WO2009136557A1 - Précurseur de polyimide, composition de précurseur de polyimide photosensible, film sec photosensible et carte de circuits imprimés flexible utilisant ces matières - Google Patents

Précurseur de polyimide, composition de précurseur de polyimide photosensible, film sec photosensible et carte de circuits imprimés flexible utilisant ces matières Download PDF

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WO2009136557A1
WO2009136557A1 PCT/JP2009/058159 JP2009058159W WO2009136557A1 WO 2009136557 A1 WO2009136557 A1 WO 2009136557A1 JP 2009058159 W JP2009058159 W JP 2009058159W WO 2009136557 A1 WO2009136557 A1 WO 2009136557A1
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polyimide precursor
photosensitive
group
bis
carbon atoms
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PCT/JP2009/058159
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English (en)
Japanese (ja)
Inventor
久遠 宮崎
隆志 早川
明宏 加藤
秀明 高橋
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旭化成イーマテリアルズ株式会社
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Priority to CN2009801157178A priority Critical patent/CN102015835A/zh
Priority to JP2010511044A priority patent/JP5417323B2/ja
Priority to KR1020107024194A priority patent/KR101308811B1/ko
Publication of WO2009136557A1 publication Critical patent/WO2009136557A1/fr

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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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • 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
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic 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
    • 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
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—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
    • 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
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • 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, a photosensitive polyimide precursor composition, a photosensitive dry film, and a flexible printed wiring board using them.
  • FPC flexible printed circuit board
  • This board has a coverlay made of polyimide film etc. on the processed FCCL (Flexible Copper Clad Laminate) and is mainly used for devices such as mobile phones, laptop computers, digital cameras, etc. It has been. Since FPC maintains its function even when it is bent, it is an indispensable material for reducing the size and weight of equipment.
  • electronic devices represented by notebook computers have been reduced in size and weight, and by adopting FPC for such products, the size and weight of the devices can be reduced, the product cost can be reduced, and the design can be reduced. Contributes to simplification.
  • the coverlay provided in this FPC is formed by bonding mainly using a polyimide film with an adhesive.
  • problems have arisen in the positional accuracy of bonding.
  • development of a photosensitive cover lay capable of finely processing only necessary portions with high precision by irradiating with an actinic ray such as ultraviolet rays has begun to be carried out energetically.
  • the dry film type photosensitive coverlay exhibits excellent dimensional accuracy and does not require a solvent drying step. Therefore, in the FPC manufacturing, the process can be simplified and is expected as a material with low environmental load.
  • Patent Document 1 discloses a heat-resistant adhesive using tetracarboxylic dianhydride and diamine.
  • Patent Document 2 discloses a film-forming photosensitive heat-resistant resin composition using a polyimide precursor, and Patent Document 3 discloses a photosensitive cover coat material containing polyamic acid.
  • Patent Document 4 discloses an adhesive film made of a specific acid dianhydride.
  • the molecular weight of the polyimide precursor is lowered due to the tackiness problem of the photosensitive dry film and the solvent removal accompanying the formation of the photosensitive dry film, and the resulting photosensitive
  • the conductive dry film is bent, there may be a problem that the photosensitive layer is broken.
  • the pattern is formed by lithography due to a decrease in the molecular weight of the polyimide precursor, the development time is not stable in the development using an alkaline aqueous solution, the pattern film thickness becomes thin, and the pattern shape is distorted. Arise.
  • the FPC may be warped due to the stress caused by the solvent removal or the ring closure reaction accompanying the imidization of the polyimide precursor.
  • warpage occurs in the FPC, 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. Therefore, it is required to improve the warpage of the FPC having a coverlay on the copper wiring.
  • the coverlay is required to exhibit flame retardancy in a flame retardancy test represented by the UL standard VTM test.
  • halogen compounds have been originally added to coverlays. However, from the viewpoint of environmental protection and biotoxicity, it is desired that non-halogen and flame retardancy be expressed.
  • JP 2004-269622 A Japanese Patent Laid-Open No. 04-18450 JP 05-158237 A Japanese Patent Laid-Open No. 10-330723
  • the present invention has been made in view of the above points, and when used for FPC, a polyimide precursor, a photosensitive polyimide precursor composition, and a photosensitive dry film that have less bending of FPC after baking and excellent bendability. And it aims at providing the flexible printed wiring board using them.
  • the polyimide precursor of this invention is characterized by including the acid dianhydride represented by following General formula (1).
  • X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms.
  • R 1 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group. .
  • the polyimide precursor of the present invention preferably contains a diamine represented by the following general formula (2).
  • Y is a divalent organic group having an alkylene group having 2 to 20 carbon atoms.
  • R 2 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group. .
  • the acid dianhydride represented by following General formula (3) is included.
  • A represents an integer of 1 to 20.
  • b represents an integer of 3 to 30.
  • R 3 represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms.
  • the diamine represented by following General formula (4) is included.
  • Z represents an alkylene group having 2 to 20 carbon atoms.
  • R 4 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.
  • C represents 2 to 30 carbon atoms. Represents an integer.
  • the acid dianhydride represented by following General formula (3) is included.
  • A represents an integer of 1 to 15.
  • b represents an integer of 5 to 20.
  • R 3 represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms.
  • the diamine represented by the general formula (4) is preferably 25 mol% to 75 mol% of all diamine components.
  • the photosensitive polyimide precursor composition of the present invention contains 100 parts by mass of the polyimide precursor and 5 to 30 parts by mass of a photosensitizer.
  • the photosensitive agent preferably contains a quinonediazide structure.
  • the photosensitive polyimide precursor composition of the present invention preferably contains a compound having a phenolic hydroxyl group as a dissolution inhibitor.
  • the photosensitive dry film of the present invention is characterized in that the above photosensitive polyimide precursor composition is applied to a support film, desolvated, and then a cover film is laminated.
  • the flexible printed wiring board of the present invention is formed using the photosensitive dry film.
  • the ratio (Mw2 / Mw1) between the weight average molecular weight (Mw1) in the varnish and the weight average molecular weight (Mw2) after desolvation at 120 ° C. or lower is 0.7 or more. It is characterized by that.
  • the photosensitive polyimide precursor composition of the present invention uses a polyimide precursor obtained from an acid dianhydride having a specific structure, so that when used for FPC, there is little warping of the FPC after baking and bending. There is an effect that it is excellent in properties.
  • (A) Polyimide precursor An acid dianhydride and diamine are used as a monomer of a polyimide precursor. It is known that the molecular weight of the polyimide precursor is reduced by solvent removal with heating. From the viewpoint of reducing the decrease in molecular weight, the acid dianhydride used for the polyimide precursor is represented by the following general formula (1). The acid dianhydride represented is used. Any acid-free dihydrate represented by the structure may be used alone or in combination of two or more. By suppressing the decrease in molecular weight in the solvent removal step, it is possible to prevent cracking during folding when the photosensitive dry film is formed, and to improve the folding property.
  • X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms.
  • R 1 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group. .
  • an acid dianhydride represented by the following general formula (3) from the viewpoint of suppressing a decrease in molecular weight in the solvent removal step.
  • A represents an integer of 1 to 20.
  • b represents an integer of 3 to 30.
  • R 3 represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms.
  • a is preferably 1 to 15, and b is preferably 5 to 20.
  • butanediol-bis-trimellitic anhydride ester pentanediol-bis-trimellitic anhydride ester, heptanediol-bis-trimellitic anhydride ester, decanediol-bis-trimellitic anhydride ester, Examples thereof include sundiol-bis-trimellitic anhydride ester, polypropylenediol-bis-trimellitic anhydride ester, polytetramethylenediol-bis-trimellitic anhydride ester, and the like. These compounds may be used alone or in combination of two or more.
  • acid dianhydrides may be used for the polyimide precursor according to the present invention.
  • aromatic tetracarboxylic acid pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1, 1-bis (3,4-dicarboxyphenyl) ethane dianhydride,
  • Aliphatic tetracarboxylic dianhydrides include cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene- Examples include 2,3,5,6 tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride. These acid dianhydrides are preferably used in the range of 0 mol% to 50 mol% with respect to the total amount of acid dianhydride of the polyimide precursor from the viewpoint of reducing warpage after baking.
  • the diamine used for the polyimide precursor is represented by the following general formula (2) from the viewpoint of suppressing a decrease in molecular weight in the solvent removal step and from the viewpoint of improving tackiness when a photosensitive dry film is obtained after the solvent removal. It is preferable to use diamines. Any diamine represented by the structure may be used alone or in combination of two or more.
  • R 2 is preferably a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms.
  • Y is a divalent organic group having an alkylene group having 2 to 20 carbon atoms.
  • R 2 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group. .
  • Z represents an alkylene group having 2 to 20 carbon atoms.
  • R 4 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.
  • C represents 2 to 30 carbon atoms. Represents an integer.
  • polydimethylene oxide-di-o-aminobenzoate polydimethylene oxide-di-o-aminobenzoate
  • polydimethylene oxide-di-m-aminobenzoate polydimethylene oxide-di-p-aminobenzoate
  • polytrimethylene oxide-di-o-aminobenzoate Polytrimethylene oxide-di-m-aminobenzoate, polytrimethylene oxide-di-p-aminobenzoate, polytetramethylene oxide-di-o-aminobenzoate, polytetramethylene oxide-di-m-aminobenzoate, poly Tetramethylene oxide-di-p-aminobenzoate, poly-3-methyltetramethylene oxide-di-o-aminobenzoate, poly-3-methyltetramethylene oxide-di-m-aminobenzoate, poly-3-methyltetramethylene oxide-di-m-aminobenzoate, poly
  • the blending amount of these diamines is such that the diamine represented by the general formula (4) is 25 mol% to 75 mol% in the total diamine components from the viewpoint of reducing warpage after baking. preferable.
  • the compound represented by the general formula (2) and the compound represented by the general formula (4) are used at the same time.
  • the compounding amount of the compound represented by the general formula (4) is preferably 25 mol% to 75 mol% with respect to the total amount of diamine.
  • the end of the polyamide precursor may be sealed with a monofunctional acid anhydride, monofunctional carboxylic acid, or monofunctional amine.
  • the polyimide precursor according to the present invention can be made into a photosensitive polyimide precursor composition by blending (B) a photosensitive agent and (C) an organic solvent.
  • the photosensitive polyimide precursor composition according to the present invention is blended with a compound that generates an acid when irradiated with actinic rays as a photosensitive agent.
  • the photosensitizer is not particularly limited as long as it generates an acid upon irradiation with actinic rays, but is preferably a compound having a quinonediazide structure, such as a benzoquinonediazide compound or a naphthoquinonediazide compound.
  • a compound having a quinonediazide structure such as a benzoquinonediazide compound or a naphthoquinonediazide compound.
  • those described in US Pat. No. 2,797,213 and US Pat. No. 3,669,658 can be used.
  • ester compounds of a phenol compound and 1,2-naphthoquinone-2-diazide-4-sulfonic acid or 1,2-naphthoquinone-2-diazide-5-sulfonic acid are preferable. These may be used alone or in combination of two or more.
  • the blending amount of the photosensitizer according to the present invention is preferably 5 to 35 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyimide precursor.
  • the blending amount of the photosensitizer is preferably 5 parts by mass or more from the viewpoint of developing photosensitivity and inhibiting dissolution in a developer composed of an alkaline aqueous solution, and 35 parts by mass or less from the viewpoint of developing sensitivity and cover toughness.
  • Organic solvent examples include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, ⁇ -butyrolactone, and dimethyl sulfoxide. Moreover, the solvent whose boiling point is lower than these solvents can be mix
  • the low boiling point solvent examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and hexylene glycol.
  • the blending amount of the organic solvent is preferably 25 to 900 parts by mass, more preferably 100 to 400 parts by mass with respect to 100 parts by mass of the polyimide precursor.
  • the blending amount is more than 900 parts by mass, it becomes difficult to maintain the film thickness after coating, and when it is less than 25 parts by mass, the polyimide precursor is not completely dissolved.
  • Dissolution inhibitor can be mix
  • the dissolution inhibitor according to the present invention refers to a compound that hydrogen bonds with a carboxyl group or a phenolic hydroxyl group of a polyimide precursor. When the carboxyl group or phenolic hydroxyl group of the polyimide precursor is hydrogen-bonded with the dissolution inhibitor, the polyimide precursor is shielded from the developer, and coupled with the hydrophobicity of the compound, it is possible to inhibit the dissolution of the polyimide precursor.
  • Examples of the compound having a carboxyl group or a group capable of hydrogen bonding with a phenolic hydroxyl group include a carboxylic acid compound, a carboxylic acid ester compound, an amide compound, and a urea compound. From the viewpoints of the effect of inhibiting dissolution in a developer composed of an alkaline aqueous solution and the storage stability, a compound represented by the following general formula (6) is preferable, and an amide compound and a urea compound are more preferable.
  • R 5 and R 6 represent an organic group consisting of all or part of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. R 5 and R 6 may be the same or different.
  • amide compound examples include N, N-diethylacetamide, N, N-diisopropylformamide, N, N-dimethylbutyramide, N, N-dibutylacetamide, N, N-dipropylacetamide, N, N-dibutylformamide N, N-diethylpropionamide, N, N-dimethylpropionamide, N, N′-dimethoxy-N, N′-dimethyloxamide, N-methyl- ⁇ -caprolactam, 4-hydroxyphenylbenzamide, salicylamide, And salicylanilide, acetanilide, 2′-hydroxyacetanilide, 3′-hydroxyacetanilide, 4′-hydroxyacetanilide.
  • a phenolic hydroxyl group from the viewpoint of lowering the glass transition point of the photosensitive layer and the film obtained by baking the photosensitive layer, controlling the solubility in a developer composed of an alkaline aqueous solution, and increasing the residual film ratio.
  • a compound is preferable, and an amide compound having a phenolic hydroxyl group is more preferable.
  • Specific examples include 4-hydroxyphenylbenzamide, 2'-hydroxyacetanilide, 3'-hydroxyacetanilide, and 4'-hydroxyacetanilide. These may be used alone or in combination of two or more.
  • the urea compound examples include 1,3-dimethylurea, tetramethylurea, tetraethylurea, 1,3-diphenylurea, and 3-hydroxyphenylurea.
  • it contains phenolic hydroxyl groups from the viewpoint of controlling the solubility in a developer composed of an aqueous alkali solution, increasing the residual film ratio, and lowering the glass transition point of the photosensitive layer and the film obtained by baking the photosensitive layer.
  • More preferred are urea compounds.
  • Specific examples include 3-hydroxyphenylurea. These may be used alone or in combination of two or more.
  • the dissolution inhibitor according to the present invention may be blended in an amount of 0.1 mol to 2.0 mol with respect to 1 mol of the carboxyl group and phenolic hydroxyl group of the polyimide precursor from the viewpoint of expression of the dissolution inhibitory effect.
  • 0.15 mol to 1.5 mol is blended.
  • the dissolution inhibitor according to the present invention is preferably from 0.1 mol to 2.0 mol with respect to 1 mol of the carboxyl group and the phenolic hydroxyl group of the polyimide precursor from the viewpoint of expression of the dissolution inhibitory effect. From the viewpoint of the dissolution inhibiting effect and the toughness of the resin obtained by baking, it is more preferable to add 0.15 mol to 1.5 mol.
  • the total amount of the amide compound and the urea compound is from 0.1 mol to 1 mol of the carboxyl group and the phenolic hydroxyl group of the polyimide precursor from the viewpoint of the dissolution inhibiting effect.
  • a range of 1.5 mol is preferred.
  • Phenol compound A phenol compound can be mix
  • the phenol compound includes a compound represented by the following general formula (7) and a structure represented by the following general formula (8) from the viewpoint of reducing warpage of the sheet composed of the film and the substrate after baking and controlling the solubility in an alkaline aqueous solution. It is a phenol compound (assuming that it does not fall under the dissolution inhibitor of the present application).
  • R 7 and R 8 each independently represents an organic group having 1 to 50 hydrogen atoms or carbon atoms and 0 to 10 oxygen atoms.
  • X is independently a hydrogen atom, hydroxyl group or carbon number 1 to 20; Represents an organic group.
  • R 9 and R 11 each independently represents an organic group having 1 to 6 carbon atoms, and R 10 represents a bonding group or an organic group having 1 to 20 carbon atoms.
  • the compounding amount of the phenol compound according to the present invention is preferably 1 part by mass to 30 parts by mass, and more preferably 5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor.
  • the blending amount is less than 1 part by mass, it becomes difficult to suppress the solubility in a developer composed of an alkaline aqueous solution, and when it exceeds 30 parts by mass, the photosensitive dry film obtained after the solvent removal step The photosensitive layer becomes brittle.
  • (F) Plasticizer In the photosensitive polyimide precursor composition according to the present invention, a compound represented by the following general formula (9) can also be suitably used as a plasticizer.
  • R 12 to R 14 are organic groups containing an ethylene glycol chain and / or a propylene glycol chain, and may be the same or different.
  • the compounding amount of the plasticizer according to the present invention is preferably 1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor.
  • the blending amount is 1 part by mass or more, a warp reduction effect is exhibited, and when it is 30 parts by mass or less, a desired pattern is obtained without adversely affecting developability.
  • crosslinking agent in this invention, can be mix
  • a crosslinking agent a tetracarboxylic acid compound or a tetracarboxylic acid ester compound represented by the following general formula (10), a polyimide precursor or a carboxyl group-containing polyimide precursor ester compound represented by the following general formula (11) is preferable.
  • R 15 is a tetravalent organic group
  • R 16 to R 19 are hydrogen or a monovalent organic group having 1 to 20 carbon atoms, which may be the same or different.
  • R 20 , R 22 and R 24 are tetravalent organic groups which may be the same or different.
  • R 21 and R 23 are divalent organic groups which may be the same or different.
  • R 25 to R 32 are hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and g is an integer of 0 to 100.
  • the amount of the crosslinking agent according to the present invention is preferably from 0.1 mol to 1.5 mol, preferably from 0.5 mol to 1.1 mol, from the viewpoint of expression of the crosslinking effect, relative to the number of moles of the remaining amino groups of the polyimide precursor. Is more preferable.
  • the amount of residual amino groups can be calculated using high performance liquid chromatography.
  • thermal base generator is a compound that generates a base by heating.
  • a thermal base generator is a compound that generates a base by heating.
  • it can be obtained by forming a salt structure with an amino group of a basic compound such as amine and an acid such as sulfonic acid, protecting with a dicarbonate compound, or protecting with an acid chloride compound.
  • a thermal base generator that generates a base by deprotection by heating.
  • thermal base generator examples include U-CAT (registered trademark) SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851 (above, trade name: San Apro), N- (isopropoxycarbonyl) -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, amino group of aromatic diamine with dibutyl dicarbonate Examples include protected compounds.
  • N- (isopropoxycarbonyl) -2,6-dimethylpiperidine N-, from the viewpoints of storage stability of the photosensitive polyimide precursor composition, molecular weight stability by solvent removal, alkali solubility, and ion migration properties.
  • the blending amount of the thermal base generator according to the present invention is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polyimide precursor, from the viewpoint of acceleration of imidization and development performance, and 0.5 parts by mass. To 20 parts by mass is more preferable.
  • Phosphate ester compound can be mix
  • the phosphoric ester compound at least one compound selected from the group consisting of compounds represented by the following general formula (12), the following general formula (13) or the following general formula (14) is used.
  • R 35 from R 33 represents a number 1 or more organic groups carbon, it may be the same or different, respectively.
  • R 36 to R 39 each represents an organic group having 1 or more carbon atoms, and may be the same or different.
  • R 40 is hydrogen or a monovalent organic group.
  • R 33 to R 35 in the general formula (12) or R 36 to R 39 in the general formula (13) are methyl.
  • An organic group selected from a group, an ethyl group, a butyl group, a 2-ethylhexyl group, a butoxyethyl group, a phenyl group, a cresyl group, a xylenyl group, and an aminophenyl group is preferable.
  • R 40 in the general formula (14) is hydrogen, dihydroxyphenyl group, dibutylhydroxybenzyl group, (meth) acrylate-containing organic group. It is preferable that it is an organic group chosen from these. Further, in consideration of the compatibility with the resin varnish and the effect of improving the warp when the photosensitive dry film is formed, R 40 is preferably hydrogen.
  • These phosphate ester compounds can be used alone or in combination of two or more.
  • the blending amount of these phosphate ester compounds is preferably 1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 20 parts by mass. When the blending amount is 1 part by mass or more, plasticity is expressed. When the blending amount is 30 parts by mass or less, the portion of the photosensitive polyimide precursor composition that is not irradiated with actinic rays is less likely to be eroded by the developer composed of an alkaline aqueous solution. A good line image can be obtained.
  • Organophosphorus Compound An organophosphorus compound represented by the following general formula (15) can be blended with the photosensitive polyimide precursor composition according to the present invention. By mix
  • R 41 represents an organic group. H represents an integer of 1 to 50.
  • the compounding amount of these organic phosphorus compounds is preferably 1 part by mass to 30 parts by mass, and more preferably 3 parts by mass to 25 parts by mass. If the blending amount is 1 part by mass or more, flame retardancy is exhibited, and if it is 30 parts by mass or less, the resin pattern obtained after baking becomes tough.
  • the compounding amount of these compounds is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass.
  • the blending amount is 0.1 parts by mass or more, an effect of improving adhesiveness is exhibited, and when it is 10 parts by mass or less, a good line image can be obtained without adversely affecting developability.
  • alcohols such as ethanol, 2-propanol and ethylene glycol, ethyl lactate, methyl benzoate
  • Esters such as ethylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as n-butyl ether, tetrahydrofuran and dioxane
  • glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monoethyl ether Can be blended.
  • the photosensitive polyimide precursor composition of the present invention can be used as a coverlay.
  • a coverlay refers to a protective film that protects wiring formed on a silicon wafer, a copper clad laminate, an FPC, or the like.
  • the photosensitive polyimide precursor composition according to the present invention is prepared by mixing the polyimide precursor and various compounds in a suitable container, and is completely dissolved in a three-rotor motor equipped with a mix rotor, non-bubbling kneader, and stirring blades. It is obtained by stirring until
  • a photosensitive dry film can be produced using the photosensitive polyimide precursor composition, and a resin pattern can be formed.
  • the resin pattern can be formed by the following steps.
  • the photosensitive dry film is obtained by applying a photosensitive polyimide precursor composition to a support film (film substrate) and drying the solvent to form a photosensitive layer.
  • a support film low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene / cyclodecene copolymer, and the like can be used.
  • These support films can be subjected to surface treatment for the purpose of controlling the wettability of the photosensitive polyimide precursor composition and the peelability of the photosensitive layer obtained from the photosensitive polyimide precursor composition.
  • Examples of the surface treatment method include corona treatment, flame treatment, plasma treatment, surface modification using silicone, alkyd resin, olefin resin, and the like.
  • the thickness of the carrier film is usually 15 ⁇ m to 100 ⁇ m, preferably 15 ⁇ m to 75 ⁇ m, in consideration of coating properties, adhesion, rollability, toughness, cost, and the like.
  • the photosensitive polyimide precursor composition can be applied to the above support film using a known method such as a reverse roll coater, a gravure roll coater, a comma coater, a lip coater, or a slot die coater.
  • Solvent removal can be performed by drying the solvent (drying using hot air, far infrared rays, or near infrared rays).
  • the drying temperature is preferably from 50 ° C. to 120 ° C. from the viewpoint of suppressing the decrease in molecular weight, and more preferably from 50 ° C. to 110 ° C. from the viewpoint of the stability of the photosensitive agent.
  • the film thickness of the photosensitive layer obtained by solvent removal is preferably 5 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m.
  • the film thickness is preferably 5 ⁇ m or more from the viewpoint of insulation reliability, and preferably 100 ⁇ m or less from the viewpoint of obtaining a good line image.
  • the ratio (Mw2 / Mw1) between the weight average molecular weight (Mw1) in the polyimide precursor varnish and the weight average molecular weight (Mw2) after solvent removal at 120 ° C. or lower is 0.7 or more, Even if the photosensitive dry film after solvent removal is folded, the photosensitive layer is not cracked.
  • a cover film can be laminated on a photosensitive dry film to form a photosensitive laminated film. By laminating the cover film, adhesion of the photosensitive layer to the support film can be prevented.
  • the cover film low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene / cyclodecene copolymer can be used.
  • a process of forming a photosensitive layer by pressure-bonding a photosensitive dry film on a substrate on which a pattern is arranged A photosensitive dry film is superimposed on a surface on which a circuit such as an FPC is formed (on a substrate on which a pattern is arranged)
  • the photosensitive layer is laminated (press-bonded) at a pressure of 0.2 MPa to 5 MPa while being heated at 40 ° C. to 130 ° C., preferably 60 ° C. to 120 ° C., by a known method such as laminating, roll laminating or vacuum pressing. Can be stacked.
  • the photosensitive dry film is a photosensitive laminated film in which a cover film is laminated
  • the cover film is peeled off before lamination.
  • the laminating temperature to 40 ° C. or higher, it is possible to eliminate troublesome work by tacking at the time of alignment before lamination, and by setting it to 130 ° C. or lower, it is possible to laminate without decomposing the photosensitive agent.
  • the temperature at which lamination is possible is that there is no problem such as remaining bubbles, and the pattern can be sufficiently embedded in the pattern, and at the same time, the photosensitive layer has a viscosity at which the photosensitive polyimide precursor composition does not flow out of the pattern. It means the temperature that can be controlled.
  • the photosensitive dry film can be suitably laminated.
  • the support film may or may not be peeled off. If the support film is not peeled after lamination, it is peeled off after the exposure step.
  • Step of irradiating the photosensitive layer with actinic rays The photosensitive layer is exposed through a photomask on which an arbitrary pattern is drawn in order to form fine holes and fine width lines. Exposure varies depending on the composition of the photosensitive polyimide precursor composition is usually 100mJ / cm 2 ⁇ 3,000mJ / cm 2. Examples of actinic rays used at this time include X-rays, electron beams, ultraviolet rays, and visible rays. As the active light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, or the like can be used.
  • i-line 365 nm
  • h-line 405 nm
  • g-line 436 nm
  • contact exposure either contact exposure or projection exposure may be used.
  • a developing solution After exposure, a developing solution is used, and development is performed by a known method such as an immersion method or a spray method to obtain a line image.
  • an aqueous alkali solution such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, or an aqueous tetramethylammonium hydroxide solution can be used.
  • the development temperature is preferably 20 ° C. to 60 ° C., more preferably 25 ° C. to 50 ° C.
  • Step of rinsing with at least one solvent selected from the group consisting of water and acidic aqueous solution After development, washing is performed by a known method such as an immersion method or a spray method.
  • the rinsing liquid water or a solution obtained by adding an organic solvent to water can be used.
  • the temperature of the rinsing liquid is preferably 15 ° C. to 60 ° C., more preferably 20 ° C. to 50 ° C. from the viewpoint of residue removal.
  • washing may be performed with an inorganic acid aqueous solution or an organic acid aqueous solution.
  • the inorganic acid aqueous solution include a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a phosphoric acid aqueous solution, and a boric acid aqueous solution.
  • the organic acid aqueous solution include a formic acid aqueous solution, an acetic acid aqueous solution, a citric acid aqueous solution, and a lactic acid aqueous solution.
  • the washing time with the inorganic acid aqueous solution or organic acid aqueous solution is preferably 5 seconds to 120 seconds, more preferably 10 seconds to 60 seconds, from the viewpoint of washing efficiency.
  • the acidic aqueous solution is preferably washed away with water.
  • this process can reduce the residual stress between the photosensitive agent-derived substrate and the photosensitive layer, reduce the warpage of the FPC and multilayer printed wiring board obtained in the resin pattern manufacturing process, and increase the folding resistance.
  • Exposure to irradiation in this step varies by the thickness of the type of photosensitive agent used and the photosensitive layer is usually 100 mJ / cm 2 at 3,000 mJ / cm 2.
  • the amount is preferably 500 mJ / cm 2 or more from the viewpoint of photodecomposition of the photosensitive agent.
  • actinic rays used at this time include X-rays, electron beams, ultraviolet rays, and visible rays.
  • the active light source a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, or the like can be used.
  • i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.
  • the heating temperature is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 100 ° C.
  • Baking process at 100 to 400 ° C A resin pattern is formed by baking the line image obtained by the above process. Baking is carried out continuously or stepwise at a temperature of 100 ° C. to 400 ° C. for 5 minutes to 5 hours. And the processed product is completed. In the case of FPC, it is preferable to cure in a temperature range of 100 ° C. to 200 ° C. from the viewpoint of preventing oxidation of the wiring. Examples of the processed product thus obtained include FPC and multilayer printed wiring boards.
  • Synthesis Example 2 Synthesis of polyimide precursor (ii) In a three-necked separable flask, 4.8 g of 1,3-bis (3-aminophenoxy) benzene, 6.8 g of polytetramethylene oxide-di-p-aminobenzoate, ⁇ -butyrolactone 82 g was added and stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was pressure filtered through a 5 ⁇ m filter to obtain a polyimide precursor (ii). Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (ii), the solid content of the polyimide precursor (ii) solution, and the weight average molecular weight.
  • Synthesis Example 3 Synthesis of polyimide precursor (iii) In a three-necked separable flask, 9.7 g of 1,3-bis (3-aminophenoxy) benzene, 13.7 g of polytetramethylene oxide-di-p-aminobenzoate, ⁇ -butyrolactone 168.8 g was added and stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 11.5 g of decanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • polyimide precursor (iii) was pressure filtered through a 5 ⁇ m filter to obtain a polyimide precursor (iii).
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (iii), the solid content of the polyimide precursor (iii) solution, and the weight average molecular weight.
  • Synthesis Example 4 Synthesis of Polyimide Precursor (iv) In a three-necked separable flask, 8.8 g of 1,3-bis (3-aminophenoxy) benzene, 12.4 g of polytetramethylene oxide-di-p-aminobenzoate, ⁇ -butyrolactone 99.7 g was added and stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 11.5 g of decanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (iv), the solid content of the polyimide precursor (iv) solution, and the weight average molecular weight.
  • Synthesis Example 5 Synthesis of polyimide precursor (v) In a three-necked separable flask, 10.0 g of trimethylene-bis (4-aminobenzoate), 13.1 g of polytetramethylene oxide-di-p-aminobenzoate, 104.1 g of ⁇ -butyrolactone And stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 11.5 g of decanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (v), the solid content of the polyimide precursor (v) solution, and the weight average molecular weight.
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (vi), the solid content of the polyimide precursor (vi) solution, and the weight average molecular weight.
  • Synthesis Example 7 Synthesis of polyimide precursor (vii) In a three-necked separable flask, 9.5 g of trimethylene-bis (4-aminobenzoate), 12.4 g of polytetramethylene oxide-di-p-aminobenzoate, 101.0 g of ⁇ -butyrolactone And stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 11.5 g of decanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • polyimide precursor (vii) was pressure filtered through a 5 ⁇ m filter to obtain a polyimide precursor (vii).
  • Table 1 shows the molar ratio between the acid dianhydride and diamine of the obtained polyimide precursor (vii), the solid content of the polyimide precursor (vii) solution, and the weight average molecular weight.
  • Synthesis Example 8 Synthesis of polyimide precursor (viii) Trimethylene-bis (4-aminobenzoate) 9.1 g, polytetramethylene oxide-di-p-aminobenzoate 15.4 g, ⁇ -butyrolactone 107.3 g in a three-necked separable flask And stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 11.5 g of decanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • polyimide precursor (viii) was pressure filtered through a 5 ⁇ m filter to obtain a polyimide precursor (viii).
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (viii), the solid content of the polyimide precursor (viii) solution, and the weight average molecular weight.
  • Synthesis Example 9 Synthesis of polyimide precursor (ix) In a three-necked separable flask, 9.8 g of trimethylene-bis (3-aminobenzoate), 12.9 g of polytetramethylene oxide-di-p-aminobenzoate, 103.1 g of ⁇ -butyrolactone And stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 11.5 g of decanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • a polyimide precursor (ix) was obtained by pressure filtration of the product with a 5 ⁇ m filter.
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (ix), the solid content of the polyimide precursor (ix) solution, and the weight average molecular weight.
  • Synthesis Example 10 Synthesis of polyimide precursor (x) 9.8 g of trimethylene-bis (4-aminobenzoate), poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate) 12 in a three-necked separable flask 9.9 g and ⁇ -butyrolactone 103.1 g were added and stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 11.5 g of decanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • polyimide precursor (x) was pressure filtered through a 5 ⁇ m filter to obtain a polyimide precursor (x).
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (x), the solid content of the polyimide precursor (x) solution, and the weight average molecular weight.
  • Synthesis Example 11 Synthesis of polyimide precursor (xi) In a three-necked separable flask, 10.1 g of trimethylene-bis (4-aminobenzoate), 13.3 g of polytetramethylene oxide-di-p-aminobenzoate, 105.7 g of ⁇ -butyrolactone And stirred until a homogeneous solution was obtained. Next, 10 g of butanediol-bis-trimellitic anhydride ester and 11.9 g of decanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • a polyimide precursor (xi) was obtained by pressure filtration of the product with a 5 ⁇ m filter.
  • Table 1 shows the molar ratio between the acid dianhydride and diamine of the obtained polyimide precursor (xi), the solid content of the polyimide precursor (xi) solution, and the weight average molecular weight.
  • Synthesis Example 12 Synthesis of Polyimide Precursor (xii) 9.8 g of trimethylene-bis (4-aminobenzoate), 12.9 g of polytetramethylene oxide-di-p-aminobenzoate, 110.4 g of ⁇ -butyrolactone in a three-necked separable flask And stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 14.6 g of icosanediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature.
  • a polyimide precursor (xii) was obtained by pressure filtered through a 5 ⁇ m filter to obtain a polyimide precursor (xii).
  • Table 1 shows the molar ratio between the acid dianhydride and diamine of the obtained polyimide precursor (xii), the solid content of the polyimide precursor (xii) solution, and the weight average molecular weight.
  • Synthesis Example 13 Synthesis of polyimide precursor (xiii) In a three-necked separable flask, 9.8 g of trimethylene-bis (4-aminobenzoate), 12.9 g of polytetramethylene oxide-di-p-aminobenzoate, 123.9 g of ⁇ -butyrolactone And stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol-bis-trimellitic anhydride ester and 20.4 g of polypropylenediol-bis-trimellitic anhydride ester were added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xiii), the solid content of the polyimide precursor (xiii) solution, and the weight average molecular weight.
  • Synthesis Example 14 Synthesis of polyimide precursor (xiv) 9.4 g of 1,3-bis (3-aminophenoxy) benzene and 73 g of ⁇ -butyrolactone were placed in a three-necked separable flask and stirred until a uniform solution was obtained. Next, 10 g of 4,4′-oxydiphthalic dianhydride was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was pressure filtered through a 5 ⁇ m filter to obtain a polyimide precursor (xiv). Table 1 shows the molar ratio between the acid dianhydride and diamine of the obtained polyimide precursor (xiv), the solid content of the polyimide precursor (xiv) solution, and the weight average molecular weight.
  • Synthesis Example 15 Synthesis of Polyimide Precursor (xv)
  • a three-necked separable flask 7.1 g of 1,3-bis (3-aminophenoxy) benzene and 64.3 g of ⁇ -butyrolactone were added and stirred until a uniform solution was obtained.
  • 10 g of ethylenediol-bis-trimellitic acid ester was added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature.
  • the product was subjected to pressure filtration with a 5 ⁇ m filter to obtain a polyimide precursor (xv).
  • Table 1 shows the molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xv), the solid content of the polyimide precursor (xv) solution, and the weight average molecular weight.
  • Synthesis Example 16 Synthesis of polyimide precursor (xvi) In a three-necked separable flask, 2.7 g of 1,3-bis (3-aminophenoxy) benzene, 26.3 g of polytetramethylene oxide-di-p-aminobenzoate, ⁇ -butyrolactone 91.0 g was added and stirred until a homogeneous solution was obtained. Next, 10 g of 4,4′-oxydiphthalic dianhydride was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was pressure filtered through a 5 ⁇ m filter to obtain a polyimide precursor (xvi). Table 1 shows the molar ratio between the acid dianhydride and diamine of the obtained polyimide precursor (xvi), the solid content of the polyimide precursor (xvi) solution, and the weight average molecular weight.
  • Synthesis Example 17 Synthesis of polyimide precursor (xvii) In a three-necked separable flask, 2.0 g of 1,3-bis (3-aminophenoxy) benzene, 19.9 g of polytetramethylene oxide-di-p-aminobenzoate, ⁇ -butyrolactone 74.4 g was added and stirred until a homogeneous solution was obtained. Next, 10 g of ethylenediol-bis-trimellitic acid ester was added, and the mixture was stirred for 1 hour with ice cooling and then for 6 hours at room temperature. Next, a polyimide precursor (xvii) was obtained by pressure filtration of the product with a 5 ⁇ m filter. Table 1 shows the molar ratio between the acid dianhydride and diamine of the obtained polyimide precursor (xvii), the solid content of the polyimide precursor (xvii) solution, and the weight average molecular weight.
  • a photosensitive polyimide precursor composition First, a predetermined amount of polyimide precursor is subdivided into a container such as a glass bottle. Next, a predetermined amount of additives such as a photosensitizer and a dissolution inhibitor are blended, and the mixture is stirred with a mix rotor until uniform. By these operations, a photosensitive polyimide precursor composition can be obtained.
  • additives such as a photosensitizer and a dissolution inhibitor
  • Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 95 ° C. for 30 minutes.
  • Molecular weight measurement 0.01 g of the photosensitive polyimide precursor composition obtained after solvent removal was measured with a precision balance and dissolved in 10 g of dimethylformamide (Wako Pure Chemical Industries, Ltd.). This solution was filtered through a 10 ⁇ m filter, and the molecular weight was measured by gel permeation chromatography (manufactured by JASCO Corporation) equipped with TSK-GEL SUPER HM-H (trade name, manufactured by Tosoh Corporation).
  • Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 95 ° C. for 30 minutes.
  • Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 95 ° C. for 30 minutes.
  • Vacuum press Using a polyimide film (Kapton EN-100, trade name, manufactured by Toray DuPont) as a base material, the photosensitive dry film obtained in the solvent removal process by a vacuum press (SA-501, manufactured by Tester Sangyo Co., Ltd.) Vacuum pressing was performed under the conditions of a pressing temperature of 100 ° C., a pressing pressure of 0.5 MPa, a degree of vacuum of 15 kPa, and a pressing time of 1 minute.
  • SA-501 manufactured by Tester Sangyo Co., Ltd.
  • Measurement of warpage The film obtained after baking was cut into a length of 5 cm and a width of 5 cm, static electricity was removed, and the warpage of the film was measured using a ruler.
  • Example 2 Evaluation of Photosensitive Polyimide Precursor Composition Using 3′-Hydroxyacetanilide as Dissolution Inhibitor 10 g of the polyimide precursor solution obtained in Synthesis Examples 1 to 3 and 20 parts by mass with respect to the polyimide precursor solid content as a photosensitive agent 0.42 g of the quinonediazide compound (formula 16) and 12.5 parts by mass of 3′-hydroxyacetanilide 0.26 g with respect to the polyimide precursor were mixed in the ratio shown in Table 3, and placed in a 20 cc glass bottle. No. 5 manufactured by ASONE Co., Ltd.) until stirring to obtain a photosensitive polyimide precursor composition (4 to 6). The evaluation results are shown in Table 3.
  • the photosensitive polyimide precursor composition When used for a cover film of a flexible printed wiring board, it is necessary to obtain a desired pattern by lithography with a developer composed of an alkaline aqueous solution. In addition to the fact that the molecular weight of the composition does not change over time, it is excellent in tackiness, the laminate in which the cover film is laminated after baking is not warped, and peels off even when bent and cracks occur. There are demands for performance such as lack of heat and the ability of the laminate to burn.
  • Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 95 ° C. for 30 minutes.
  • Molecular weight measurement 0.01 g of the photosensitive polyimide precursor composition obtained after solvent removal was measured with a precision balance and dissolved in 10 g of dimethylformamide (Wako Pure Chemical Industries, Ltd.). This solution was filtered through a 10 ⁇ m filter, and the molecular weight was measured by gel permeation chromatography (manufactured by JASCO Corporation) equipped with TSK-GEL SUPER HM-H (trade name, manufactured by Tosoh Corporation).
  • Lithographic performance evaluation Coating A polyester film (manufactured by Unitika) was placed on a coating table (manufactured by Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, and the polyester film was adhered by vacuum-adsorbing. On the polyester film, the photosensitive polyimide precursor composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 67.5 ⁇ m.
  • Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 95 ° C. for 30 minutes.
  • Vacuum press First, FCCL was washed with a 15 wt% sodium persulfate aqueous solution. Next, the photosensitive dry film obtained in the solvent removal step was subjected to a press temperature of 100 ° C., a press pressure of 0.5 MPa, a vacuum degree of 15 kPa, and a press time of 1 minute using a vacuum press machine (SA-501, manufactured by Tester Sangyo Co., Ltd.). A vacuum press was performed.
  • SA-501 manufactured by Tester Sangyo Co., Ltd.
  • Actinic ray irradiation The support film of the laminate obtained in the vacuum pressing process was peeled off, and irradiated with ultraviolet rays under an exposure amount of 1.5 J / cm 2 using an ultrahigh pressure mercury lamp (manufactured by HMW-201KB Oak).
  • Lithography Using a spray-type developing machine, a time until a UV irradiation part is completely dissolved under the conditions of a developing temperature of 30 ° C. and a spray pressure of 0.18 MPa using a 1 wt% sodium carbonate aqueous solution as a developing solution (hereinafter referred to as a breakpoint) To be described). Next, development was performed with a development time 1.2 times the breakpoint. After development, washing was performed for 1/3 of the development time with distilled water in a spray type washer, and further for 30 seconds with a 0.2 wt% aqueous sulfuric acid solution.
  • Lithographic performance Lithographic performance was judged by development time, remaining film rate and pattern shape.
  • Development time A photosensitive polyimide precursor composition having a development time of 90 seconds or less was indicated by ⁇ , and a photosensitive polyimide precursor composition having a development time exceeding 90 seconds was indicated by ⁇ .
  • Pattern shape The pattern after lithography was observed using a light microscope (ECLIPS LV100, manufactured by Nikon Corp.) with a bright field at 100 times the shape of a 100 ⁇ m circle pattern. An object holding the shape of the pattern was indicated as “ ⁇ ”, and an object that collapsed was indicated as “X”.
  • Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 95 ° C. for 30 minutes.
  • Evaluation of tackiness The presence or absence of tackiness of the photosensitive layer after solvent removal was evaluated by palpation. Those with fingerprints were marked with ⁇ , and those without fingerprints were marked with ⁇ .
  • Warpage evaluation Coating A polyester film (manufactured by Unitika Ltd.) was placed on a coating table (manufactured by Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, and the polyester film was adhered by vacuum-adsorbing. On the polyester film, the photosensitive polyimide precursor composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 67.5 ⁇ m.
  • Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 95 ° C. for 30 minutes.
  • Vacuum press Using a polyimide film (Kapton EN-100, trade name, manufactured by Toray DuPont) as a base material, the photosensitive dry film obtained in the solvent removal process by a vacuum press (SA-501, manufactured by Tester Sangyo Co., Ltd.) Vacuum pressing was performed under the conditions of a pressing temperature of 100 ° C., a pressing pressure of 0.5 MPa, a degree of vacuum of 15 kPa, and a pressing time of 1 minute.
  • SA-501 manufactured by Tester Sangyo Co., Ltd.
  • Measurement of warpage The film obtained after baking was cut into a length of 5 cm and a width of 5 cm, static electricity was removed, and the warpage of the film was measured using a ruler.
  • Vacuum press Using a polyimide film (Kapton EN-100, trade name, manufactured by Toray DuPont) as a base material, the photosensitive dry film obtained in the solvent removal process was obtained using a vacuum press (SA-501 Tester Sangyo Co., Ltd.). Vacuum pressing was performed on both sides of the polyimide film under the conditions of a pressing temperature of 100 ° C., a pressing pressure of 0.5 MPa, a degree of vacuum of 15 kPa, and a pressing time of 1 minute.
  • Examples 1 to 3 using the polyimide precursor according to the present invention show no decrease in molecular weight (M2 / M1). Moreover, the goby folding strength was also good. This result is considered to be because by using the acid dianhydride according to the present invention, decomposition of the polyimide precursor at the time of solvent removal was suppressed and molecular weight reduction was suppressed. On the other hand, in Comparative Examples 1 to 3 using other acid dianhydrides, it can be seen that the molecular weight decreases and the goby folding strength decreases.
  • Examples 4 to 22 using the polyimide precursor composition according to the present invention show that the remaining film ratio is good. . In particular, in Example 8, the remaining film ratio is 90% without adding a dissolution inhibitor. These results are considered to be because decomposition of the polyimide precursor in the development process was suppressed by using the acid dianhydride according to the present invention. Examples 4 to 22 show that the tackiness is also good. On the other hand, under any conditions using other acid dianhydrides, the remaining film ratio is reduced, indicating that the tackiness is poor.
  • the polyimide precursor of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, a rewiring insulating film, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper-clad plate, Moreover, it can utilize suitably as a liquid crystal aligning film etc.

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  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)
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  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

L'invention porte sur un précurseur de polyimide qui permet la fabrication d'un film sec photosensible tel qu'un film qui ne présente pas de caractère collant, qui ne provoque pas de craquelure dans une couche photosensible de celui-ci lorsqu'il est plié après élimination d'un solvant de celui-ci et qui permet de réaliser une bonne lithographie sur celui-ci ; qui peut être appliqué à un circuit imprimé flexible (FPC) qui provoque moins de gondolage après cuisson ; et qui peut présenter un caractère ignifuge sans avoir besoin d'y ajouter un quelconque composé halogéné. L'invention porte également sur une composition de précurseur de polyimide photosensible. L'invention porte en outre sur un film sec photosensible. L'invention porte encore en outre sur une carte de circuits imprimés flexible produite à l'aide de l'une quelconque des matières susmentionnées. Le précurseur de polyimide est caractérisé par le fait qu'il comprend un dianhydride d'acide représenté par la formule générale (1) [dans laquelle X représente un groupe organique divalent ayant un groupe alkylène en C3-30 ; et R1 représente un atome d'hydrogène, un groupe alkyle monovalent en C1-10, un groupe alcoxy ou un groupe halogène].
PCT/JP2009/058159 2008-05-09 2009-04-24 Précurseur de polyimide, composition de précurseur de polyimide photosensible, film sec photosensible et carte de circuits imprimés flexible utilisant ces matières WO2009136557A1 (fr)

Priority Applications (3)

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CN2009801157178A CN102015835A (zh) 2008-05-09 2009-04-24 聚酰亚胺前体、感光性聚酰亚胺前体组合物、感光性干膜及使用它们的柔性印刷布线基板
JP2010511044A JP5417323B2 (ja) 2008-05-09 2009-04-24 感光性ポリイミド前駆体組成物、感光性ドライフィルム及びフレキシブルプリント配線基板
KR1020107024194A KR101308811B1 (ko) 2008-05-09 2009-04-24 폴리이미드 전구체, 감광성 폴리이미드 전구체 조성물, 감광성 드라이 필름 및 그들을 사용한 플렉시블 프린트 배선 기판

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WO2011135887A1 (fr) * 2010-04-28 2011-11-03 旭化成イーマテリアルズ株式会社 Composition de résine photosensible
JP2012185291A (ja) * 2011-03-04 2012-09-27 Nof Corp 感光性樹脂組成物およびその用途
JP2012247762A (ja) * 2011-05-31 2012-12-13 Sumitomo Bakelite Co Ltd ポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜、半導体装置、および表示体装置
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
JP2013174774A (ja) * 2012-02-27 2013-09-05 Nof Corp 感光性樹脂組成物およびその用途
JP2014205827A (ja) * 2013-03-21 2014-10-30 東洋紡株式会社 透明ポリエステルイミド樹脂フィルム、並びにこれに用いる樹脂および樹脂組成物
WO2015199219A1 (fr) * 2014-06-27 2015-12-30 富士フイルム株式会社 Générateur de base thermique, composition de résine thermodurcissable, film durci, procédé de fabrication de film durci, et dispositif semi-conducteur
WO2019107250A1 (fr) * 2017-11-28 2019-06-06 旭化成株式会社 Composition de résine photosensible de type négative ainsi que procédé de fabrication de celle-ci, et procédé de fabrication de motif en relief durci
WO2022039028A1 (fr) * 2020-08-17 2022-02-24 東レ株式会社 Composition de résine photosensible, produit durci, dispositif d'affichage, dispositif à semi-conducteur et procédé de production dudit produit durci
US11687002B2 (en) 2020-07-30 2023-06-27 Lg Chem, Ltd. Binder resin, positive-type photosensitive resin composition, insulating film and semiconductor device

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JP6958332B2 (ja) * 2017-12-20 2021-11-02 Ｈｄマイクロシステムズ株式会社 感光性樹脂組成物、パターン硬化膜の製造方法、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品
CN110857332B (zh) * 2018-08-22 2022-10-21 臻鼎科技股份有限公司 高分子树脂、高分子树脂组合物及覆铜板
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WO2011059089A1 (fr) * 2009-11-16 2011-05-19 旭化成イーマテリアルズ株式会社 Précurseur de polyimide et composition de résine photosensible contenant le précurseur de polyimide
JP5758300B2 (ja) * 2009-11-16 2015-08-05 旭化成イーマテリアルズ株式会社 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
WO2011135887A1 (fr) * 2010-04-28 2011-11-03 旭化成イーマテリアルズ株式会社 Composition de résine photosensible
JP2012027490A (ja) * 2010-04-28 2012-02-09 Asahi Kasei E-Materials Corp 感光性樹脂組成物
CN102439520A (zh) * 2010-04-28 2012-05-02 旭化成电子材料株式会社 感光性树脂组合物
CN102439520B (zh) * 2010-04-28 2014-08-27 旭化成电子材料株式会社 感光性树脂组合物
JP2012185291A (ja) * 2011-03-04 2012-09-27 Nof Corp 感光性樹脂組成物およびその用途
JP2012247762A (ja) * 2011-05-31 2012-12-13 Sumitomo Bakelite Co Ltd ポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜、半導体装置、および表示体装置
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
JP2013174774A (ja) * 2012-02-27 2013-09-05 Nof Corp 感光性樹脂組成物およびその用途
JP2014205827A (ja) * 2013-03-21 2014-10-30 東洋紡株式会社 透明ポリエステルイミド樹脂フィルム、並びにこれに用いる樹脂および樹脂組成物
WO2015199219A1 (fr) * 2014-06-27 2015-12-30 富士フイルム株式会社 Générateur de base thermique, composition de résine thermodurcissable, film durci, procédé de fabrication de film durci, et dispositif semi-conducteur
JPWO2015199219A1 (ja) * 2014-06-27 2017-06-01 富士フイルム株式会社 熱塩基発生剤、熱硬化性樹脂組成物、硬化膜、硬化膜の製造方法および半導体デバイス
WO2019107250A1 (fr) * 2017-11-28 2019-06-06 旭化成株式会社 Composition de résine photosensible de type négative ainsi que procédé de fabrication de celle-ci, et procédé de fabrication de motif en relief durci
JPWO2019107250A1 (ja) * 2017-11-28 2020-07-27 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
TWI700554B (zh) * 2017-11-28 2020-08-01 日商旭化成股份有限公司 負型感光性樹脂組合物及其製造方法、及硬化浮凸圖案之製造方法
US11687002B2 (en) 2020-07-30 2023-06-27 Lg Chem, Ltd. Binder resin, positive-type photosensitive resin composition, insulating film and semiconductor device
WO2022039028A1 (fr) * 2020-08-17 2022-02-24 東レ株式会社 Composition de résine photosensible, produit durci, dispositif d'affichage, dispositif à semi-conducteur et procédé de production dudit produit durci

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JP2013241607A (ja) 2013-12-05
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CN102015835A (zh) 2011-04-13
JP5603977B2 (ja) 2014-10-08

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