problem that the screen printing resolution is lowered. For this reason, it is desired that the photosensitive resin composition be formed into a dry film from the viewpoint of the industrial process and the resolution.
  • a photosensitive resin composition for solving these problems a photosensitive resin composition containing a polyimide precursor having both a polyamic acid structure and a polyimide structure, a negative photosensitive resin composition in which an exposed portion is insoluble ( Patent Document 1) and a photosensitive resin composition (Patent Document 2) containing a polyimide precursor having a polyamic acid structure have been proposed.
  • Patent Document 1 the photosensitive resin composition described in Patent Document 1
  • Patent Document 2 the polyimide precursor The body has a polyamic acid structure. For this reason, the molecular weight fall of the varnish which dissolved the photosensitive resin composition in the solvent becomes large.
  • the decrease in the molecular weight in the baking (heat drying) step in the production of the dry film is also increased, and there is a problem that the photosensitive layer is cracked when the photosensitive dry film that can reduce the toughness of the film is folded.
  • the pattern is formed by lithography due to the decrease in the molecular weight of the polyimide precursor, the development performance such as the development time is not stable, the remaining film ratio is decreased, and the pattern shape is distorted in development using an aqueous alkaline solution. Tended to decrease.
  • the FPC may be warped due to stress resulting from solvent removal or a ring closure reaction accompanying imidization of the polyimide precursor.
  • problems such as poor adhesion between the FCCL and the coverlay and an increase in driving power of an electronic device equipped with the FPC arise. For this reason, it is required to improve the warpage of the FPC having a coverlay on the copper wiring.
  • the present invention has been made in view of the above points.
  • the photosensitive layer is not cracked, developability is good, and when used for a flexible printed circuit board (FPC), firing is performed.
  • FPC flexible printed circuit board
  • Use of a polyimide precursor suitable as an FPC coverlay with less warping of subsequent FPC, a photosensitive resin composition containing the polyimide precursor, a photosensitive film using the photosensitive resin composition, and the photosensitive film It aims at providing the flexible printed circuit board obtained by this, and its laminated body.
  • the present inventors have determined that a polyimide precursor having a polyamic acid structure and a polyimide structure as repeating structural units and selectively introducing an aliphatic diamine having a specific alkyl ether structure into the polyimide structure,
  • a photosensitive resin composition using a polyimide precursor, a photosensitive film using the photosensitive resin composition, a flexible printed board obtained using the photosensitive film, and a laminate thereof solve the above problems.
  • the present invention has been completed. That is, the present invention is as follows.
  • the polyimide precursor of the present invention is a polyimide precursor having a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units
  • the tetracarboxylic dianhydride constituting the polyimide precursor includes at least one tetracarboxylic dianhydride selected from the group consisting of the following general formula (3) and the following general formula (4).
  • the constituent diamine contains the following general formula (5).
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , R 14 are each independently a hydrogen atom or carbon.
  • R 3 represents formula (3 ) Or a tetravalent organic group derived from a tetracarboxylic dianhydride represented by the formula (4), and R 17 represents a divalent organic group having 1 to 90 carbon atoms.
  • X represents a single bond, a carbonyl group, or a sulfonyl group.
  • Y represents a divalent organic group having an aromatic ring or 2 having 1 to 20 carbon atoms. Is .a representing the organic group represents an integer of 1 to 20.)
  • the diamine represented by the general formula (5) is preferably a diamine represented by the following general formula (5-1).
  • R 18 is C 2 H 4 or C 4 H 8
  • m, n, and p are each independently an integer of 0 or more and 40 or less, and 12 ⁇ (m + n + p) ⁇ 40.
  • the polyimide precursor of the present invention is preferably represented by the following general formula (6).
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , R 14 are each independently a hydrogen atom or carbon number 1 to carbon.
  • R 3 , R 6 , R 9 , R 12 , and R 15 represent a tetravalent organic group having 1 to 20 carbon atoms.
  • m, n and p each independently represents an integer of 0 to 100.
  • R 16 represents a tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4).
  • R 17 represents a divalent organic group having 1 to 90 carbon atoms
  • X represents a single bond, a carbonyl group, or a sulfonyl group
  • Y represents an aromatic ring.
  • .A, B, C represents the mol% of each unit, satisfy 0 ⁇ A ⁇ 100,0 ⁇ B ⁇ 100,0 ⁇ C ⁇ 100,0.05 ⁇ C / (A + B + C) ⁇ 0.95.)
  • the polyimide precursor of the present invention is preferably represented by the following general formula (6-1).
  • R 16 represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4)
  • R 17 represents Represents a divalent organic group having 1 to 90 carbon atoms
  • R 18 is C 2 H 4 or C 4 H 8
  • m, n, and p are each independently an integer of 0 or more and 40 or less. Yes 12 ⁇ (m + n + p) ⁇ 40)
  • the photosensitive resin composition of the present invention is characterized by containing (A) the polyimide precursor and (B) a photosensitive agent.
  • the photosensitive agent contains at least two (meth) acrylate compounds having a photopolymerizable unsaturated double bond, and (C) a photopolymerization initiator. It is preferable to contain.
  • the (meth) acrylate compound having at least two or more photopolymerizable unsaturated double bonds is composed of a compound having two double bonds and three double bonds. It is preferable to contain both of the above compounds.
  • the photosensitive agent contains a quinonediazide compound.
  • the photosensitive resin composition of the present invention preferably contains (D) a reactive compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor.
  • (D) the reactive compound which has reactivity with a polyimide precursor is included, and this reactive compound is represented by following formula (7).
  • R 19 is —Ar—Z—Ar— or Ar—Z—Ar—Z—Ar—, Z is O or SO 2 and R 20 has 2 carbon atoms. To an alkyl group having 10 carbon atoms.
  • the photosensitive resin composition of the present invention preferably contains (E) a phosphorus compound.
  • the (E) phosphorus compound has at least one structure selected from the group consisting of a phosphate ester structure and a phosphazene structure.
  • the photosensitive film of the present invention includes a support film layer and the photosensitive resin composition provided on the support film.
  • the photosensitive film of the present invention preferably has a carrier film on one side.
  • the photosensitive film of the present invention preferably includes a cover film.
  • the coverlay of the present invention is characterized in that it has a structure imidized from the photosensitive resin composition.
  • the flexible printed wiring board of the present invention has a structure in which the above photosensitive resin composition is imidized.
  • the laminate of the present invention includes the above cover lay and a copper clad laminate.
  • a polyimide precursor suitable as a coverlay, a photosensitive resin composition containing the polyimide precursor, a photosensitive film using the photosensitive resin composition, a flexible printed circuit board obtained using the photosensitive film, and its A laminate can be provided.
  • the polyimide precursor is a polyimide precursor having a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units, respectively.
  • the tetracarboxylic dianhydride constituting the polyimide precursor comprises at least one tetracarboxylic dianhydride selected from the group consisting of the following general formula (3) and the following general formula (4),
  • the diamine constituting the polyimide structure is the following general formula (5).
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , R 14 are respectively Independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, which may be the same or different, and in formula (1) and formula (5), R 3 , R 6 , R 9, R 12, R 15 represents a tetravalent organic group having 20 having 1 to carbon atoms, m, n, p each independently represents an integer of 0 or more and 100 or less.
  • R 16 represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by formula (3) or formula (4)
  • R 17 represents a divalent organic group having 1 to 90 carbon atoms.
  • X represents a single bond, a carbonyl group or a sulfonyl group
  • Y represents a divalent organic group having an aromatic ring or a carbon number of 1 to .a representing a divalent organic group of prime 20 represents an integer of 1 to 20.
  • the polyimide precursor according to the present invention is obtained by the following synthesis method. First, a tetracarboxylic dianhydride represented by at least one selected from the group consisting of the general formula (3) and the general formula (4), and an aliphatic diamine represented by the general formula (5) And, after obtaining a polyimide by polymerization and cyclization, tetracarboxylic dianhydride represented by at least one selected from the group consisting of the general formula (3) and the general formula (4), A polyimide precursor can be obtained by polymerizing a diamine represented by the following general formula (8).
  • R 17 represents a divalent organic group having 1 to 90 carbon atoms.
  • the obtained polyimide precursor has a structure represented by the following general formula (6).
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , R 14 are each independently a hydrogen atom or carbon number 1 to carbon.
  • R 3 , R 6 , R 9 , R 12 , and R 15 represent a tetravalent organic group having 1 to 20 carbon atoms.
  • m, n and p each independently represents an integer of 0 to 100.
  • R 16 represents a tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4).
  • R 17 represents a divalent organic group having 1 to 90 carbon atoms
  • X represents a single bond, a carbonyl group, or a sulfonyl group
  • Y represents an aromatic ring.
  • .A, B, C represents the mol% of each unit, satisfy 0 ⁇ A ⁇ 100,0 ⁇ B ⁇ 100,0 ⁇ C ⁇ 100,0.05 ⁇ C / (A + B + C) ⁇ 0.95.)
  • Examples of the tetracarboxylic dianhydride represented by the general formula (3) include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as BPDA), benzophenone-3, Examples thereof include 3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as BTDA), diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, and the like.
  • BPDA 4,4′-tetracarboxylic dianhydride
  • BTDA 4,4′-tetracarboxylic dianhydride
  • diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride and the like.
  • TMEG ethylene glycol bis (trimellitic acid monoester acid anhydride)
  • p-phenylene bis trimellitic acid monoanhydride
  • the diamine represented by the general formula (5) is not limited as long as it has the structure represented by the general formula (5), but may be 1,8-diamino-3,6-dioxyoctane or the like.
  • the skeleton having these oxyalkylene groups can reduce the warpage of FPC after baking of the polyimide.
  • m, n, and p are each independently an integer of 0 or more and 100 or less.
  • m + n + p> 5 is preferable, and m + n + p> 10 is more preferable.
  • the polyimide precursor according to the present invention has a polyimide structure and a polyamic acid structure as repeating structural units, respectively. By introducing the diamine represented by the general formula (5) into the polyimide structure, the polyimide precursor is obtained. The molecular weight of the varnish and film is stabilized.
  • the diamine of the general formula (5) When the diamine of the general formula (5) is introduced into the polyamic acid structure, the basicity of the aliphatic diamine is high, and the depolymerization of the polyamic acid proceeds and the molecular weight is significantly reduced as compared with the conventional polyamic acid.
  • the diamine represented by the general formula (5) By introducing the diamine represented by the general formula (5) into the polyimide structure, the molecular weight is stabilized without being affected by the basicity of the aliphatic diamine.
  • diamines represented by the general formula (5) are more preferable.
  • R 18 is C 2 H 4 or C 4 H 8 , and m, n, and p are each independently an integer of 0 or more and 40 or less, and 12 ⁇ (m + n + p) ⁇ 40.)
  • R 18 is preferably C 2 H 4 or C 4 H 8 . Moreover, it is preferable to satisfy
  • fill 12 ⁇ (m + n + p) from the point of the melt
  • dissolution rate in developability, and it is (m + n + p) ⁇ 40 from the point which suppresses the tackability (adhesiveness) of a film and expresses a flame retardance. preferable.
  • a diamine represented by any one of the following general formula (5-2), the following general formula (5-3), or the following general formula (5-4) is particularly preferable.
  • Formula (5-2) corresponds to Jeffamine D-2000
  • Formula (5-3) corresponds to Jeffamine ED-900
  • Formula (5-4) represents Jeffamine XTJ-542 ( Both correspond to Huntsman's).
  • Examples of the diamine represented by the general formula (8) include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy). ) Alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4, 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone (hereinafter abbreviated as DAS), 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3,3'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-dimethyl-4,4'-d
  • the polyimide precursor is effective even when used as a negative photosensitive resin composition or as a positive photosensitive resin composition.
  • the polyimide precursor is not limited as long as it has the structure represented by the general formula (1) and the general formula (2) as a structural unit.
  • the general formula (6) is further used.
  • block copolymers each having a repeating structure unit of a polyimide structure and a polyamic acid structure represented by formula (6-1).
  • Each of the polyimide structure and the polyamic acid structure represented by the following general formula (6-1) is repeated. More preferably, it is a block copolymer as a structural unit.
  • R 16 represents a tetravalent organic group derived from the above general formula (3) or the tetracarboxylic dianhydride represented by the above general formula (4)
  • R 17 is Represents a divalent organic group having 1 to 90 carbon atoms
  • R 18 is C 2 H 4 or C 4 H 8
  • m, n, and p are each independently an integer of 0 or more and 40 or less. Yes 12 ⁇ (m + n + p) ⁇ 40)
  • a polyimide precursor satisfying 1 ⁇ C / (A + B + C) ⁇ 0.9 is preferable, a polyimide precursor satisfying 0.2 ⁇ C / (A + B + C) ⁇ 0.8 is more preferable, and 0.5 ⁇ C / (A + B + C).
  • a polyimide precursor satisfying ⁇ 0.75 is most preferred.
  • the tetracarboxylic dianhydride may contain a tetracarboxylic dianhydride other than the above general formula (3) and the above general formula (4) as long as the performance is not adversely affected.
  • tetracarboxylic dianhydrides include pyromellitic anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5 6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid
  • the content of other tetracarboxylic dianhydrides is 50 parts by mass or less when the tetracarboxylic dianhydride represented by the general formula (3) and the general formula (4) is 100 parts by mass. .
  • the main chain terminal of the polyimide precursor is not particularly limited as long as it does not affect the performance.
  • a terminal derived from an acid dianhydride or a diamine used for producing a polyimide precursor may be used, or the terminal may be sealed with another acid anhydride, an amine compound, or the like.
  • the weight average molecular weight of the polyimide precursor is preferably 1,000 or more and 1,000,000 or less.
  • the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography (GPC) using polystyrene having a known weight average molecular weight as a standard.
  • the weight average molecular weight is preferably 1000 or more from the viewpoint of the strength of the polyimide film, and is preferably 1000000 or less from the viewpoint of the viscosity and moldability of the polyimide-containing resin composition.
  • the weight average molecular weight is more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 300,000, and most preferably from 25,000 to 50,000.
  • a polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a step of reacting acid dianhydride and diamine in a non-equal molar amount to synthesize a first-stage polyimide site (step 1), followed by It can be produced by a step of synthesizing the second stage polyamic acid (step 2).
  • step 1 A polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a step of reacting acid dianhydride and diamine in a non-equal molar amount to synthesize a first-stage polyimide site (step 1), followed by It can be produced by a step of synthesizing the second stage polyamic acid (step 2).
  • the process of synthesizing the first-stage polyimide site will be described.
  • the step of synthesizing the first-stage polyimide site is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, and acid dianhydride powder is added thereto. Then, a solvent that is azeotroped with water is added, and the mixture is heated and stirred for 0.5 hours to 96 hours, preferably 0.5 hours to 30 hours, while removing by-product water azeotropically using a mechanical stirrer. In this case, the monomer concentration is 0.5% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass or less.
  • the polyimide site can be synthesized either by adding a known imidization catalyst or without a catalyst.
  • the imidation catalyst is not particularly limited, but an acid anhydride such as acetic anhydride, a lactone such as ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -tetronic acid, ⁇ -phthalide, ⁇ -coumarin, and ⁇ -phthalido acid. Examples thereof include compounds, tertiary amines such as pyridine, quinoline, N-methylmorpholine and triethylamine. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a mixed system of ⁇ -valerolactone and pyridine and a non-catalyst are particularly preferable from the viewpoint of high reactivity and influence on the next reaction.
  • the amount of the imidization catalyst added is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less when the polyamic acid is 100 parts by mass.
  • the reaction solvent used in the synthesis of the polyimide moiety includes 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether.
  • Hydrocarbon compounds aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, tetralin; methyl acetate, ethyl acetate Ester compounds such as ⁇ -butyrolactone and methyl benzoate having 3 to 12 carbon atoms; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; Nitrogen-containing compounds having 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-
  • Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and carbon atoms having 2 to carbon atoms.
  • a nitrogen-containing compound of several tens or less is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.
  • the synthesis of the polyimide site is preferably carried out at a reaction temperature of 15 ° C. or higher and 250 ° C. or lower. If it is 15 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no deactivation of a catalyst. Preferably they are 20 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less.
  • the time required for the reaction for synthesizing the polyimide moiety varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.
  • Step 2 the process for synthesizing the second stage polyamic acid moiety will be described.
  • the synthesis of the polyamic acid moiety in the second stage can be carried out by using the polyimide moiety obtained in Step 1 as a starting material and adding diamine and / or acid dianhydride for polymerization.
  • the polymerization temperature in the synthesis of the second stage polyamic acid is preferably 0 ° C. or higher and 250 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower, and particularly preferably 0 ° C. or higher and 80 ° C. or lower.
  • the time required for the reaction for synthesizing the polyamic acid varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.
  • reaction solvent the same solvent used for the synthesis of the polyimide moiety in Step 1 can be used. In that case, the reaction solution of step 1 can be used as it is. Moreover, you may use the solvent different from what was used for the synthesis
  • solvents examples include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like.
  • Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and carbon atoms having 2 to carbon atoms.
  • a nitrogen-containing compound of several tens or less is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.
  • the polyimide precursor may be used as it is dissolved in the reaction solvent, or may be recovered and purified by the following method.
  • the recovery of the polyimide precursor after the completion of production can be carried out by distilling off the solvent in the reaction solution under reduced pressure.
  • Examples of the method for purifying the polyimide precursor include a method of removing insoluble acid dianhydride and diamine in the reaction solution by vacuum filtration, pressure filtration, or the like.
  • a so-called reprecipitation purification method in which the reaction solution is precipitated by adding it to a poor solvent can be carried out.
  • an extraction method by a carbon dioxide supercritical method is also possible.
  • the photosensitive resin composition according to the present invention contains the polyimide precursor and a photosensitizer.
  • a photosensitizer is a compound having a property that its structure is changed by light irradiation and its solubility in a solvent is changed. Examples of such a compound include a so-called positive type in which the light irradiation site is dissolved and a so-called negative type in which the light irradiation site is insoluble.
  • Examples of the negative type photosensitizer include a combination of (B-1) a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds and (C) a photopolymerization initiator.
  • Examples of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds include tricyclodecane dimethylol diacrylate, ethylene oxide (EO) modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi ( (Meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethyl Propanetri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethyl
  • EO-modified bisphenol A dimethacrylate EO-modified hydrogenated bisphenol A diacrylate, and pentaerythritol tri / tetra (meth) acrylate are preferable from the viewpoint of reducing warpage after firing.
  • a combination of a compound having two double bonds and a compound having three or more double bonds is preferred.
  • the amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is from 5 parts by weight to 60 parts by weight from the viewpoint of developability when the amount of the polyimide precursor is 100 parts by weight. Is preferably 10 parts by mass or more and 40 parts by mass or less.
  • Photopolymerization initiators include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyl dipropyl ketals, benzyl diphenyl ketals, benzoin Methyl ethers, benzoin ethyl ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-isopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4′-bis (dimethylamino) benzophenone [Michler'
  • the amount of the photopolymerization initiator is preferably 0.01 parts by mass or more and 40 parts by mass or less from the viewpoint of sensitivity and resolution when the amount of the polyimide precursor is 100 parts by mass. 0.5 parts by mass or more and 35 parts by mass or less are more preferable.
  • (B-2) Quinonediazide compound examples include compounds containing a quinonediazide structure, aromatic diazonium salt compounds, compounds having an azide structure, and the like. From the viewpoint of solubility contrast, a compound containing a quinonediazide structure is preferred.
  • Examples of the compound containing a quinonediazide structure include 1,2-benzoquinonediazidesulfonic acid esters, 1,2-benzoquinonediazidesulfonic acid amides, 1,2-naphthoquinonediazidesulfonic acid esters, 1,2-naphthoquinonediazidesulfonic acid Amides are mentioned.
  • 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2 ′, 4, 4'-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonic acid ester, 2,2 ′, 3 ′, 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 3 ′, 4-tetrahydroxybenzophenone-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenoneone
  • 1,2-naphthoquinone diazide sulfonic acid esters are preferable, and 1,2-naphthoquinone diazide-4-sulfonic acid esters and 1,2-naphthoquinone diazide-5-sulfonic acid esters are photosensitive. More preferable from the viewpoint of contrast. Among these, a compound represented by the following general formula (9) is particularly preferable.
  • Q is a structure or a hydrogen atom represented by Formula (10).
  • compound b used in Examples described later has a structure in which 2.9 of the three Qs in the general formula (9) are represented by the general formula (10) on average. Point to.
  • the amount of the positive photosensitive agent in the photosensitive resin composition is preferably 1 part by mass or more and 50 parts by mass or less, more preferably from the viewpoint of photosensitive contrast, when the amount of the polyimide precursor is 100 parts by mass. 5 parts by mass or more and 30 parts by mass or less. If it is 1 mass part or more, since there exists a tendency for dissolution suppression of an unexposed part to be enough, it is preferable. If it is 50 mass parts or less, since it exists in the tendency for a sensitivity to be high enough, it is preferable.
  • thermosetting resin and a polyimide precursor A compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor In order to improve the toughness, solvent resistance, and heat resistance (thermal stability) of the film after firing.
  • a reactive compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor can be contained.
  • thermosetting resins examples include epoxy resins, cyanate ester resins, unsaturated polyester resins, benzoxazine resins, benzoxazolines, phenol resins, melamine resins, maleimide compounds, and blocked isocyanates.
  • Examples of the compound having reactivity with the polyimide precursor include compounds capable of reacting with a carboxyl group, amino group or terminal acid anhydride in the polymer to form a three-dimensional crosslinked structure.
  • a thermal base generator compound that generates an amino group that is a base by heating is preferable.
  • it can be obtained by protecting an amino group of a base compound such as an amine with an acid chloride compound, which is protected with a dicarbonate compound represented by the general formula (7), which forms a salt structure with an acid such as sulfonic acid.
  • the thermal base generator has the effect of increasing the molecular weight of the polymer skeleton by reacting with the terminal acid anhydride in the polymer (stretching the molecule), and to the alkali such as TMAH (tetramethylammonium hydroxide) of the cured film It is useful in that it exhibits performance such as solvent resistance.
  • TMAH tetramethylammonium hydroxide
  • a compound obtained by protecting the amino group of a basic compound such as an amine with the dicarbonate compound represented by the general formula (7) is used as the thermal base generator.
  • R 19 is —Ar—Z—Ar—, —Ar—Z—Ar—Z—Ar—, or —Ar—Z—Ar—Z—.
  • Ar—Z—Ar—, and Z is preferably O or SO 2 , C (CH 3 ) 2 .
  • R 19 is -Ar-Z-Ar- or -Ar-Z-Ar-Z- Ar- in and, Z is particularly preferably O or SO 2 (wherein Ar represents an aromatic ring ).
  • R 20 corresponding to a protecting group is preferably an alkyl group having 2 to 10 carbon atoms from the viewpoint of easy deprotection. This is presumed that deprotection at a temperature lower than the temperature at which the polyimide precursor is calcined becomes possible by having 2 to 10 carbon atoms.
  • the addition amount of the compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor is 50 mass from the viewpoint of developability when the amount of the polyimide precursor is 100 mass parts. Part or less is preferable, and 40 parts by weight or less is more preferable.
  • the photosensitive resin composition according to the present invention preferably contains a phosphorus compound.
  • the phosphorus compound is not limited as long as it is a compound containing a phosphorus atom in the structure. Examples of such phosphorus compounds include phosphate ester compounds and phosphazene compounds.
  • Phosphoric acid ester compounds such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, phosphate ester compounds having tris (2-ethylhexyl) phosphate as substituents, tris (butoxyethyl) phosphate Aromatic organic groups such as phosphate ester compounds, triphenyl phosphates, tricresyl phosphates, trixylenyl phosphates, resorcinol bis (diphenyl phosphates) with aliphatic organic groups containing oxygen atoms as substituents And phosphoric acid ester compounds. Among these, tris (butoxyethyl) phosphate and triisobutyl phosphate are preferable from the viewpoint of developability.
  • Examples of the phosphazene compound include structures represented by the following general formula (11) and the following general formula (12).
  • R 21 , R 22 , R 23 , and R 24 in the phosphazene compound represented by the general formula (11) and the general formula (12) are not limited as long as they are organic groups having 1 to 20 carbon atoms.
  • a carbon number of 1 or more is preferable because flame retardancy tends to be exhibited.
  • a carbon number of 20 or less is preferred because it tends to be compatible with the polyimide precursor.
  • a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable.
  • Such functional groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-cyanophenyl.
  • V in the phosphazene compound represented by the general formula (11) is not limited as long as it is 3 or more and 25 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 25 or less, the solubility in an organic solvent is high. Among these, it is preferable that v is 3 or more and 10 or less because of availability.
  • W in the phosphazene compound represented by the general formula (12) is not limited as long as it is 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.
  • D and E in the phosphazene compound represented by the general formula (12) are not limited as long as they are organic groups having 3 to 30 carbon atoms.
  • E includes -P (OC 6 H 5 ) 4 , -P (OC 6 H 5 ) 3 (OC 6 H 4 OH), -P (OC 6 H 5 ) 2 (OC 6 H 4 OH) 2 ,- P (OC 6 H 5) ( OC 6 H 4 OH) 3, -P (OC 6 H 4 OH) 4, -P (O) (OC 6 H 5) 2, -P (O) (OC 6 H 4 OH) 2 , —P (O) (OC 6 H 5 ) (OC 6 H 4 OH), —N ⁇ P (OC 6 H 5 ) 2 (OC 6 H 4 CN), —N ⁇ P (OC 6 H 5 ) (OC 6 H 4 CN) 2 , —N ⁇ P (OC 6 H 4 CN) 3 , —N ⁇ P (O) (OC 6 H 4 CN) and the like are preferable.
  • the phosphorus compound one kind may be used, or two or more kinds may be used in combination.
  • the addition amount of the phosphorus compound is preferably 50 parts by mass or less from the viewpoint of developability and the like when the amount of the polyimide precursor is 100 parts by mass. From the viewpoint of flame retardancy of the cured product, 45 parts by mass or less is preferable, and 40 parts by mass or less is more preferable.
  • the photosensitive resin composition can contain other compounds as long as the performance is not adversely affected. Specific examples thereof include heterocyclic compounds for improving adhesion and pigments and dyes for coloring the film.
  • the heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom.
  • the hetero atom include oxygen, sulfur, nitrogen, and phosphorus.
  • Specific examples of the heterocyclic compound include 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, substituted imidazole such as 2-phenylimidazole, and N-type such as 1,2-dimethylimidazole.
  • Aromatic group-containing imidazole such as alkyl group-substituted imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4- Imidazole compounds such as methylimidazole, 1-cyanoethyl-2-undecylimidazole, cyano group-containing imidazole such as 1-cyanoethyl-2-phenylimidazole, and silicon-containing imidazole such as imidazolesilane, 5-mercaptotriazol , 5-methylbenzotriazole, 1- (1 ′, 2′-dicarboxyethylbenzotriazole), 1- (2-ethylhexylaminomethylbenzotriazole) and other triazole compounds, 2-methyl-5-phenylbenzoxazole And oxazole compounds.
  • pigments and dyes examples include phthalocyanine compounds.
  • the addition amount of other compounds is not limited as long as it is 0.01 parts by mass or more and 30 parts by mass or less. If it is 0.01 mass part or more, there exists a tendency for adhesiveness and the coloring property to a film to fully improve, and if it is 30 mass parts or less, there will be no bad influence on photosensitivity.
  • the photosensitive resin composition may optionally contain an organic solvent.
  • the organic solvent is not limited as long as it can uniformly dissolve and / or disperse the polyimide precursor.
  • organic solvents include dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and other ether compounds having 2 to 9 carbon atoms; acetone, methyl ethyl ketone A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; benzene, toluene, Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as xylene, mesitylene and tetralin; methyl acetate, ethyl acetate,
  • organic solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and 2 or more carbon atoms. Examples thereof include nitrogen-containing compounds having 10 or less carbon atoms.
  • one kind or a mixture of two or more kinds may be used as necessary.
  • triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.
  • the concentration of the polyimide precursor in the resin composition comprising the polyimide precursor and the organic solvent is not particularly limited as long as it is a concentration capable of synthesizing the resin molding.
  • the concentration of the polyimide precursor is preferably 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the concentration of the polyimide precursor is preferably 90% by mass or less from the uniformity of the film thickness of the resin molded body. From the viewpoint of the film thickness of the obtained resin molding, it is more preferably 2% by mass or more and 80% by mass or less.
  • the photosensitive resin composition which concerns on this invention can be used suitably as a photosensitive film.
  • the photosensitive film which concerns on this invention is equipped with the support film as a base material, and the said photosensitive resin composition provided on the support film.
  • a carrier film may be provided on one side.
  • the concentration of the polyimide precursor in the photosensitive resin composition is preferably 1% by mass or more and 90% by mass or less.
  • the concentration of the polyimide precursor is preferably 1% by mass or more from the viewpoint of the film thickness of the photosensitive film, and preferably 90% by mass or less from the viewpoint of the viscosity and film thickness uniformity of the photosensitive resin composition. From the viewpoint of the film thickness of the resulting photosensitive film, it is more preferably 2% by mass or more and 80% by mass or less.
  • the substrate is coated with the photosensitive resin composition.
  • a base material if it is a base material which is not damaged in the case of photosensitive dry film formation, it will not be limited.
  • the substrate include a silicon wafer, glass, ceramic, heat resistant resin, and carrier film.
  • the carrier film include a polyethylene terephthalate film and a metal film. A heat-resistant resin and a carrier film are preferable from the viewpoint of easy handling, and a polyethylene terephthalate film is particularly preferable from the viewpoint of peelability after pressure bonding to the substrate.
  • Examples of the coating method include bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating.
  • a heat treatment called pre-baking may be performed with a hot plate or the like.
  • the solution of the photosensitive resin composition is coated on an arbitrary substrate by an arbitrary method and then dried to form a dry film, for example, a carrier film and a photosensitive film. It is set as the laminated film which has a film.
  • a laminate film may be formed by providing at least one layer of an optional antifouling or protective cover film on the photosensitive film.
  • the cover film is not limited as long as it is a film that protects a photosensitive film such as low-density polyethylene.
  • a flexible printed wiring board can be obtained by pressure-bonding the photosensitive film to a substrate having wiring so as to cover the wiring, performing alkali development, and firing.
  • Examples of the substrate having wiring in the flexible printed wiring board include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a copper clad laminate. Among these, a flexible substrate is preferable from the viewpoint of bendability.
  • the method for forming the flexible printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring.
  • a thermal vacuum press and a thermal vacuum lamination are preferable.
  • the heating temperature for laminating the photosensitive film on the substrate having the wiring is not limited as long as the photosensitive film can be in close contact with the substrate. From the viewpoint of adhesion to the substrate and from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or more and 400 ° C. or less are preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.
  • the surface treatment of the substrate having the wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.
  • positive type photolithography can be performed by dissolving the light irradiation part by alkali development after the light irradiation.
  • negative type photolithography can be performed by dissolving the portion other than the light irradiated portion by alkali development after the light irradiation.
  • the light source used for light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser.
  • a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.
  • the alkaline aqueous solution used for development is not limited as long as it is a solution that can dissolve the light irradiation site when the photosensitive film is positive, and the other than the light irradiation site when the photosensitive film is negative.
  • a solution include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a tetramethylammonium hydroxide aqueous solution. From the viewpoint of developability, an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred.
  • Examples of the development method include spray development, immersion development, and paddle development.
  • a printed wiring board is formed by firing the printed wiring board to which the photosensitive film is pressure-bonded. Firing is preferably carried out at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoints of solvent removal, side reactions and decomposition. More preferably, it is 100 degreeC or more and 300 degrees C or less.
  • the reaction atmosphere in the firing can be carried out in an air atmosphere or an inert gas atmosphere.
  • the time required for the baking varies depending on the reaction conditions, but is usually within 24 hours, particularly preferably in the range of 1 to 8 hours.
  • the polyimide precursor and photosensitive resin composition according to the present invention have good warpage after curing and good developability, and exhibit chemical resistance when used as a cured product.
  • Protective layer formation of printed wiring boards and circuit boards used for operation panels of electronic devices insulating layer formation of laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, peripheral members of semiconductor devices, semiconductor mounting substrates It is used for film formation on electronic parts for protection, insulation and adhesion of heat sinks, lead pins, semiconductors, etc.
  • a protective film that protects wiring formed on a silicon wafer, a copper clad laminate, a printed wiring board, or the like is called a coverlay.
  • the resin composition according to the present invention can be made into a coverlay or a flexible printed wiring board by imidization. Furthermore, it is good also as a laminated body by providing the coverlay which imidized the resin composition which concerns on this invention on a copper clad laminated board.
  • the polyimide precursor and the photosensitive resin composition according to the present invention include a flexible printed circuit (FPC) substrate, a tape automation bonding (TAB) substrate, an electrical insulating film and a liquid crystal display substrate in various electronic devices, It can be suitably used for an organic electroluminescence (EL) display substrate, an electronic paper substrate, a solar cell substrate, particularly a coverlay for a flexible printed circuit.
  • FPC flexible printed circuit
  • TAB tape automation bonding
  • EL organic electroluminescence
  • EL organic electroluminescence
  • TMEG trade name: TMEG-100 (manufactured by Shin Nippon Chemical Co., Ltd.)
  • BTDA manufactured by Daicel Chemical
  • BPDA manufactured by Mitsui Chemicals
  • 5BTA black) Kinsei
  • TMAB trade name: CUA-4, manufactured by Ihara Chemical Industry Co., Ltd.
  • BAPP manufactured by Wakayama Seika Kogyo Co., Ltd.
  • APB trade name: APB-N (manufactured by Mitsui Chemicals)
  • DAS Huntsman
  • Jeffermin trade name: Jeffermin XTJ-542, manufactured by Huntsman
  • Jeffermin trade name: Jeffermin ED-900, manufactured by Huntsman
  • Jeffermin trade name: Jeffermin D-2000
  • the weight average molecular weight was measured under the following conditions using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • N N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) was used as a solvent, and 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity) before measurement. 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
  • the dry film was manufactured by coating a photosensitive resin composition on a PET film (N152Q, manufactured by Teijin DuPont Films) as a base material.
  • the coating method of the photosensitive resin composition was performed by a doctor blade method using FILMCOATER (manufactured by TESTER SANGYO, PI1210).
  • the photosensitive resin composition was dropped onto a PET film and coated with a clearance of 150 ⁇ m.
  • the coated film was dried at 95 ° C. for 30 minutes using a dryer (SPHH-10L, manufactured by ESPEC) to obtain a photosensitive dry film.
  • ⁇ Tack evaluation> The presence or absence of tackiness of the photosensitive layer after drying at 95 ° C. for 30 minutes was evaluated by palpation. Those with fingerprints were marked with ⁇ , and those without fingerprints were marked with ⁇ .
  • Lamination was performed using a vacuum press (manufactured by Meiki Seisakusho).
  • the press temperature was 70 ° C.
  • the press pressure was 0.5 MPa
  • the press time was 30 seconds.
  • ⁇ Developability evaluation> The developability was evaluated with an optical microscope under the following conditions. After laminating on a copper-clad laminate using a photosensitive dry film under the above laminating conditions, in the case of a positive photosensitive resin composition, using a positive mask, the irradiation dose is 1.0 J / cm 2 . In the case of a negative photosensitive resin composition, exposure was performed at 30 to 270 mJ / cm 2 . Next, alkali development with an aqueous sodium carbonate solution and rinsing with water were performed, and the pattern was evaluated with an optical microscope after drying. A circular pattern having a 100 ⁇ m diameter (interval of 100 ⁇ m pitch) was used as the mask. A case where the copper surface appeared in the exposed area due to development and the remaining film ratio was 75% or more was evaluated as ⁇ , and a case where the resolution was inferior or the film thickness was less than 75% was evaluated as x.
  • the obtained photosensitive dry film was laminated on Kapton (registered trademark) under the above-mentioned lamination conditions, and then baked at 120 ° C. for 1 hour and then at 180 ° C. for 1 hour.
  • the film after baking was cut out into 5 cm square, the thing with the floating height of the edge part within 10 mm was set as (circle), and the thing with the floating height more than it was set as x.
  • the flame retardancy was evaluated by a flame retardancy test under the following conditions. After laminating on a polyimide film (Kapton EN-100 trade name, manufactured by Toray DuPont) using a photosensitive dry film under the above-mentioned laminating conditions, firing was performed at 120 ° C. for 1 hour and subsequently at 180 ° C. for 1 hour. It was.
  • a polyimide film Kerpton EN-100 trade name, manufactured by Toray DuPont
  • the obtained film was cut into a width of 1 cm and a length of 5 cm. Next, the process of igniting one end of the test piece and spreading it was visually observed. A sample that was extinguished during the course was marked with ⁇ , and a sample that had all burned was marked with ⁇ .
  • the thermal stability was evaluated by the rate of change of the weight average molecular weight of the polyimide precursor before and after coating.
  • a polyimide precursor was produced by the dry film production method, and the obtained dry film was dissolved in the GPC measurement solvent, and then the weight average molecular weight was measured by GPC.
  • the obtained weight average molecular weight it performed by calculating
  • IR spectrum measurement> The IR spectrum was measured under the following conditions. A polyimide resin precursor and / or a photosensitive resin composition is applied onto the copper foil using a hand coater so that the film thickness after drying is 17 ⁇ m, and the coated sample is placed in a dryer at 30 ° C. for 30 minutes. Heated for minutes and dried. About the obtained film, IR spectrum was measured by ATR method and / or transmission method using an infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR-460Puls).
  • ⁇ Glass transition temperature Tg> The glass transition temperature was measured using a thermomechanical analyzer (manufactured by Shimadzu Corporation, TMA-50). By thermomechanical analysis, the test piece elongation was measured in the temperature range of 50 to 450 ° C under a load of 5 g, a heating rate of 10 ° C / min, under a nitrogen atmosphere (flow rate 20 ml / min), and the inflection point of the obtained curve. The glass transition temperature of the polyimide film after firing was determined.
  • ion-exchanged water (4.8 L) and ethyl acetate (3.6 L) were added to a 30 L extractor, and extraction and liquid separation were performed to obtain a reddish brown transparent organic layer.
  • the solvent was distilled off from the organic layer with a 50 L evaporator.
  • the residue was crystallized from hexane (3.6 L) and ethanol (360 ml), filtered, and then dried in vacuo to obtain a thermal base generator 1 represented by the following general formula (13) as a light brown solid. .
  • the results of the IR spectrum of the thermal base generator 1 measured by the IR spectrum measurement method are shown in FIG. 1, and the peak appearance positions are shown below.
  • Peak appearance position (cm ⁇ 1 ): 3300, 2978, 1691, 1602, 1541, 1508, 1440, 1367, 1281, 1243, 1214, 1157, 1055, 984, 879, 838, 776
  • Example 1 In a nitrogen atmosphere, Jeffermine XTJ-542 (18.6 mmol), ⁇ -butyrolactone (60 g), 5BTA (60 mmol), and toluene (75 g) were placed in a separable flask equipped with a Dean-Stark apparatus and a reflux condenser at 50 ° C. And stirred for 1 hour. Subsequently, the mixture was heated and stirred at 180 ° C. for 2 hours. Further, toluene as an azeotropic solvent was removed over 2.5 hours, and then cooled to 25 ° C.
  • Peak appearance position (cm ⁇ 1 ): 2941, 2866, 1780, 1719, 1594, 1542, 1480, 1438, 1376, 1288, 1249, 1179, 1111, 987, 864, 731
  • Table 1 shows the results of weight average molecular weight, C / (A + B + C), and thermal stability evaluation.
  • photosensitive resin composition (1) evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 3%.
  • Example 2 In Example 1, a photosensitive resin composition (2) was prepared according to the method described in Example 1, except that FP-300 was used instead of FP-390 as the phosphazene compound.
  • photosensitive resin composition (2) evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 4%.
  • Example 3 Under a nitrogen atmosphere, put Jeffamine XTJ-542 (6.2 mmol), ⁇ -butyrolactone (30 g), 5BTA (20 mmol), and toluene (25 g) in a 500 mL separable flask equipped with a Dean-Stark apparatus and a refluxer. Pyridine (4.8 mmol) and ⁇ -valerolactone (2.4 mmol) were added as the catalyst, and the mixture was heated and stirred at 140 ° C. for 6 hours under a nitrogen stream (400 mL / min) to remove toluene and the catalyst as an azeotropic solvent. .
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (2). And a photosensitive resin composition (3) was prepared.
  • Example 4 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (42.0 g), triethylene glycol dimethyl ether (18.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 18.85 mmol) and 5BTA (60.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., then APB-N (37.2 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (3).
  • the weight average molecular weight, C / (A + B + C) of the polyimide precursor (3) and the results of thermal stability evaluation are shown in Table 1 below.
  • the IR spectrum result of the polyimide precursor (3) measured by the above IR spectrum measurement method is shown in FIG. 3, and the peak appearance position is shown below.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (3). And a photosensitive resin composition (4) was prepared.
  • Example 5 In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 14.85 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., then APB-N (21.41 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (4).
  • the weight average molecular weight, C / (A + B + C) of the polyimide precursor (4) and the results of thermal stability evaluation are shown in Table 1 below.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (4). And a photosensitive resin composition (5) was prepared.
  • Example 6 In Example 5, a photosensitive resin composition (6) was prepared according to the method described in Example 5, except that FP-300 was used instead of FP-390 as the phosphazene compound.
  • Example 7 In Example 5, a polyimide precursor (5) was used according to the method described in Example 5 except that (trade name: Jeffamine ED-900 (manufactured by Huntsman)) was used as the diamine instead of Jeffamine XTJ-542. ) was polymerized. The weight average molecular weight, C / (A + B + C) of the polyimide precursor (5) and the results of thermal stability evaluation are shown in Table 1 below.
  • a photosensitive resin composition (7) was prepared.
  • About 1% by weight sodium carbonate of the photosensitive resin composition (7), evaluation of alkali developability in a 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, warping of the film after firing Measurement and glass transition temperature measurement were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 2%.
  • Example 8 In Example 5, a polyimide precursor (6) was used according to the method described in Example 5 except that (trade name: Jeffamine D-2000 (manufactured by Huntsman)) was used instead of Jeffamine XTJ-542 as the diamine. ) was polymerized. The weight average molecular weight, C / (A + B + C) of the polyimide precursor (6) and the results of thermal stability evaluation are shown in Table 1 below.
  • a photosensitive resin composition (8) was prepared in the same manner as in Example 5.
  • the results are shown in Table 2 below.
  • the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 2%.
  • Example 9 In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 10 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., APB-N (21.41 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (7).
  • the weight average molecular weight, C / (A + B + C) of the polyimide precursor (7) and the results of thermal stability evaluation are shown in Table 1 below.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (7). And a photosensitive resin composition (9) was prepared.
  • Example 10 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (42.0 g), triethylene glycol dimethyl ether (18.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 14.3 mmol) and BTDA (52.14 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., APB-N (33.18 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (8).
  • the weight average molecular weight, C / (A + B + C) of the polyimide precursor (8) and the results of thermal stability evaluation are shown in Table 1 below.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass), TPA with respect to 100 parts by mass of the polyimide precursor (8) -B80E (5 parts by mass) was mixed to prepare a photosensitive resin composition (10).
  • Example 11 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 12.4 mmol) and BPDA (47.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., then APB-N (31.13 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (9). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (9) and the results of thermal stability evaluation are shown in Table 1 below.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (9). And a photosensitive resin composition (11) was prepared.
  • FIG. 4 shows the results of IR spectrum of the baked photosensitive resin composition measured by the IR spectrum measurement method, and the peak appearance positions are shown below.
  • Example 12 a photosensitive resin composition (12) was prepared according to the method described in Example 11, except that FP-300 was used instead of FP-390 as the phosphazene compound.
  • Example 13 In Example 11, a photosensitive resin composition (13) was prepared according to the method described in Example 11 except that TPA-B80E (5 parts by mass) was further mixed.
  • a photosensitive resin composition (14) was prepared according to the method described in Example 11 except that TPA-B80E (5 parts by mass) was further mixed in Example 12.
  • Example 15 A photosensitive resin composition (15) was prepared according to the method described in Example 11 except that SBN-70DT (5 parts by mass) was further mixed in Example 12.
  • Example 16 A photosensitive resin composition (16) was prepared according to the method described in Example 11 except that Karenz MOI-BP (5 parts by mass) was further used in Example 12.
  • Example 17 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 16.9 mmol) and BPDA (47.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., then DAS (25.08 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (10). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (10) and the results of thermal stability evaluation are shown in Table 1 below.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (10). And a photosensitive resin composition (17) was prepared.
  • Example 18 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 12.4 mmol), BPDA (31.72 mmol), and ODPA (15.86 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour.
  • ⁇ -butyrolactone 35.0 g
  • triethylene glycol dimethyl ether 15.0 g
  • toluene 20.0 g
  • Jeffamine XTJ-542 12.4 mmol
  • BPDA 31.72 mmol
  • ODPA 15.86 mmol
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (11). And a photosensitive resin composition (18) was prepared.
  • Example 19 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 16.9 mmol), BPDA (31.72 mmol), and ODPA (15.86 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour.
  • ⁇ -butyrolactone 35.0 g
  • triethylene glycol dimethyl ether 15.0 g
  • toluene 20.0 g
  • Jeffamine XTJ-542 16.9 mmol
  • BPDA 31.72 mmol
  • ODPA 15.86 mmol
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (12). And a photosensitive resin composition (19) was prepared.
  • Example 20 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 12.4 mmol), BPDA (44.0 mmol), and maleic anhydride (3.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour.
  • ⁇ -butyrolactone 35.0 g
  • triethylene glycol dimethyl ether 15.0 g
  • toluene 20.0 g
  • Jeffamine XTJ-542 12.4 mmol
  • BPDA 44.0 mmol
  • maleic anhydride 3.58 mmol
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (13). And a photosensitive resin composition (20) was prepared.
  • Example 21 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 12.4 mmol), BPDA (44.0 mmol) and nadic anhydride (3.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour.
  • ⁇ -butyrolactone 35.0 g
  • triethylene glycol dimethyl ether 15.0 g
  • toluene 20.0 g
  • Jeffamine XTJ-542 12.4 mmol
  • BPDA 44.0 mmol
  • nadic anhydride 3.58 mmol
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (14). And a photosensitive resin composition (21) was prepared.
  • Example 22 In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 16.9 mmol), BPDA (44.0 mmol) and maleic anhydride (3.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour.
  • ⁇ -butyrolactone 35.0 g
  • triethylene glycol dimethyl ether 15.0 g
  • toluene 20.0 g
  • Jeffamine XTJ-542 16.9 mmol
  • BPDA 4.0 mmol
  • maleic anhydride 3.58 mmol
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (15). And a photosensitive resin composition (22) was prepared.
  • Example 23 In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 16.0 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene which is an azeotropic solvent, the solution was cooled to 25 ° C., then BAPP (19.49 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (16). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (16) and the results of thermal stability evaluation are shown in Table 1 below.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (16). And a photosensitive resin composition (23) was prepared.
  • Example 24 In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 10.4 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the solution was cooled to 25 ° C., followed by addition of TMAB (25.13 mmol), and stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (17).
  • the weight average molecular weight, C / (A + B + C) of the polyimide precursor (17) and the results of thermal stability evaluation are shown in Table 1 below.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (17). Then, a photosensitive resin composition (24) was prepared.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor (1) obtained in Example 1.
  • a photosensitive resin composition (25) was prepared.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor (3) obtained in Example 4.
  • a photosensitive resin composition (26) was prepared.
  • Example 27 1,2-naphthoquinonediazide-5-sulfonic acid ester (PA6) (20 parts by mass) is mixed with 100 parts by mass of the polyimide precursor (1) obtained in Example 1, and a photosensitive resin composition ( 27) was adjusted.
  • PA6 1,2-naphthoquinonediazide-5-sulfonic acid ester
  • Example 28 With respect to 100 parts by mass of the polyimide precursor (3) obtained in Example 4, BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (28).
  • the photosensitive resin composition (28) About the photosensitive resin composition (28), the alkali developability evaluation in 1 mass% sodium carbonate aqueous solution, tack property, the bending test after baking, a flame retardance test, and the curvature measurement of the film after baking were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 95%.
  • Example 29 a photosensitive resin composition (29) was prepared according to the method described in Example 28, except that the thermal base generator 2 was used instead of the thermal base generator 1.
  • Example 30 In Example 28, a photosensitive resin composition (30) was prepared according to the method described in Example 28 except that the thermal base generator 3 was used instead of the thermal base generator 1.
  • Example 31 BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 with respect to 100 parts by mass of the polyimide precursor (9) obtained in Example 12 (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (31).
  • the photosensitive resin composition (31) About the photosensitive resin composition (31), the alkali developability evaluation in 1 mass% sodium carbonate aqueous solution, tack property, the bending test after baking, a flame retardance test, and the curvature measurement of the film after baking were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 98%.
  • Example 32 In Example 31, a photosensitive resin composition (32) was prepared according to the method described in Example 31 except that the thermal base generator 2 was used instead of the thermal base generator 1.
  • Example 33 In Example 31, a photosensitive resin composition (33) was prepared according to the method described in Example 31 except that the thermal base generator 3 was used instead of the thermal base generator 1.
  • Example 34 BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 with respect to 100 parts by mass of the polyimide precursor (13) obtained in Example 20 (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (34).
  • the photosensitive resin composition (34) was evaluated for alkali developability in a 1% by weight aqueous sodium carbonate solution, tackiness, a bending test after firing, a flame retardance test, and a warp measurement of the film after firing. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 81%.
  • Example 35 a photosensitive resin composition (35) was prepared according to the method described in Example 34 except that the thermal base generator 2 was used instead of the thermal base generator 1.
  • Example 36 In Example 34, a photosensitive resin composition (36) was prepared according to the method described in Example 34 except that the thermal base generator 3 was used instead of the thermal base generator 1.
  • Example 37 BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 with respect to 100 parts by mass of the polyimide precursor (14) obtained in Example 21. (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (37).
  • the photosensitive resin composition (37) was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, a bending test after firing, a flame retardance test, and a warp measurement of the film after firing. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 84%.
  • Example 38 In Example 37, a photosensitive resin composition (38) was prepared according to the method described in Example 37, except that the thermal base generator 2 was used instead of the thermal base generator 1.
  • Example 39 In Example 37, a photosensitive resin composition (39) was prepared according to the method described in Example 37, except that the thermal base generator 3 was used instead of the thermal base generator 1.
  • Example 40 BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 with respect to 100 parts by mass of the polyimide precursor (10) obtained in Example 17 (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (40).
  • the photosensitive resin composition (40) was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, a bending test after firing, a flame retardance test, and warpage of the film after firing. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 82%.
  • Example 41 the photosensitive resin composition (41) was prepared according to the method described in Example 40 except that the thermal base generator 2 was used instead of the thermal base generator 1.
  • photosensitive resin composition (41) Evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 81%.
  • Example 42 the photosensitive resin composition (42) was prepared according to the method described in Example 40 except that the thermal base generator 3 was used instead of the thermal base generator 1.
  • Example 43 With respect to 100 parts by mass of the polyimide precursor (15) obtained in Example 22, BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (43).
  • Example 44 In Example 43, a photosensitive resin composition (44) was prepared according to the method described in Example 43, except that the thermal base generator 2 was used instead of the thermal base generator 1.
  • Example 45 In Example 44, a photosensitive resin composition (45) was prepared according to the method described in Example 44, except that the thermal base generator 3 was used instead of the thermal base generator 1.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor of Comparative Example 1, and the photosensitivity of Comparative Example 1 is obtained.
  • a resin composition was prepared.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor of Comparative Example 2, and the photosensitivity of Comparative Example 2 is obtained.
  • a resin composition was prepared.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor of Comparative Example 3, and the photosensitivity of Comparative Example 3 is obtained.
  • a resin composition was prepared.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor of Comparative Example 4, and the photosensitivity of Comparative Example 4 was obtained.
  • a resin composition was prepared.
  • BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor of Comparative Example 5, and the photosensitivity of Comparative Example 5 was obtained.
  • a resin composition was prepared.
  • the polyimide precursors (Example 1 to Example 45) have a lower weight average molecular weight when dried at 95 ° C. than Comparative Examples 1 to 5. It can be seen that the thermal stability, the bending test, flame retardancy, warpage, developability, tackiness, and solvent resistance are good.
  • Example 28 to Example 45 in the case where the thermal base generator 1 to the thermal base generator 3 having a specific structure is used, the remaining film ratio is greatly increased. It can be seen that the solvent property is good. As described above, this is considered to be due to an interaction between a diamine having an aromatic ring generated by thermal decomposition and a polyimide precursor having an aromatic ring. Further, as can be seen from Comparative Example 5, it can be seen that when the diamine having the specific structure is not contained in the polyimide structure, the thermal stability, the bending test, the flame retardancy, the developability, and the tackiness are lowered.
  • the polyimide precursor is a semiconductor device surface protective film, an interlayer insulating film, a rewiring insulating film, a bump protective film, a multilayer circuit interlayer insulating film, a flexible copper clad cover coat, and a liquid crystal alignment It can be suitably used as a film or the like.

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Abstract

L'invention concerne : un précurseur de polyimide avec lequel il est possible de produire un film ne présentant aucune fissure dans une couche photosensible lorsque le film est plié, qui peut présenter une bonne capacité de développement, qui peut être utilisé dans une carte de circuit imprimé flexible (FPC) pour réduire le gauchissement de la FPC après le traitement thermique de la FPC et qui convient par conséquent en tant que couche de revêtement pour une FPC ; une composition de résine photosensible contenant le précurseur de polyimide ; un film photosensible produit en utilisant la composition de résine photosensible ; un substrat produit en utilisant le film photosensible ; et un stratifié du substrat. Le précurseur de polyimide est caractérisé en ce qu'il contient, en tant qu'unités constitutives de répétition, une structure polyimide qui est représentée par la formule générale (1) et contient une diamine représentée par la formule générale (5) et une structure acide polyamique qui est représentée par la formule générale (2) et contient des dianhydrides d'acide tétracarboxylique représentés respectivement par les formules générales (3) et (4). (Dans les formules (1) à (5), R1 à R17 représentent indépendamment un atome d'hydrogène ou un groupe organique spécifié ; X représente un substituant spécifié ; Y représente un groupe organique spécifié ; et a, m, n et p représentent indépendamment un entier spécifié.)
PCT/JP2010/070306 2009-11-16 2010-11-15 Précurseur de polyimide et composition de résine photosensible contenant le précurseur de polyimide Ceased WO2011059089A1 (fr)

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JP2011540575A JP5758300B2 (ja) 2009-11-16 2010-11-15 ポリイミド前駆体を含む感光性樹脂組成物、感光性フィルム、カバーレイ、及びフレキシブルプリント配線板並びにその積層体
KR1020127009908A KR101392539B1 (ko) 2009-11-16 2010-11-15 폴리이미드 전구체 및 이 폴리이미드 전구체를 포함하는 감광성 수지 조성물
CN201080049271.6A CN102597061B (zh) 2009-11-16 2010-11-15 聚酰亚胺前体和包含该聚酰亚胺前体的感光性树脂组合物

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JP2009261102 2009-11-16
JP2009-261102 2009-11-16

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JP2014225031A (ja) * 2010-03-11 2014-12-04 エルジー ケム． エルティーディ． 絶縁膜
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JP2013101741A (ja) * 2011-10-18 2013-05-23 Dainippon Printing Co Ltd 回路基板、サスペンション用基板、サスペンション、素子付サスペンションおよびハードディスクドライブ
JP2013095894A (ja) * 2011-11-04 2013-05-20 Asahi Kasei E-Materials Corp ポリイミド前駆体又はポリイミド及び感光性樹脂組成物
JP2013216776A (ja) * 2012-04-09 2013-10-24 Sumitomo Electric Ind Ltd ポリイミド前駆体溶液の製造方法及びこれを用いたポリイミド前駆体溶液、多孔質ポリイミド
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WO2014024951A1 (fr) * 2012-08-08 2014-02-13 旭化成イーマテリアルズ株式会社 Stratifié de film photosensible, carte de circuit imprimé flexible et procédé de fabrication de ceux-ci
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US9454078B2 (en) 2012-09-25 2016-09-27 Toray Industries, Inc. Positive-type photosensitive resin composition, method for producing semiconductor device including cured film using the same
JP2014172994A (ja) * 2013-03-08 2014-09-22 Asahi Kasei E-Materials Corp ポリイミド前駆体、ポリイミド及び感光性樹脂組成物
JP2018501497A (ja) * 2014-12-10 2018-01-18 太陽油墨（蘇州）有限公司Ｔａｉｙｏ Ｉｎｋ（Ｓｕｚｈｏｕ）Ｃｏ．，Ｌｔｄ． 光硬化性熱硬化性樹脂組成物、ドライフィルム、硬化物、及びプリント配線板
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WO2018117047A1 (fr) * 2016-12-20 2018-06-28 旭化成株式会社 Rouleau à couche photosensible à deux couches
JPWO2018117047A1 (ja) * 2016-12-20 2019-08-08 旭化成株式会社 ２層感光層ロール
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JP7146014B2 (ja) 2017-11-28 2022-10-03 旭化成株式会社 ネガ型感光性樹脂組成物及びその製造方法、並びに硬化レリーフパターンの製造方法
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JP2020076092A (ja) * 2018-11-06 2020-05-21 イノックス・アドバンスト・マテリアルズ・カンパニー・リミテッドＩＮＮＯＸ Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． Ｆｐｉｃフィルム及びその製造方法
EP3896521A1 (fr) * 2020-04-14 2021-10-20 Shin-Etsu Chemical Co., Ltd. Polymère, composition de résine photosensible, procédé de formation de motifs, procédé de formation d'un film durci, film d'isolation intercouche, film protecteur de surface et composant électronique
US11333975B2 (en) 2020-04-14 2022-05-17 International Business Machines Corporation Polymer, photosensitive resin composition, patterning method, method of forming cured film, interlayer insulating film, surface protective film, and electronic component
US11572442B2 (en) 2020-04-14 2023-02-07 International Business Machines Corporation Compound, polyimide resin and method of producing the same, photosensitive resin composition, patterning method and method of forming cured film, interlayer insulating film, surface protective film, and electronic component
WO2024216910A1 (fr) * 2023-04-19 2024-10-24 明士(北京)新材料开发有限公司 Composition de résine photosensible positive à haute résistance chimique, son procédé de préparation et son utilisation

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KR20120068923A (ko) 2012-06-27
TWI440656B (zh) 2014-06-11
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