WO2012098734A1 - 樹脂組成物、硬化物、樹脂フィルム及び配線板 - Google Patents

樹脂組成物、硬化物、樹脂フィルム及び配線板 Download PDF

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WO2012098734A1
WO2012098734A1 PCT/JP2011/071494 JP2011071494W WO2012098734A1 WO 2012098734 A1 WO2012098734 A1 WO 2012098734A1 JP 2011071494 W JP2011071494 W JP 2011071494W WO 2012098734 A1 WO2012098734 A1 WO 2012098734A1
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compound
resin composition
group
polyimide
polyfunctional
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PCT/JP2011/071494
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English (en)
French (fr)
Japanese (ja)
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足立　弘明
透 日下部
洋朗 佐々木
山本　正樹
康史 飯塚
華菜子 水村
下田　浩一朗
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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 CN201180061317.0A priority Critical patent/CN103270070B/zh
Priority to KR1020137016231A priority patent/KR101516103B1/ko
Priority to JP2012553556A priority patent/JP5820825B2/ja
Publication of WO2012098734A1 publication Critical patent/WO2012098734A1/ja

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    • 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
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/60—Polyamides or polyester-amides
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • 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
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a resin composition useful as a material for a surface protective film of a semiconductor element, an interlayer insulating film, a semiconductor package substrate, a bonding sheet, and a protective insulating film for a printed wiring board, a cured product using the resin composition, and a resin composition
  • the present invention relates to a resin film using, and a wiring board using them.
  • polyimide resin compositions As a material for the surface protection film of semiconductor elements, interlayer insulation films, and protection insulation films for printed wiring boards, polyimide resin compositions having excellent heat resistance are being used. In particular, when a polyimide resin composition is used as an insulating material for a flexible printed wiring board, it is required that there is little warpage after curing in addition to heat resistance.
  • a polyimide-based ink composed of an ester-terminated oligomer and an amine-terminated oligomer has been proposed as a polyimide-based resin composition that has excellent heat resistance and can reduce warping after curing (see, for example, Patent Document 1).
  • the polyimide-based ink described in Patent Document 1 is used after being applied onto a flexible wiring circuit and then heat-treated at a temperature of 250 ° C. or higher to be imidized.
  • the polyimide resin to be formed contracts due to the stress caused by the ring closure reaction accompanying solvent removal and oligomer imidization. For this reason, suppression of curvature is not necessarily sufficient, and a problem also arises in workability.
  • copper foil is used as the circuit material, there is a problem that the carboxyl group and the wiring material react with each other by heat treatment at 250 ° C. or more, and the wiring material is oxidized.
  • polyimide precursors that can be imidized at low temperatures and can reduce warping after curing have been developed.
  • examples of such polyimide precursors include non-silicone polyimide precursors using alkyl ether diamines (for example, see Patent Document 2), and silicone-based polyimide precursors using diaminosiloxane as a diamine component (for example, patents). Reference 3 and Patent Document 4).
  • the polyimide precursor described in Patent Document 2 has a polyamic acid structure derived from an alkyl ether diamine and a polyimide structure derived from an aromatic diamine as structural units. For this reason, when it uses for the insulating material of a flexible printed wiring board as a polyimide-type resin composition, the polyimide site
  • the polyimide precursors described in Patent Document 3 and Patent Document 4 are silicone-based polyimide precursors, they are applied to a circuit board as a polyimide-based resin composition and imidized to form a circuit protective film.
  • the silicone part segregates on the surface in the subsequent prepreg or bonding process, and the surface of the protective film may have low surface tension and high water repellency, which may repel the adhesive component. For this reason, the adhesive force between a protective film and an adhesive sheet is insufficient, and there is a problem that sufficient performance as a protective film is not necessarily obtained.
  • the present invention has been made in view of the above points, and can reduce warping during curing, has excellent heat resistance, and is a surface protective film for semiconductor elements, an interlayer insulating film, a protective insulating film for printed wiring boards, and an interlayer insulating film. It aims at providing the resin composition which can be used conveniently as materials, such as a film
  • the resin composition of the present invention comprises (A) a polymer compound, (B) a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups, and (C) the polymer compound and / or the polyfunctional hydroxyl group-containing compound.
  • the polymer compound has an imide group and / or an amide group, and the three-dimensional crosslinking includes a C ⁇ O group and / or an NH group.
  • the polyfunctional hydroxyl group-containing compound and / or the polyfunctional crosslinkable compound is preferably trifunctional or more.
  • the polymer compound preferably has a hydroxyl group and / or a carboxyl group.
  • the polyfunctional hydroxyl group-containing compound includes at least one selected from both-end phenol-modified silicone, polybutadiene polyol, hydrogenated polybutadiene polyol, and polycarbonate polyol.
  • the polyfunctional hydroxyl group-containing compound preferably has an aliphatic structure.
  • the polyfunctional hydroxyl group-containing compound is preferably a polycarbonate polyol.
  • the resin composition of the present invention preferably contains a polyfunctional isocyanate compound having two or more isocyanate groups as the polyfunctional crosslinkable compound.
  • the polyfunctional crosslinkable compound preferably contains two or more blocked isocyanate groups.
  • the content of the polyfunctional hydroxyl group-containing compound is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polymer compound.
  • the content of the polyfunctional crosslinkable compound is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polymer compound.
  • the polyfunctional hydroxyl group-containing compound preferably has a number average molecular weight of 500 to 3,000.
  • the said high molecular compound has a repeating structure represented by following General formula (1).
  • Y 1 represents a divalent organic group
  • Z 1 represents a tetravalent organic group
  • a represents an integer of 1 to 50.
  • the polymer compound is preferably polyimide.
  • the said high molecular compound has a repeating structure represented by following General formula (2).
  • Z 1 and Z 2 represent a tetravalent organic group, and Y 1 , Y 2 , Y 3 , Y 4 , and Y 5 are each independently 1 to 5 carbon atoms. And may be branched.
  • B, c and d each independently represents an integer of 1 to 50.
  • the polymer compound may have a polyimide structure represented by the following general formula (3) and a polyamic acid structure represented by the following general formula (4) as repeating structural units, respectively. preferable.
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom.
  • it represents a monovalent organic group having 1 to 20 carbon atoms
  • R 3 , R 6 , R 9 , R 12 , and R 15 are each independently 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 tetravalent organic group
  • R 17 represents a divalent group having 1 to 90 carbon atoms. Represents an organic group of
  • the diamine represented by the following general formula (5) is included as a diamine component which comprises the polyimide represented by the said General formula (3).
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms
  • R 3 , R 6 , R 9 , R 12 , and R 15 each independently represents a tetravalent organic group having 1 to 20 carbon atoms
  • N and p are each independently an integer of 0 or more and 30 or less and satisfy 1 ⁇ (m + n + p) ⁇ 30.)
  • the polymer compound preferably has a structure represented by the following general formula (6) as a repeating unit.
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms
  • R 3 , R 6 , R 9 , R 12 , and R 15 represent a tetravalent organic group having 1 to 20 carbon atoms
  • m, n, p Each independently represents an integer of 0 to 30.
  • R 16 represents a tetravalent organic group
  • R 17 represents a divalent organic group having 1 to 90 carbon atoms
  • A, B, C represents mol% of each unit and satisfies 0.10 ⁇ (A + B) / (A + B + C) ⁇ 0.85.
  • the polymer compound preferably has a polyimide structure represented by the following general formula (7) and a polyamic acid structure represented by the following general formula (8) as structural units.
  • Z 3 and Z 4 are tetravalent organic groups derived from tetracarboxylic dianhydride represented by the following General Formula (9), and are the same as each other.
  • R 18 is a divalent organic group having 1 to 30 carbon atoms
  • R 19 is a monovalent organic group having 1 to 30 carbon atoms
  • e is 1 or more and 20 Represents the following integers.
  • the resin composition of the present invention preferably contains (D) a (meth) acrylate compound having two or more unsaturated groups capable of photopolymerization and (E) a photopolymerization initiator.
  • the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds preferably includes a (meth) acrylate compound having three or more double bonds.
  • the compound represented by following General formula (10) is included as a (meth) acrylate compound which has three or more of the said double bonds.
  • R 20 represents a hydrogen atom or a methyl group, and a plurality of E's each independently represents an alkylene group having 2 to 5 carbon atoms, which may be the same or different.
  • f is an integer of 1 to 10.
  • the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is a (meth) acrylate compound having two double bonds and three double bonds. It is preferable to contain the (meth) acrylate compound having the above.
  • the resin composition of the present invention preferably contains (F) a phosphorus compound.
  • the resin composition of the present invention has an interlayer insulation resistance of 10 9 ⁇ or more in an insulation reliability test at a temperature of 85 ° C., a humidity of 85%, and 1000 hours, and a viscosity at 120 ° C. to 220 ° C. of 5000 Pa ⁇ S to 100000 Pa ⁇ S. And having an elastic region with an elongation of less than 20% and a plastic region with an elongation of 50% or more, and the film thickness of the interlayer insulating layer is 40 ⁇ m or less.
  • the cured product of the present invention is obtained by heating the resin composition at 100 ° C. to 130 ° C. for 5 minutes to 60 minutes and then heating at 160 ° C. to 200 ° C. for 15 minutes to 60 minutes. .
  • the resin film of the present invention includes a base material and the resin composition provided on the base material.
  • the substrate is preferably a carrier film.
  • the resin film of the present invention preferably includes a cover film provided on the resin composition.
  • the base material is preferably a copper foil.
  • the wiring board of the present invention is characterized by comprising a base material having wiring and the resin composition provided so as to cover the wiring.
  • warpage during curing can be reduced, heat resistance is excellent, and it can be suitably used as a material for a surface protection film of a semiconductor element, an interlayer insulating film, a protective insulating film for a printed wiring board, an interlayer insulating film, and the like.
  • a resin composition, a resin film using the resin composition, and a wiring board using them can be provided.
  • Epoxy resins and polyimide resins are used in the manufacturing process of flexible printed circuit boards, but when using an epoxy resin as a protective film, the high insulation reliability required for thinning the flexible printed circuit board , Flexibility, low resilience, and flame retardancy are not always sufficiently obtained. Moreover, since epoxy resin has reactivity, it lacks storage stability. In addition, even when a conventional polyimide resin is used, a polyimide resin that can realize a reduction in warpage and heat resistance is expensive, and a resin composition that has a good reduction in warpage and heat resistance of a cured product accompanying imidization. Is desired.
  • the present inventors paid attention to a polyfunctional crosslinkable compound capable of forming a three-dimensional crosslink with a polymer compound or a polyfunctional hydroxyl group-containing compound. And the present inventors heated the resin composition containing a polymer compound and / or a polyfunctional hydroxyl group-containing compound and a polyfunctional crosslinkable compound, thereby producing a polyfunctional crosslinkable compound and a polyfunctional hydroxyl group-containing compound. The idea was to form a three-dimensional network by three-dimensional crosslinking formed between the two. Furthermore, the present inventors have found that this three-dimensional network can reduce warping during curing and can realize a resin composition having excellent heat resistance, and have completed the present invention.
  • the resin composition according to the present invention includes (A) a polymer compound, (B) a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups, and (C) a polymer compound and / or a polyfunctional hydroxyl group-containing compound.
  • a three-dimensional bridge can be formed.
  • the polymer compound has an imide group and / or an amide group
  • the three-dimensional crosslinking formed between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound is C ⁇ O. It preferably contains groups and / or NH groups.
  • an interaction mainly including hydrogen bonding occurs between the C ⁇ O group and / or NH group included in the three-dimensional crosslinking and the imide group and / or amide group of the polymer compound.
  • the compatibility between the compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound is further improved. Thereby, the curvature at the time of hardening can be reduced more and heat resistance improves further.
  • the polyfunctional hydroxyl group-containing compound and / or the polyfunctional crosslinkable compound is trifunctional or more.
  • a plurality of hydroxyl groups of the polyfunctional hydroxyl group containing compound and a plurality of crosslinkable functional groups of the polyfunctional crosslinkable compound for example, , An isocyanate group, an oxazoline group
  • a three-dimensional network including a plurality of C ⁇ O groups and / or NH groups
  • shrinkage of the polymer compound can be suppressed by a three-dimensional network between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound formed without using the polymer compound, and sufficient warpage can be reduced. And excellent heat resistance is exhibited.
  • the shrinkage of the polymer compound is suppressed by the three-dimensional network formed between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound.
  • the effects of the present invention can be achieved without being limited by the molecular structure of the polymer compound. For this reason, for example, even when an inexpensive polymer compound having no complicated molecular structure is used, warpage during curing of the resin composition can be reduced, and excellent heat resistance is exhibited.
  • the polymer compound has a hydroxyl group and / or a carboxyl group.
  • the hydroxyl group and / or carboxyl group of the polymer compound and the crosslinkable functional group of the polyfunctional crosslinkable compound for example, isocyanate group, oxazoline.
  • Crosslinks are also formed between these groups.
  • a three-dimensional network is formed between the polymer compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound via the polymer compound.
  • the compatibility of the functional compound is improved, and the shrinkage of the polymer compound can be further suppressed. In particular, the warpage during curing of the resin composition can be reduced, and excellent heat resistance is exhibited.
  • three-dimensional crosslinking is formed via the polymer compound, so that at least one of the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinking compound is not trifunctional or higher. In both cases, a three-dimensional network can be formed. Moreover, since a three-dimensional network is formed via the polymer compound, the compatibility between the polymer compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound is further improved. For this reason, even when a polymer compound having low compatibility with the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound is used, a practical resin composition that can be used in the production process of a flexible printed wiring board is obtained. .
  • each component will be described in detail.
  • polymer compound As the polymer compound, various polymer compounds can be used as long as the effects of the present invention are exhibited.
  • the polymer compound include polyamide, polyamideimide, polyamic acid, polyimide obtained by imidizing polyamic acid, and the like.
  • the term “polyimide” includes both a polyimide precursor in which a part of polyamic acid is imidized with all polyamic acids and a polyimide in which all polyamic acids are imidized.
  • the polymer compound is not limited to the molecular structure, and various polymer compounds such as polyimide described above can be used. Among these, as the polymer compound, it is preferable to use polyimide from the viewpoints of heat resistance and moisture absorption resistance.
  • a polymer compound having a hydroxyl group and / or a carboxyl group in the molecular chain is used.
  • a polymer compound polyamic acid, polyimide having a hydroxyl group or a carboxyl group in a molecular chain, or the like can be used.
  • Polyimide is obtained by reacting acid dianhydride and diamine.
  • polyimide for example, polyimide having mainly a polyimide structure as a repeating structural unit may be used, or polyimide having a polyimide structure and a polyamic acid structure as repeating structural units may be used.
  • polymer compound for example, a compound having a repeating structural unit represented by the following general formula (1) can be used.
  • Y 1 represents a divalent organic group
  • Z 1 represents a tetravalent organic group
  • a represents an integer of 1 to 50.
  • the non-silicone-type polyimide obtained by making alkyl ether diamine and acid dianhydride react The silicone type obtained by making diaminosiloxane and acid dianhydride react.
  • the polyimide may be used.
  • the polymer compound it is preferable to use a compound having a repeating structure represented by the following general formula (2). Since the polymer compound has an oxyalkylene group, the molecular chain is given flexibility and the solvent solubility of the polymer compound is improved.
  • Z 1 and Z 2 represent a tetravalent organic group, and Y 1 , Y 2 , Y 3 , Y 4 , and Y 5 are each independently 1 to 5 carbon atoms. And may be branched.
  • B, c and d each independently represents an integer of 1 to 50.
  • each the polyimide structure represented by following General formula (3), and the polyamic acid structure represented by following General formula (4) as a repeating structural unit.
  • This polymer compound contains an alkyl ether structure in the polyimide structure and a polyamic acid structure, so that flexibility is imparted to the molecular chain without impairing the molecular weight stability, thereby improving development stability.
  • the carboxyl group of the polyamic acid structure contained in the following general formula (4) reacts with the crosslinkable functional group (for example, isocyanate group, oxazoline group, etc.) of the polyfunctional crosslinkable compound.
  • the crosslinkable functional group for example, isocyanate group, oxazoline group, etc.
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom.
  • R 3 , R 6 , R 9 , R 12 , and R 15 are each independently 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 tetravalent organic group, and R 17 represents a divalent group having 1 to 90 carbon atoms. Represents an organic group of
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom or a carbon atom having 1 to carbon atoms.
  • R 3 , R 6 , R 9 , R 12 and R 15 each independently represents a tetravalent organic group having 1 to 20 carbon atoms, m, n , P are each independently an integer of 0-30, which satisfies 1 ⁇ (m + n + p) ⁇ 30.)
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms
  • R 3 , R 6 , R 9 , R 12 , and R 15 represent a tetravalent organic group having 1 to 20 carbon atoms
  • m, n, p Each independently represents an integer of 0 or more and 30 or less
  • R 16 represents a tetravalent organic group
  • R 17 represents a divalent organic group having 1 to 90 carbon atoms.
  • C represents mol% of each unit, and satisfies 0.10 ⁇ (A + B) / (A + B + C) ⁇ 0.85.)
  • the alkyl ether structure in the molecular chain is increased, and the molecular chain of the polymer compound is increased. Since the flexibility is improved, warping after curing can be reduced. Further, by satisfying (A + B) / (A + B + C) ⁇ 0.85, the carboxyl group in the molecular chain increases, so that the solubility of the cured product in the alkaline developer is developed and the developability is improved.
  • a high molecular compound it is preferable to use what has a polyimide structure represented by the following general formula (7) and a polyamic acid structure represented by the following general formula (8) as a repeating structural unit.
  • the siloxane part is contained in the polyimide structure, the polyimide structure is imparted with appropriate flexibility, so that the shrinkage of the molecular chain of the high molecular compound can be suppressed, and the warpage after curing can be suppressed.
  • Z 3 and Z 4 are tetravalent organic groups derived from tetracarboxylic dianhydride represented by the following general formula (9), and are the same as each other.
  • R 18 is a divalent organic group having 1 to 30 carbon atoms
  • R 19 is a monovalent organic group having 1 to 30 carbon atoms
  • e is 1 or more and 20 or less. Represents an integer.
  • a polyamic acid structure is used.
  • the carboxyl group contained in reacts with the crosslinkable functional group (for example, isocyanate group) of the polyfunctional crosslinkable compound.
  • a high molecular compound is taken in into the three-dimensional network between a polyfunctional hydroxyl-containing compound and a polyfunctional crosslinkable compound, and can suppress the segregation to the surface of the hardened
  • a good adhesive force can be obtained even when a protective film is used.
  • polyfunctional hydroxyl group-containing compound a common polyfunctional hydroxyl group-containing compound can be used in the resin composition according to the first and second embodiments.
  • polyfunctional hydroxyl group-containing compound various hydroxyl group-containing compounds can be used as long as they have two or more hydroxyl groups in the molecular chain within the scope of the effects of the present invention.
  • polyfunctional hydroxyl group-containing compound for example, various diols as a bifunctional hydroxyl group-containing compound containing two hydroxyl groups may be used, or various polyols containing three or more hydroxyl groups may be used.
  • polyfunctional hydroxyl group-containing compound for example, polyfunctional isocyanate or polyfunctional oxazoline compound
  • polyfunctional crosslinkable compound for example, polyfunctional isocyanate or polyfunctional oxazoline compound
  • the polyfunctional hydroxyl group-containing compound preferably contains at least one selected from both-ends phenol-modified silicones, polybutadiene polyols, hydrogenated polybutadiene polyols, and polycarbonate polyols from the viewpoint of enhancing insulation.
  • a polyfunctional hydroxyl-containing compound what has an aliphatic structure is preferable. Thereby, since water resistance improves and it becomes low elasticity, curvature and insulation reliability can be improved.
  • the polyfunctional hydroxyl group-containing compound among the specific examples given above, hydrogenated polybutadiene polyol and polycarbonate polyol are preferable, and polycarbonate polyol is preferably used from the viewpoint of reducing warpage.
  • the content of the polyfunctional hydroxyl group-containing compound is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polyimide.
  • the polyfunctional hydroxyl group-containing compound is 5 parts by mass or more, sufficient crosslinking can be formed with the polyfunctional crosslinkable compound, so that it is possible to reduce warpage during curing.
  • the excessive hydroxyl group in a resin composition reduces because a polyfunctional hydroxyl-containing compound is 60 mass parts or less, the insulation reliability after hardening of a resin composition improves.
  • the content of the polyfunctional hydroxyl group-containing compound is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyimide.
  • the polyfunctional hydroxyl group-containing compound those having a number average molecular weight of 500 to 3000 are preferably used.
  • the number average molecular weight means the number average molecular weight of styrene conversion molecular weight measured by gel permeation chromatography. If the polyfunctional hydroxyl group-containing compound has a number average molecular weight of 500 or more, the resin composition has low elasticity, and thus warpage can be reduced. Moreover, since the viscosity of a resin composition can be reduced if the number average molecular weight of a polyfunctional hydroxyl-containing compound is 3000 or less, the embedding property to the wiring part and through-hole part of a wiring board becomes favorable. Furthermore, the number average molecular weight of the polyfunctional hydroxyl group-containing compound is preferably 500 to 2,000 from the viewpoint of low elasticity and viscosity reduction of the resin composition.
  • polyfunctional crosslinkable compound As a polyfunctional crosslinkable compound, the common polyfunctional crosslinkable compound can be used in the resin composition which concerns on a 1st aspect and a 2nd aspect.
  • various polyfunctional crosslinkable compounds can be used as long as they have two or more crosslinkable functional groups within the scope of the effects of the present invention.
  • the crosslinkable functional group refers to a functional group capable of forming a crosslink between the hydroxyl group or carboxyl group of the polymer compound and the hydroxyl group of the polyfunctional hydroxyl group-containing compound.
  • the crosslinkable functional group include, but are not limited to, an isocyanate group and an oxazoline group.
  • the bifunctional crosslinkable compound which has two crosslinkable functional groups may be used, and the crosslinkable compound which has 3 or more crosslinkable functional groups may be used.
  • the polyfunctional crosslinking compound include a polyfunctional isocyanate compound having two or more isocyanate groups and a polyfunctional oxazoline compound having two or more oxazoline groups.
  • the polyfunctional crosslinkable compound it is preferable to use a polyfunctional isocyanate compound containing two or more isocyanate groups. With this configuration, a three-dimensional network is formed via a urethane bond between the isocyanate group of the polyfunctional isocyanate compound and the hydroxyl group of the polyfunctional hydroxyl group-containing compound, and the imide group and amide group contained in the polymer compound. Alternatively, an interaction due to a hydrogen bond occurs between a hydroxyl group and a carboxyl group and a C ⁇ O group and an NH group contained in the urethane structure.
  • the low resilience of the resin composition can be improved, and appropriate fluidity is expressed in the resin composition by combining the plasticity of the polymer compound and the elasticity of the resin composition.
  • two conflicting physical properties (fluidity and viscosity) required when the resin composition is used as an interlayer insulating film of a multilayer flexible printed wiring board can be achieved. Performance can be ensured.
  • the polyfunctional isocyanate compound various isocyanate compounds can be used as long as they have two or more isocyanate groups within the scope of the effects of the present invention.
  • the resin composition according to the present invention is used as an interlayer insulating film such as a multilayer flexible wiring board
  • the resin composition is required to flow into the wiring part or through-hole part of the wiring board. Is required to be held to some extent without flowing out of the end of the wiring board. This is because the resin composition generally flows out from the end of the wiring board when attempting to sufficiently flow into the through hole in the press process under high pressure, and the thickness of the insulating layer at the end of the wiring board It is because there exists a possibility that insulation may fall and it may become thin.
  • the polyfunctional crosslinkable compound a blocked isocyanate containing a blocked isocyanate group obtained by reacting a blocking agent with a polyfunctional isocyanate compound containing two or more isocyanate groups may be used.
  • the polyfunctional crosslinkable compound contains two or more blocked isocyanate groups from the viewpoints of polymerization by reaction with a hydroxyl group of the polyfunctional hydroxyl group-containing compound, heat resistance improvement by crosslink formation, and chemical resistance. Those that do are preferred.
  • a polyfunctional isocyanate compound or a blocked isocyanate containing two or more isocyanates it is preferable to use a polyfunctional isocyanate compound or a blocked isocyanate containing two or more isocyanates as the polyfunctional hydroxyl group-containing compound.
  • a polyfunctional oxazoline compound having two or more oxazoline groups as the polyfunctional crosslinkable compound.
  • the oxazoline group of the polyfunctional oxazoline compound reacts with the hydroxyl group of the polyfunctional hydroxyl group-containing compound to form an amide bond.
  • the polymer compound has a hydroxyl group or a carboxyl group
  • the oxazoline group of the polyfunctional oxazoline compound reacts with the hydroxyl group or the carboxyl group to contain an amide bond and / or an amide ester (three-dimensional Cross-linking) is formed.
  • a three-dimensional network is formed between the polymer compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound by three-dimensional crosslinking including an amide bond and / or an amide ester.
  • the flexibility of the polyfunctional hydroxyl group-containing compound can be effectively reflected in the polymer compound by the interaction such as hydrogen bond and chemical bond with the polymer compound, and sufficient warpage reduction and excellent heat resistance can be realized.
  • the polyfunctional oxazoline compound various oxazoline compounds can be used as long as they have two or more oxazoline groups as long as the effects of the present invention are achieved.
  • the content of the polyfunctional crosslinkable compound is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polymer compound. If content of a polyfunctional crosslinking compound is 5 mass parts or more, since sufficient bridge
  • the resin composition according to the present invention can be used as a photosensitive resin composition by containing a photosensitizer.
  • a photosensitizer a common photosensitizer can be used in the resin composition according to the first aspect and the second aspect.
  • the photosensitizer is not particularly limited as long as it is a compound having a property that the structure is changed by light irradiation and the solubility in a solvent is changed, and various compounds can be used.
  • the photosensitive agent for example, a (meth) acrylate compound having two or more unsaturated double bonds capable of photopolymerization can be preferably used.
  • 3 double bonds are used as a (meth) acrylate compound which has two or more unsaturated double bonds which can be photopolymerized. It is preferable to include at least one (meth) acrylate compound.
  • the (meth) acrylate compound having three or more double bonds is a compound represented by the following general formula (10).
  • the compound represented by the following general formula (10) is not incorporated into the skeleton of the polymer compound and forms a crosslinked product as the second component, so that the polymer compound can be prevented from shrinking during curing and curving is suppressed. can do.
  • the compound represented by the following general formula (10) does not have a functional group such as a hydroxyl group that reduces electrical insulation, a rigid cross-linked body is formed, and the glass transition point (Tg) of the cured film is formed.
  • R 20 represents a hydrogen atom or a methyl group, and a plurality of E's each independently represents an alkylene group having 2 to 5 carbon atoms, which may be the same or different.
  • F is an integer from 1 to 10.
  • the resin composition of the present invention has two (meth) double bonds as a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds from the viewpoint of developability and insulation reliability. It is preferable to include an acrylate compound and a (meth) acrylate compound having three or more double bonds. Since the (meth) acrylate compound having three or more double bonds forms a rigid cross-linked body with the polyfunctional hydroxyl group-containing compound, the elastic modulus and glass transition point (Tg) of the cured film are increased, and the insulation It is estimated that reliability is improved.
  • (E) Photopolymerization initiator In the resin composition according to the present invention, when the above-described photosensitive agent is used, it is preferably used in combination with a photopolymerization initiator.
  • a photoinitiator the common photoinitiator can be used in the resin composition which concerns on a 1st aspect and a 2nd aspect.
  • the photopolymerization initiator various compounds can be used as long as they are compounds activated by various actinic rays, ultraviolet rays and the like to start polymerization.
  • the photopolymerization initiator for example, oxime esters can be suitably used.
  • the resin composition according to the present invention preferably contains a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds and a photopolymerization initiator. Thereby, it can use suitably as a photosensitive resin composition.
  • the resin composition according to the present invention preferably contains a flame retardant.
  • a flame retardant a common flame retardant can be used in the resin composition according to the first aspect and the second aspect.
  • a halogen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, an inorganic flame retardant, etc. are mentioned.
  • a phosphorus compound if it is a compound which contains a phosphorus atom in a structure as a phosphorus compound, it will not specifically limit.
  • Examples of phosphorus compounds include phosphate ester compounds and phosphazene compounds.
  • One kind of these flame retardants may be used, or two or more kinds may be mixed and used.
  • the addition amount of the flame retardant is not particularly limited, and can be appropriately changed according to the type of the flame retardant used.
  • the resin composition according to the present invention preferably contains a phosphorus compound. Thereby, the flame retardance of a resin composition improves.
  • a phosphoric acid ester compound and / or a phosphazene compound is included as the phosphorus compound.
  • a phosphoric acid ester compound and / or a phosphazene compound is included as the phosphorus compound.
  • a cured product (cured film) can be obtained by heating or drying at a predetermined temperature.
  • cured material can be used as a resin film, for example by apply
  • the photosensitive resin composition containing the photosensitive agent can also be used as a photosensitive film. These resin films and photosensitive films can be suitably used, for example, as an interlayer insulating film / wiring protective film of a flexible printed board.
  • the cured product according to the present invention can be obtained by heating the resin composition at 100 ° C. to 130 ° C. for 5 minutes to 60 minutes and then heating at 160 ° C. to 200 ° C. for 15 minutes to 60 minutes.
  • the resin film according to the present invention includes a base material and a resin composition provided on the base material.
  • a base material copper foil, a carrier film, etc. can be used as a base material.
  • a copper foil is used as a base material, and the resin composition can be provided on the copper foil.
  • the resin composition can use suitably as interlayer insulation films, such as a multilayer flexible wiring board, by providing and drying a resin composition on copper foil.
  • the resin composition according to the present invention since it contains a low molecular weight polyfunctional hydroxyl group-containing compound and a polyfunctional crosslinkable compound that are well compatible with the polymer compound, the viscosity of the resin composition is reduced and the fluidity is reduced. improves. Thereby, in the manufacturing process of the flexible printed wiring board, the through hole provided in the insulating substrate of the wiring board and the embedding property in the wiring pattern are improved, so it is suitable as an interlayer insulating film for multilayer flexible wiring boards and a wiring protective film. Can be used.
  • a double-sided flexible substrate 10 including an insulating substrate 11 and copper foils 12a and 12b provided on both main surfaces of the insulating substrate layer 11 is used for manufacturing a multilayer flexible wiring board.
  • a part of the copper foils 12a and 12b is removed by exposure / development of the dry film and etching of the copper foils 12a and 12b. Hole 13 is formed.
  • copper plating 14 is formed on the surface of the through hole 13 to electrically connect the copper foils 12a and 12b on both sides (see FIG. 1B).
  • the copper foil 12b in the region to be the flexible portion 16 is removed by etching.
  • the resin composition according to the present invention is filled in the through holes 13 and insulated.
  • the resin composition according to the present invention when a polyfunctional isocyanate compound is used as the polyfunctional crosslinkable compound and a hydroxyl group and / or a carboxyl group is used as the polymer compound, the resin composition Appropriate fluidity and viscosity are developed in the object. Thereby, even if the minute through hole 13 is provided, the through hole 13 can be filled.
  • the resin composition according to the present invention when polyimide is used as the polymer compound, imidization after coating becomes unnecessary. Thereby, the post-curing process after lamination
  • the copper plating 14 is applied to the copper foil 15a as the external conductive layer and the copper foils 12a and 12b as the internal conductive layers. And electrically connect.
  • the copper foil 15a is patterned by a subtractive method or the like to form a wiring pattern.
  • the protective film 17 is formed by applying the resin composition according to the present invention on the copper foil 15a having the wiring pattern processed.
  • the resin composition according to the present invention when a polyfunctional isocyanate compound is used as the polyfunctional crosslinkable compound and a hydroxyl group and / or a carboxyl group is used as the polymer compound, the resin composition Appropriate fluidity and viscosity are developed in the object. Thereby, even when a fine wiring pattern is formed, the resin composition is filled between the wiring patterns, and insulation protection can be performed.
  • the resin film according to the present invention has an interlayer insulation resistance of 10 9 ⁇ or more in an insulation reliability test at a temperature of 85 ° C., a humidity of 85%, and 1000 hours, and a viscosity of 120 ° C. to 220 ° C. is 5000 Pa ⁇ S to 100000 Pa.
  • -It is S
  • the through-hole portion can be satisfactorily filled and used suitably without the resin flow at the end of the wiring board.
  • the resin composition is required to be held to some extent without flowing out from the end portion of the wiring board. This is because the resin composition generally flows out from the end of the wiring board when attempting to sufficiently flow into the through hole in the press process under high pressure, and the thickness of the insulating layer at the end of the wiring board It is because there exists a possibility that insulation may fall and it may become thin.
  • the resin composition flows out from the end of the wiring board. If prevention and good embedding property are obtained and the viscosity is 100000 Pa ⁇ S or less, the film can be well laminated by a general-purpose laminating apparatus such as a vacuum press. In addition, the resin composition can be prevented from flowing out from the end of the wiring board in an elastic region of less than 20% elongation of the resin film, and good embedding can be achieved by the plastic region of the resin film having an elongation of 50% or more. it can.
  • the film thickness of the interlayer insulating layer is 40 ⁇ m or less, it exhibits very good low resilience, so that it can be easily incorporated into a small portable electronic device, and the insulation reliability test at a temperature of 85 ° C., a humidity of 85%, and 1000 hours.
  • the interlayer insulation resistance at 10 is 9 9 ⁇ or more, good insulation reliability can be obtained even when the thickness of the interlayer insulation layer is 40 ⁇ m or less.
  • the resin composition according to the second aspect will be mainly described.
  • the following first to fourth embodiments will be described.
  • the present inventors have focused on (A) using a polyimide containing a polyamic acid structure and a polyimide structure as structural units as a polymer compound.
  • the inventors of the present invention contain (A) a polyimide as a polymer compound, (B) a polyfunctional hydroxyl group-containing compound, and (C) an isocyanate compound (block isocyanate compound) as a polyfunctional crosslinkable compound.
  • the polyfunctional hydroxyl group-containing compound is not incorporated into the polyimide skeleton and is present as the second component, and three-dimensional crosslinking is formed between the polyfunctional hydroxyl group-containing compound and the blocked isocyanate compound.
  • the shrinkage of the molecular chain of the polyimide during curing can be suppressed, the warpage can be suppressed, and the melt viscosity of the resin composition before curing can be reduced to improve the through-hole embedding property.
  • a polyimide has the polyamic acid structure which has a heat crosslinkable functional group as a structural unit, the three-dimensional network through a polyimide is formed between a polyfunctional hydroxyl-containing compound and a block isocyanate compound.
  • the isocyanate group reacts with a hydroxyl group to form a urethane structure, but the isocyanate group remains because the amount of the isocyanate group is excessive with respect to the hydroxyl group.
  • the surplus isocyanate group reacts with the carboxyl group of the polyamic acid structure contained in the polyimide remaining after the imidation reaction to form an amide structure, a urea structure, or the like.
  • the polyimide used for the resin composition according to the present embodiment can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine.
  • tetracarboxylic dianhydride A conventionally well-known tetracarboxylic dianhydride can be used.
  • tetracarboxylic dianhydride aromatic tetracarboxylic acid, aliphatic tetracarboxylic dianhydride, etc. are applicable.
  • limiting in the diamine to be used A conventionally well-known diamine can be used.
  • aromatic tetracarboxylic acid examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic 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, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicadicar
  • aliphatic tetracarboxylic dianhydride examples include cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic Acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] oct-7 -Ene-2,3,5,6 tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride and the like.
  • tetracarboxylic dianhydrides may be used alone or in combination of two or more.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic acid from the viewpoint of heat resistance and polymerization rate of polyimide.
  • Particularly preferred are dianhydrides, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and bis (3,4-dicarboxyphenyl) sulfone dianhydride.
  • diamines include, for example, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,3-bis (3-amino Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, bis (3- (3-aminophenoxy) phenyl) ether, bis (4- (4-aminophenoxy) phenyl) ether, 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,4-bis (4- (4-aminophenoxy) phenoxy) benzene, bis (3- (3- (3-aminophenoxy) phenoxy) phenyl) ether, Bis (4- (4-aminophenoxy) phenoxy) phenyl) ether, 1,3-bis ( -(3- (3-aminophenoxy)
  • diamine examples include ⁇ , ⁇ -bis (2-aminoethyl) polydimethylsiloxane, ⁇ , ⁇ -bis (3-aminopropyl) polydimethylsiloxane, and ⁇ , ⁇ -bis (4-aminobutyl) polydimethylsiloxane.
  • ⁇ , ⁇ -bis (4-aminophenyl) polydimethylsiloxane, ⁇ , ⁇ -bis (3-aminopropyl) polydiphenylsiloxane, and the like are also preferable.
  • polyoxyethylene diamine polyoxypropylene diamine
  • polyoxyalkylene diamines containing oxyalkylene groups having different numbers of carbon chains from the viewpoint of reducing the warpage of the cured product of the resin composition.
  • polyoxyalkylenediamines include polyoxyethylenediamines such as Jeffamine ED-600, ED-900, ED-2003, EDR-148, and HK-511 manufactured by Huntsman, Inc., and Jeffamine D-230 and D-400.
  • polyoxypropylene diamines such as polyetheramines D-230, D-400, and D-2000 manufactured by BASF, Germany
  • polytetramethylenes such as Jeffamine XTJ-542, XTJ533, and XTJ536 Examples thereof include those having an ethylene group.
  • EDR-148, D-230, D-400, HK-511, etc. having a relatively low molecular weight can be polymers having a relatively high glass transition temperature, and thus are preferable in applications requiring heat resistance and chemical resistance. Used.
  • D-2000 having a relatively high molecular weight is excellent in flexibility.
  • the weight average molecular weight of polyoxyalkylene diamine is preferably 400 to 3000, particularly preferably 400 to 2000, D-400, D- 2000, ED-600, ED-900, and XTJ-542 are preferably used.
  • the polyimide used in the resin composition according to the present embodiment has a polyimide structure and a polyamic acid structure as structural units.
  • a polyimide structure part having good compatibility with other components and a polyamic acid structure part having a heat-crosslinkable functional group the remaining carboxyl group at the time of low-temperature curing can be reacted with a blocked isocyanate. It can be inactivated and warpage can be suppressed by the blocked isocyanate and the polyfunctional hydroxyl group-containing compound.
  • the polyimide used in the resin composition according to the present embodiment includes a polyimide having a polyether structure. This is because by having the polyether structure in the skeleton, the glass transition temperature and the elastic modulus of the cured product after thermosetting can be controlled, and warpage can be further reduced. In addition, after thermosetting, chemical crosslinking is formed between the polyimide having a polyether structure and the compound having a thermally crosslinkable functional group, and the polyimide having a polyether structure has a polyoxyalkylene chain. This is because a three-dimensional network is formed by local interaction between polymer chains, and heat resistance can be expressed.
  • polyimide it is preferable to use a polyimide including a polyimide part having a structure of the following general formula (2). This is for improving the solvent solubility of polyimide.
  • Z 1 and Z 2 represent a tetravalent organic group.
  • Y 1 , Y 2 , Y 3 , Y 4 , and Y 5 represent an alkylene group having 1 to 5 carbon atoms. And may have a side chain.
  • B, c, and d represent an integer of 1 to 50.
  • polyimide it is also preferable to use a polyimide including a polyimide portion having a structure of the following general formula (11).
  • the solvent solubility of polyimide is also improved by including a polyimide part having the structure of the following general formula (11).
  • polyimide it is preferable to use a polyimide containing a polyimide part having the structure of the above general formula (2) or the following general formula (11).
  • Z 5 and Z 6 it is .
  • Y 6, Y 7, Y 8 , Y 9, Y 10, Y 11, Y 12 and Y 13 which represents a tetravalent organic group, a hydrocarbon group (G represents an integer of 3 to 100)
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 are alkylene groups having 1 to 5 carbon atoms, such as methylene group, ethylene group, propylene group, isopropylene. Group, butylene group and isobutylene group.
  • b, c, and d represent an integer of 1 to 50, preferably 3 to 40, and more preferably 5 to 30.
  • Z 5 and Z 6 represent a tetravalent organic group, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a benzophenone group, a diphenyl sulfone group, and a naphthalene group.
  • a biphenyl group, a diphenyl ether group, a benzophenone group, and a diphenyl sulfone group are preferable, and a diphenyl ether group is more preferable.
  • Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 and Y 13 represent a hydrocarbon group.
  • Y 6 and Y 7 include alkylene groups having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group.
  • Examples of Y 8 , Y 9 , Y 10 , Y 11 , Y 12 and Y 13 include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.
  • a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group, an ethyl group, and a propyl group are more preferable.
  • g represents an integer of 3 to 100, preferably 5 to 70, and more preferably 10 to 50.
  • the content of diamine having the structure of the following general formula (12) is 15 mol% or more and 85 mol% or less. This is for improving the solvent solubility and lowering the elastic modulus of polyimide.
  • Y 1 , Y 2 , Y 3 , Y 4 , and Y 5 represent an alkylene group having 1 to 5 carbon atoms and may have a side chain.
  • B, c, and d represents an integer of 1 to 50.
  • Y 2 , Y 3 , Y 4 and Y 5 preferably have two or more types of alkylene groups from the viewpoint of adhesion to the substrate.
  • the content rate of the diamine which has the structure of following General formula (13) is 15 mol% or more and 95 mol% or less in all the diamines in a polyimide. This is for improving the solvent solubility and lowering the elastic modulus of polyimide.
  • Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 and Y 13 represent a hydrocarbon group.
  • G represents an integer of 3 to 100
  • the imidation ratio of the polyimide is preferably 25% or more and less than 100% from the viewpoint of forming a crosslink between the polyimide and an isocyanate compound as a polyfunctional crosslinkable compound having a crosslinkable functional group. % To 98% is more preferable. If the imidization ratio of the polyimide is 98% or less, the carboxyl group in the polyimide precursor that crosslinks with the compound having a thermally crosslinkable functional group remains sufficiently, and thus exhibits chemical resistance and heat resistance after curing. Moreover, if the imidation ratio of polyimide is 25% or more, the carboxyl residue soluble in the alkaline solution decreases after curing, and chemical resistance and heat resistance can be exhibited.
  • the resin composition according to the second aspect using a polyimide containing a polyimide structure and a polyamic acid structure has been described.
  • the polyamic acid structure is within the scope of the effects of the present invention.
  • Examples of the solvent used in such a reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 1,3 -Dioxane, 1,4-dioxane, dimethyl sulfoxide, benzene, toluene, xylene, mesitylene, phenol, cresol, ethyl benzoate, butyl benzoate and the like. These may be used alone or in combination of two or more.
  • the concentration of the reaction raw material in this reaction is usually 2% by mass to 80% by mass, preferably 30% by mass to 70% by mass.
  • the molar ratio of tetracarboxylic dianhydride to be reacted and diamine is in the range of 0.8 to 1.2. Within this range, the molecular weight can be increased, and the elongation and the like are excellent. Preferably it is 0.9 to 1.1, more preferably 0.95 to 1.05.
  • the weight average molecular weight of the polyimide is preferably 5000 or more and 100,000 or less.
  • the weight average molecular weight means a weight average molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard.
  • the weight average molecular weight is more preferably from 10,000 to 60,000, and most preferably from 20,000 to 50,000.
  • the warp of the protective film obtained using the resin composition is improved, and the low resilience and heat resistance are excellent.
  • printing can be performed without bleeding at a desired film thickness during coating printing, and mechanical properties such as elongation of the obtained protective film are excellent.
  • a polyimide having a polyimide structure and a polyamic acid structure by carrying out a reaction at 80 ° C. to 220 ° C. to advance both the production of a polyimide having a polyamic acid structure and a thermal imidization reaction. That is, by suspending or dissolving a diamine component and an acid dianhydride component in an organic solvent and reacting them under heating at 80 ° C. to 220 ° C., both generation of polyimide and dehydration imidization are performed. It is also preferable to obtain a polyimide.
  • the end of the polymer main chain of polyimide can be end-capped with an end-capping agent made of a monoamine derivative or a carboxylic acid derivative.
  • an end-capping agent made of a monoamine derivative or a carboxylic acid derivative.
  • terminal blocking agent comprising a monoamine derivative
  • examples of the terminal blocking agent comprising a monoamine derivative include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, and 3,5-xylidine.
  • the polyimide obtained by the above-described method can be used in the resin composition according to the present embodiment as it is or without further solvent addition, without further solvent removal.
  • the polyfunctional hydroxyl group-containing compound used in the resin composition according to the present embodiment refers to a compound containing two or more hydroxyl groups per molecular chain.
  • the skeleton include those containing hydrocarbon groups such as aliphatic, aromatic, and alicyclic groups, and those having a structure represented by the following formula (14) in the skeleton from the viewpoint of enhancing the insulating properties. It is preferable that it is an aliphatic compound from the viewpoint of warpage suppression. This is because by having an aliphatic skeleton, hygroscopicity can be suppressed without impairing the effect of suppressing warpage, and high insulating properties can be expressed even during moisture absorption.
  • X is an aromatic
  • Y is an aliphatic having 1 to 10 carbon atoms
  • Z is a functional group selected from an ether group, an ester group, a carbonate group, a urethane group, and a urea group.
  • H represents an integer from 0 to 2
  • i represents an integer from 0 to 1
  • j represents an integer from 1 to 1000.
  • polyfunctional hydroxyl group-containing compound examples include polytetramethylene diol such as PTMG1000 (manufactured by Mitsubishi Chemical Corporation), polybutadiene diol such as G-1000 (manufactured by Nippon Soda Co., Ltd.), and GI-1000 (manufactured by Nippon Soda Co., Ltd.).
  • PTMG1000 manufactured by Mitsubishi Chemical Corporation
  • G-1000 manufactured by Nippon Soda Co., Ltd.
  • GI-1000 manufactured by Nippon Soda Co., Ltd.
  • polybutadiene diol hydrogenated polybutadiene diol, and polycarbonate diol are preferable from the viewpoint of enhancing the insulating properties, and polycarbonate diol is preferable from the viewpoint of reducing warpage.
  • the polyfunctional hydroxyl group-containing compound is preferably a liquid compound at room temperature in terms of warpage reduction and solubility in an organic solvent.
  • the molecular weight is preferably 500 to 3000, and particularly preferably 500 to 2000.
  • the polyfunctional hydroxyl group-containing compound is preferably contained in an amount of 3 parts by mass to 70 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of achieving both reduction in warpage, solder heat resistance and chemical resistance. More preferably, it is contained in parts by mass.
  • polyfunctional hydroxyl-containing compound containing two hydroxyl groups was demonstrated as (B) polyfunctional hydroxyl-containing compound, it contains two or more hydroxyl groups in the range with the effect of this invention. Polyols can also be used.
  • (C-1) Blocked isocyanate compound The blocked isocyanate compound used in the resin composition according to this embodiment is obtained by reacting a blocking agent with an isocyanate having two or more isocyanate groups in the molecule. The resulting compound.
  • isocyanate compounds having two or more isocyanate groups in the molecule include 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4-tolylene diisocyanate.
  • Blocking agents include alcohols, phenols, ⁇ -caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, carbamates , Imines, or sulfites.
  • the blocked isocyanate compound examples include trade names Duranate SBN-70D, TPA-B80E, TPA-B80X, 17B-60PX, MF-B60X, E402-B80T, ME20-B80S, MF-K60X, K6000 manufactured by Asahi Kasei Chemicals Corporation. And hexamethylene diisocyanate (hereinafter also referred to as “HDI”) block isocyanate.
  • the Mitsui Chemicals Polyurethane products include the product name Takenate B-882N, the product name Takenate B-830, which is a tolylene diisocyanate block isocyanate, and the 4,4′-diphenylmethane diisocyanate block isocyanate.
  • the resin composition may contain an organic solvent in addition to the polyimide, the polyfunctional hydroxyl group-containing compound, and the blocked isocyanate compound. It is because it can use preferably as a varnish by setting it as the state melt
  • organic solvents may be used alone or in combination.
  • ⁇ -butyrolactone triglyme, butyl benzoate, and ethyl benzoate.
  • the resin composition may further contain a flame retardant.
  • the kind of flame retardant is not particularly limited, and examples thereof include halogen-containing compounds, phosphorus-containing compounds, and inorganic flame retardants. One kind of these flame retardants may be used, or two or more kinds may be mixed and used.
  • the addition amount of the flame retardant is not particularly limited, and can be appropriately changed according to the type of the flame retardant used. For example, it can be used in the range of 5% by mass to 50% based on the polyimide content.
  • halogen-containing compounds include organic compounds containing chlorine and compounds containing bromine. Specific examples include pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane tetrabromobisphenol A, and the like.
  • phosphorus-containing compound phosphorus compounds such as phosphazene, phosphine, phosphine oxide, phosphate ester, and phosphite ester are fried.
  • phosphazene, phosphioxide, or phosphate ester it is preferable to use phosphazene, phosphioxide, or phosphate ester.
  • phosphorus-containing compounds include phosphazene derivatives FP100, FP110, FP300, and FP400 manufactured by Fushimi Pharmaceutical Co., Ltd.
  • Inorganic flame retardants include antimony compounds and metal hydroxides.
  • Antimony compounds include antimony trioxide and antimony pentoxide.
  • Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.
  • the particle size of the powder is preferably 100 ⁇ m or less. If the particle size is 100 ⁇ m or less, it is easy to be mixed into the polyimide composition, and the transparency of the cured resin is not impaired. In order to sufficiently increase the flame retardancy, the particle size of the powder is preferably 50 ⁇ m or less, particularly preferably 10 ⁇ m or less.
  • a nitrogen-containing compound may be used as the flame retardant.
  • One of the nitrogen-containing compounds may be used as a flame retardant, or two or more of the above-described halogen-containing compounds, phosphorus-containing compounds, and indefinite flame retardants and nitrogen-containing compounds may be mixed and used as a flame retardant.
  • the amount of the nitrogen-containing compound added is not particularly limited and can be changed according to the type of flame retardant used. As addition amount of a nitrogen-containing compound, it can use in the range of 5 mass% to 50 mass% on the basis of content of a polyimide like the flame retardant mentioned above, for example.
  • Examples of the nitrogen-containing compound include melamine cyanurate manufactured by Nissan Chemical Co., Ltd. and Sakai Chemical Industry Co., Ltd.
  • the viscosity and thixotropy are adjusted according to the coating method. If necessary, a filler or a thixotropic agent can be added and used. It is also possible to add additives such as known antifoaming agents, leveling agents and pigments.
  • a urethanization catalyst may be added and used.
  • U-CAT SA registered trademark
  • U-CAT registered trademark 1102 manufactured by San Apro
  • an organozirconium compound manufactured by Matsumoto Fine Chemical Co. an organozirconium compound manufactured by Matsumoto Fine Chemical Co.
  • zirconium K-KAT manufactured by Enomoto Kasei Co., Ltd. Etc.
  • the resin composition may further contain a compound having a thermally crosslinkable functional group.
  • a compound having a thermally crosslinkable functional group examples include triazine compounds, benzoxazine compounds, and epoxy compounds.
  • melamines and melamine cyanurates are preferable.
  • melamines include melamine derivatives, condensates of compounds having a structure similar to melamine and melamine, and the like.
  • Specific examples of melamines include, for example, methylolated melamine, ammelide, ammelin, formoguanamine, guanylmelamine, cyanomelamine, arylguanamine, melam, melem, melon and the like.
  • melamine cyanurates include molar reactants such as cyanuric acid and melamines.
  • some of the amino groups or hydroxyl groups in melamine cyanurate may be substituted with other substituents.
  • the benzoxazine compound may be composed only of monomers, or several molecules may be polymerized into an oligomer state. Moreover, you may use the benzoxazine compound which has a different structure simultaneously. Among these, bisphenol benzoxazine is preferably used.
  • the resin composition can be used as a negative photosensitive resin composition by further adding an acrylic monomer and a photo radical generator. Moreover, it can be used as a positive photosensitive resin composition by adding a photoacid generator.
  • a cured product can be obtained by heating the resin composition described above.
  • the mode of heating is not particularly limited, but it is preferable to heat for 5 minutes to 60 minutes in a two-step temperature range. After heating at 100 ° C. to 130 ° C. for 5 minutes to 60 minutes, 15 ° C. at 160 ° C. to 200 ° C. It is more preferable to heat for 60 minutes.
  • cure in two types of temperature ranges, the reaction between the compounds contained in a resin composition can be controlled, and a three-dimensional network can be formed. And thereby, the heat resistance and chemical resistance of hardened
  • the maximum temperature is set in the range of 150 ° C. to 220 ° C. with an oven or a hot plate, for 5 to 100 minutes, air or nitrogen, etc.
  • the solvent is removed by heating in an inert atmosphere.
  • the heating temperature may be constant over the entire processing time or may be gradually raised.
  • the resin composition film can be formed by printing on the surface of a flexible printed circuit board or a semiconductor wafer by known screen printing or a precision dispensing method.
  • the resin composition exhibits excellent heat resistance when thermally cured, it is useful as a surface cured film for semiconductor elements, interlayer insulating films, bonding sheets, protective insulating films for printed wiring boards, surface protective films for printed circuit boards, etc. And is applied to various electronic components.
  • Espanex M manufactured by Nippon Steel Chemical Co., Ltd.
  • insulating layer thickness 25 ⁇ m
  • conductor layer copper foil F2-WS (18 ⁇ m)
  • the composition is applied and cured.
  • the part not coated can be used as an external terminal by applying electrolytic nickel-gold plating.
  • the surface protective film thus formed exhibits good insulating properties.
  • thermosetting of the resin composition in the present embodiment is performed under relatively low temperature conditions (for example, 160 ° C. to 200 ° C.), copper oxidation does not occur.
  • Such low-temperature curing is possible because carboxylic acid reacts with a blocked isocyanate compound (more precisely, an isocyanate compound that has been unblocked by heating), so complete imidization is unnecessary and high-temperature heating as high as 250 ° C is not required. Because it becomes.
  • the resin composition according to the present embodiment can be used as a resin film by coating on a substrate and drying.
  • the thickness of the surface protective film is preferably 1 ⁇ m to 50 ⁇ m. When the film thickness is 1 ⁇ m or more, the handling becomes easy, and when the film thickness is 50 ⁇ m or less, it is easy to bend and incorporate easily.
  • the resin composition which concerns on this Embodiment can also be used as a photosensitive resin composition by containing the (D) photosensitive agent.
  • the photosensitive film can also be obtained by apply
  • the resin composition according to the present embodiment can be suitably used as an interlayer insulating film such as a multilayer flexible wiring board by providing a resin composition on a copper foil and drying it.
  • the resin composition according to the present embodiment can be suitably used as a protective film for a wiring pattern on a wiring board by providing the resin composition so as to cover the wiring pattern formed on the substrate.
  • the hydroxyl group of the bifunctional hydroxyl group-containing compound and the isocyanate group of the blocked isocyanate compound react to form a urethane structure, and the bifunctional hydroxyl group-containing compound is not taken into the polyimide skeleton, Present as the second component in the photosensitive resin composition.
  • skeleton at the time of hardening can be prevented, and reduction of curvature can be achieved.
  • an aliphatic diamine component is contained in the polyimide structure of polyimide, it is possible to suppress a decrease in molecular weight due to depolymerization of the polyamic acid structure.
  • the photosensitive resin composition according to the second embodiment of the present invention includes (a) a polyimide, (b) a bifunctional hydroxyl group-containing compound, (c-1) an isocyanate compound (block isocyanate compound), and a photosensitive agent.
  • polyimide in the photosensitive resin composition according to the present embodiment will be described.
  • polyimide can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine.
  • tetracarboxylic dianhydride A conventionally well-known tetracarboxylic dianhydride can be used.
  • tetracarboxylic dianhydride aromatic tetracarboxylic acid, aliphatic tetracarboxylic dianhydride, etc. are applicable.
  • diamine there is no restriction
  • limiting in the diamine to be used A conventionally well-known diamine can be used.
  • the polyimide is represented by the polyimide structure represented by the following general formula (3) and the following general formula (4) from the viewpoint of developability and molecular weight stability. It is preferable that each has a polyamic acid structure as a repeating structural unit.
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom.
  • a monovalent organic group having 1 to 20 carbon atoms which may be the same or different, and R 3 , R 6 , R 9 , R 12 , and R 15 each have 1 to carbon atoms 20 represents a tetravalent organic group, and m, n, and p each independently represent an integer of 0 to 100.
  • R 16 represents a tetravalent organic group, and R 17 represents 1 carbon atom. Represents a divalent organic group having 90 carbon atoms.
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms, and may be the same or different, and R 3 , R 6 , R 9 , R 12 , and R 15 are tetravalent having 1 to 20 carbon atoms.
  • M, n, and p are each independently an integer of 0 to 30, and satisfy 1 ⁇ (m + n + p) ⁇ 30.)
  • tetracarboxylic dianhydride and aliphatic diamine represented by the general formula (15) are polymerized and cyclized to obtain a polyimide, and then tetracarboxylic dianhydride and the following: Examples include a synthesis method in which the diamine represented by the general formula (16) is polymerized.
  • R 17 represents a divalent organic group having 1 to 90 carbon atoms.
  • tetracarboxylic dianhydride examples include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as “BPDA”), benzophenone-3,3 ′, 4,4′- Tetracarboxylic dianhydride (hereinafter abbreviated as “BTDA”), oxydiphthalic dianhydride (hereinafter abbreviated as “ODPA”), diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic acid dianhydride
  • TMEG ethylene glycol bis (trimellitic acid monoester acid anhydride)
  • TMEG ethylene glycol bis (trimellitic acid monoester acid anhydride)
  • TMEG ethylene glycol bis (trimellitic acid monoester acid anhydride)
  • TMEG ethylene glycol bis (trimellitic acid monoester acid anhydride)
  • TMEG p-phenylene bis (
  • tetracarboxylic dianhydrides described above may be used alone or in combination of two or more. From the viewpoint of polyimide developability, BPDA, ODPA, BTDA, TMEG, 5-BTA, and decanediol bis (trimellitic acid monoester acid anhydride) are more preferable.
  • the diamine represented by the general formula (15) is not limited as long as it has the structure represented by the general formula (15), but may be 1,8-diamino-3,6-dioxyoctane or the like.
  • Polyoxyethylenediamine compounds, polyoxyalkylenediamine compounds such as Huntsman's Jeffamine EDR-148 and EDR-176, Jeffamine D-230, D-400, D-2000, D-4000, polyether amine manufactured by BASF Examples include polyoxypropylenediamine compounds such as D-230, D-400, and D-2000, and compounds having different oxyalkylene groups such as HK-511, ED-600, ED-900, ED-2003, and XTJ-542. It is done. By using these compounds having an oxyalkylene group, warpage of FPC after baking of the polyimide can be reduced.
  • m, n, and p are each independently an integer of 0 or more and 30 or less. From the viewpoint of insulation reliability, 1 ⁇ (m + n + p) ⁇ 30 is preferable, and 3 ⁇ (m + n + p) ⁇ 10 is more preferable. Since the skeleton having an oxyalkylene group is short as 1 ⁇ (m + n + p) ⁇ 30, it can be estimated that the elastic modulus of polyimide is increased and the insulation reliability is improved. In addition, usually when such an oxyalkylene group skeleton is short, warping tends to occur. In this embodiment, warpage is in a good state by using a bifunctional hydroxyl group-containing compound and blocked isocyanate in combination. It is estimated that the insulation reliability can be further improved while maintaining the above.
  • the polyimide which concerns on this Embodiment has a polyimide structure and a polyamic-acid structure as a repeating structural unit, respectively, by introduce
  • the diamine of the above general formula (15) is introduced into the polyamic acid structure, the aliphatic diamine has a high basicity, and the depolymerization of the polyamic acid proceeds and the molecular weight decreases remarkably as compared with the conventional polyamic acid.
  • the molecular weight is stabilized without being affected by the basicity of the aliphatic diamine.
  • Examples of the diamine represented by the general formula (16) 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, 3, 3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3, 7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diamin
  • the polyimide has a structure represented by the following general formula (6) as a repeating unit.
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms, and may be the same or different, and R 3 , R 6 , R 9 , R 12 , and R 15 are tetravalent having 1 to 20 carbon atoms.
  • M, n, and p each independently represents an integer of 0 or more and 30 or less, R 16 represents a tetravalent organic group, and R 17 represents a divalent having 1 to 90 carbon atoms.
  • A, B, and C represent mol% of each unit, and satisfy 0.10 ⁇ (A + B) / (A + B + C) ⁇ 0.85.
  • (A + B) which is a structure containing the diamine represented by the general formula (15) is 0.85 or less with respect to the whole, a decrease in elastic modulus and glass transition point (Tg) is suppressed, Insulation reliability is maintained. Furthermore, when (A + B) which is a polyimide structure is 0.85 or less with respect to the whole, the solubility with respect to the alkaline developer is developed, and the developability is improved.
  • the main chain terminal of the polyimide 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 polyimide may be used, or the terminal may be sealed with another acid anhydride or an amine compound.
  • the weight average molecular weight of the polyimide is preferably from 1,000 to 1,000,000.
  • the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography 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. Moreover, it is preferable that it is 1000000 or less from a viewpoint of the viscosity of a polyimide containing resin composition and a moldability.
  • 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 20,000 to 50,000.
  • a polyimide having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a process of synthesizing a first-stage polyimide site by reacting acid dianhydride and diamine in an unequal molar amount (process 1), followed by a second stage. It can be produced by the step of synthesizing the polyamic acid moiety (step 2).
  • process 1 the process of synthesizing a first-stage polyimide site by reacting acid dianhydride and diamine in an unequal molar amount
  • step 2 the step of synthesizing the polyamic acid moiety
  • 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 to 96 hours, preferably 0.5 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 part can be obtained by adding a known imidation catalyst or by using no catalyst.
  • the imidization catalyst is not particularly limited, but an acid anhydride such as acetic anhydride, a lactone compound such as ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -tetronic acid, ⁇ -phthalide, ⁇ -coumarin, and ⁇ -phthalido acid, Examples thereof include 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.
  • ketone compound having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; benzene, Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as toluene, xylene, mesitylene, tetralin; methyl acetate, ethyl acetate, ⁇ -butyrolactone Ester compounds having 3 to 12 carbon atoms such as methyl benzoate; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing compounds having 2
  • Particularly preferred 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 nitrogen-containing compounds having 2 to 10 carbon atoms. Can be mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.
  • the reaction temperature is preferably 15 ° C. or higher and 250 ° C. or lower. If the reaction temperature is 15 ° C. or higher, the reaction starts, and if it is 250 ° C. or lower, there is no deactivation of the 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 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.
  • 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 moiety 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 during the synthesis of 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.
  • 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.
  • Ketone compounds having 2 to 6 carbon atoms saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; benzene, toluene, xylene, mesitylene, tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms, such as methyl acetate, ethyl acetate, ⁇ -butyrolactone, methyl benzoate More than 12 ester compounds; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Nitrogen-containing compounds having 2 to 10 carbon atoms such as -2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide.
  • polyimide purification method examples include a method of removing insoluble acid dianhydride and diamine in the reaction solution by vacuum filtration, pressure filtration, or the like. Moreover, the purification method by what is called reprecipitation which adds a reaction solution to a poor solvent and precipitates can be implemented. Furthermore, when a particularly high-purity polyimide is required, a purification method by extraction using supercritical carbon dioxide is also possible.
  • insulation reliability is improved and warpage can be suppressed by containing a bifunctional hydroxyl group-containing compound and blocked isocyanate. It is presumed that the insulation reliability is improved by the formation of a crosslinked body by the reaction between the hydroxyl group contained in the bifunctional hydroxyl group-containing compound and the isocyanate group contained in the blocked isocyanate.
  • the bifunctional hydroxyl group-containing compound is present as the second component without being taken into the polyimide skeleton, shrinkage of the polyimide skeleton during curing can be prevented and warpage can be suppressed.
  • the inclusion of the blocked isocyanate inactivates the carboxyl group at a low temperature and enables low-temperature curing. Therefore, it is considered that the shrinkage of the polyimide skeleton during curing can be prevented and the warpage can be suppressed.
  • polyimide is used as the polymer compound (A)
  • polymer compound polyimide that does not include a polyamic acid structure
  • polyamide that does not include a polyimide structure it is also possible to use a polyamideimide containing both a polyamic acid structure and a polyimide structure.
  • bifunctional hydroxyl group-containing compound is the same as the polyfunctional hydroxyl group-containing compound used in the resin composition according to the first embodiment as long as the effects of the present invention are achieved. Can be used.
  • (C-1) Blocked isocyanate compound As the blocked isocyanate compound, the same compounds as those used for the resin composition according to the first embodiment can be used. Moreover, similarly to the resin composition according to the first embodiment, other polyfunctional isocyanate compounds and polyfunctional oxazoline compounds can also be used within the range where the effects of the present invention are exhibited.
  • the photosensitive resin composition according to the present embodiment includes a (meth) acrylate compound having at least two or more photopolymerizable unsaturated double bonds as a photosensitive agent, and further includes (E) light. It preferably contains a polymerization initiator.
  • the photosensitive agent in the photosensitive resin composition according to the present embodiment represents a compound having a property that the structure is changed by light irradiation and the solubility in a solvent is changed.
  • two or more light is contained by including the (meth) acrylate compound and photoinitiator which have two or more photopolymerizable unsaturated double bonds. Since a crosslinked body is formed also by the (meth) acrylate compound having a polymerizable unsaturated double bond, developability and insulation reliability are improved.
  • 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, tris (2-acryloxyethyl) isocyanurate, ⁇ -caprolactone modified tris (acryloxyethyl) isocyanurate, glycerol tri (meth) acrylate, trimethylolprop Tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxye
  • EO-modified bisphenol A dimethacrylate EO-modified hydrogenated bisphenol A diacrylate, and pentaerythritol tri / tetra (meth) acrylate are preferable from the viewpoint of developability and warpage after firing.
  • a combination of a compound having two double bonds and a compound having three or more double bonds is preferable. It is estimated that the compound having three or more double bonds forms a rigid cross-linked body, whereby the elastic modulus and glass transition point (Tg) of the cured film are increased, and the insulation reliability is improved.
  • the bifunctional hydroxyl group-containing compound is present as a second component in the photosensitive resin composition without forming a crosslinked structure with the compound having a double bond, thereby reducing warpage. can do.
  • Examples of the compound having three or more double bonds include pentaerythritol tri / tetraacrylate (trade name: Aronix (registered trademark) M-306, manufactured by Toagosei Co., Ltd.), trimethylolpropane PO-modified triacrylate (trade name: Aronix M).
  • the amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is preferably 5 parts by mass or more and 60 parts by mass or less from the viewpoint of developability when the amount of polyimide is 100 parts by mass. 10 parts by mass or more and 40 parts by mass or less are more preferable.
  • 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 polyimide is 100 parts by mass. 0.5 parts by mass or more and 35 parts by mass or less are more preferable.
  • the photosensitive resin composition contains a phosphorus compound.
  • a phosphorus compound will not be limited if it is a phosphorus atom containing compound which contains a phosphorus atom in a structure. Examples of such phosphorus compounds include phosphate ester compounds having a phosphate ester structure and phosphazene compounds having a phosphazene structure.
  • Phosphoric acid ester compounds such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, etc., phosphoric acid ester substituted with an aliphatic hydrocarbon group, tris (butoxyethyl) phosphate, etc.
  • Phosphorus ester, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, resorcinol bis (diphenyl phosphate) and other aromatic organic groups as substituents Examples include 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 (17) and the following general formula (18).
  • R 21 , R 22 , R 23 , and R 24 in the phosphazene compound represented by the general formula (17) and the general formula (18) 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 polyimide.
  • a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable from the viewpoint of flame retardancy.
  • 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 (17) 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 (18) 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.
  • G and J in the phosphazene compound represented by the general formula (18) are not limited as long as they are organic groups having 3 to 30 carbon atoms.
  • G —N ⁇ P (OC 6 H 5 ) 3 , —N ⁇ P (OC 6 H 5 ) 2 (OC 6 H 4 OH), —N ⁇ P (OC 6 H 5 ) ( OC 6 H 4 OH) 2 , —N ⁇ P (OC 6 H 4 OH) 3 , —N ⁇ P (O) (OC 6 H 5 ), —N ⁇ P (O) (OC 6 H 4 OH) preferable.
  • J 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) and the like are preferable.
  • phosphorus compound one type of phosphorus compound may be used, or two or more types of phosphorus compounds may be used in combination.
  • the addition amount of the phosphorus compound in the photosensitive resin composition is preferably 50 parts by mass or less from the viewpoint of developability and the like when the amount of polyimide is 100 parts by mass. From the viewpoint of flame retardancy of the cured product, 45 parts by mass or less is more preferable. Moreover, if it is 5 mass parts or more, an effect is exhibited.
  • the photosensitive resin composition may contain other compounds as long as the performance is not adversely affected.
  • specific examples include thermosetting resins used for improving the toughness, solvent resistance, and heat resistance (thermal stability) of the fired film, and compounds having reactivity with polyimide.
  • the heterocyclic compound used for adhesiveness improvement, the pigment, dye, etc. which are used for coloring of a film are mentioned.
  • thermosetting resin examples include epoxy resins, cyanate ester resins, unsaturated polyester resins, benzoxazine resins, benzoxazolines, phenol resins, melamine resins, and maleimide compounds.
  • Examples of the compound having reactivity with polyimide include a compound capable of reacting with a carboxyl group, amino group or terminal acid anhydride in a polymer to form a three-dimensional crosslinked structure.
  • a so-called thermal base generator compound that generates an amino group as a base by heating is preferable.
  • a compound obtained by protecting the amino group of a base compound such as an amine with an acid chloride compound, which forms a salt structure with an acid such as sulfonic acid is protected with a dicarbonate compound. Thereby, it is stable without exhibiting basicity at room temperature, and can be a thermal base generator that generates a base by deprotection by heating.
  • the heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom.
  • the hetero atoms in this embodiment include oxygen, sulfur, nitrogen, and phosphorus.
  • Specific examples include 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, imidazole such as 2-phenylimidazole, N-alkyl group-substituted imidazole such as 1,2-dimethylimidazole, Aromatic group-containing imidazole such as 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl Cyano group-containing imidazoles such as -2-undecylimidazole and 1-cyanoethyl-2-phenylimidazole, imidazole
  • 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.
  • organic solvents 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, triethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like.
  • Ketone compounds having 2 to 6 carbon atoms saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; benzene, toluene, xylene, mesitylene, tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as: carbons such as methyl acetate, ethyl acetate, ⁇ -butyrolactone, methyl benzoate 3 to 9 ester compounds; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N- Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as methyl-2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide
  • 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 nitrogen-containing compounds having 2 to 10 carbon atoms. Or a mixture of two or more of them. From the viewpoint of polyimide solubility, triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.
  • the concentration of polyimide in the resin composition composed of polyimide and an organic solvent is not particularly limited as long as it is a concentration capable of forming a resin molded body.
  • the polyimide concentration is preferably 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the polyimide concentration 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 Embodiment can be used suitably for formation of a photosensitive film.
  • the photosensitive film which concerns on this Embodiment is obtained by apply
  • the photosensitive film according to the present embodiment includes a carrier film, the photosensitive resin composition provided on the carrier film, and a cover film formed on the photosensitive resin. Is preferred.
  • the polyimide concentration in the photosensitive resin composition is preferably 1% by mass or more and 90% by mass or less.
  • concentration of a polyimide 1 mass% or more is preferable from a viewpoint of the film thickness of a photosensitive film, and 90 mass% or less is preferable from a viewpoint of the viscosity of the photosensitive resin composition, and the uniformity of a film thickness. From a viewpoint of the film thickness of the obtained photosensitive film, 2 mass% or more and 80 mass% or less are more preferable.
  • 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 film formation, it will not be limited.
  • examples of such a 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.
  • coating methods 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 apply
  • drying the photosensitive resin composition into a dry film for example, a laminated film having a carrier film and a photosensitive film is obtained.
  • 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.
  • the photosensitive film which concerns on this Embodiment can be used suitably for a flexible printed wiring board.
  • the flexible printed wiring board according to the present embodiment includes a base material having wiring and the photosensitive film provided so as to cover the wiring on the base material.
  • This flexible wiring board can be obtained by pressure-bonding a photosensitive film on a substrate having wiring, alkali-developing, and then baking.
  • 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 formation method of 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 forming method hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating, or the like is performed in a state where the wiring side of the substrate having wiring and the photosensitive film according to the present embodiment are in contact with each other.
  • the method etc. are mentioned.
  • a heat vacuum press or a heat vacuum laminate is preferable.
  • the heating temperature when laminating the photosensitive film on the substrate having 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 wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.
  • the photosensitive film can be subjected to negative photolithography by irradiating with light and then dissolving the portion other than the light irradiated portion by alkali development.
  • 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 aqueous alkali solution used for development is not limited as long as it is a solution that can dissolve other than the light irradiation site.
  • aqueous sodium carbonate solution an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution.
  • 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 performed in an air atmosphere or an inert gas atmosphere.
  • the time required for the firing varies depending on the reaction conditions, but is usually within 24 hours, and particularly preferably in the range of 1 to 8 hours.
  • the polyimide and the photosensitive resin composition according to the present embodiment have good warpage after curing, good developability, and chemical resistance when used as a cured product.
  • 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 polyimide and the photosensitive resin composition according to the present embodiment 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
  • a resin composition containing a polyimide having a polyamic acid structure having a siloxane moiety using silicone diamine as a diamine component and a polyimide structure has been proposed as a material used in the manufacturing process of the flexible printed circuit board.
  • the siloxane moiety exists only in the polyamic acid structure.
  • the polyimide structure shrinks and warps during curing, the molecular weight of the polyamic acid structure is remarkably lowered, and the development time of the dry film (resin film) becomes unstable.
  • a high acceleration test HAST
  • a material with high insulation reliability having HAST resistance and warpage suppressed for improving connection reliability Is required.
  • the inventors of the present invention have focused on (A) using a polyimide structure having a siloxane moiety and a polyamic acid structure as a structural unit as a polymer compound.
  • A a polyimide having a siloxane moiety as a polymer compound and a polyimide having a polyamic acid structure as a structural unit,
  • D a (meth) acrylate compound having a specific structure as a photosensitizer
  • E light It has been found that a photosensitive resin composition having excellent HAST resistance can be realized by a photosensitive resin composition containing a polymerization initiator.
  • the siloxane portion is contained in the polyimide structure, it is possible to suppress a decrease in the molecular weight of the polyamic acid structure, and thus it is possible to suppress a decrease in developability. Moreover, since moderate softness
  • the third embodiment of the present invention will be described in detail.
  • the photosensitive resin composition according to the third embodiment of the present invention includes (a) a polyimide having a polyimide structure and a polyamic acid structure as constituent units, and (D) two unsaturated double bonds capable of photopolymerization.
  • the (meth) acrylate compound having the above and (E) a photopolymerization initiator are contained.
  • each component will be described in detail.
  • the polyimide according to the present embodiment is a block copolymer having a polyimide structure represented by the following general formula (7) and a polyamic acid structure represented by the following general formula (8) as repeating structural units. It is a coalescence.
  • the polyimide according to the present embodiment is synthesized using an acid dianhydride and a diamine.
  • Z 3 and Z 4 are tetravalent organic groups derived from tetracarboxylic dianhydride represented by the following general formula (9), and are the same.
  • R 18 represents a divalent organic group having 1 to 30 carbon atoms
  • R 19 represents a monovalent organic group having 1 to 30 carbon atoms
  • e is 1 represents an integer of 1 to 20.
  • the polyimide since the polyimide includes a polyimide structure represented by the general formula (7), a siloxane site is included in the polyimide structure. Thereby, since moderate softness
  • polyamic acid structure and polyimide structure of polyimide contain a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the general formula (9), moderate rigidity is imparted to the molecular chain, Heat resistance is improved and insulation reliability (HAST resistance) is improved.
  • Examples of the acid dianhydride used in this embodiment include pyromellitic anhydride (hereinafter also abbreviated as “PMDA”), oxydiphthalic dianhydride (hereinafter also abbreviated as “ODPA”), biphenyltetracarboxylic dianhydride. Product (hereinafter also abbreviated as “BPDA”).
  • PMDA pyromellitic anhydride
  • ODPA oxydiphthalic dianhydride
  • BPDA biphenyltetracarboxylic dianhydride
  • BPDA biphenyltetracarboxylic dianhydride
  • 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene Is mentioned.
  • 1,3-bis (3-aminophenoxy) benzene having flexibility is preferable.
  • silicone diamine used in the present embodiment is not particularly limited as long as it is a structure represented by the following general formula (19).
  • e is an integer that satisfies 1 ⁇ e ⁇ 20. If e is 20 or less, alkali solubility and HAST resistance will become favorable.
  • the e in the general formula (19) is preferably 1 or more and 15 or less, more preferably 1 or more and 12 or less, from the viewpoint of Tg of the polyimide to be produced and flame retardancy.
  • R 18 is not limited as long as it is a divalent organic group having 1 to 30 carbon atoms.
  • the divalent organic group (R 19 ) having 1 to 30 carbon atoms is represented by CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , etc. from the viewpoint of flame retardancy.
  • a divalent organic group derived from an aliphatic saturated hydrocarbon having 10 or less carbon atoms is preferred.
  • R 19 represents an organic group having 1 to 30 carbon atoms, which may be the same or different.
  • Examples of the organic group (R 19 ) having 1 to 30 carbon atoms include an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, an organic group containing a cyclic structure, and a group obtained by combining them.
  • Examples of the aliphatic saturated hydrocarbon group include primary hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group, secondary hydrocarbon groups such as isobutyl group and isopentyl group, and tertiary hydrocarbon groups such as a t-butyl group.
  • Examples of the aliphatic unsaturated hydrocarbon group include a hydrocarbon group containing a double bond such as a vinyl group and an allyl group, and a hydrocarbon group containing a triple bond such as an ethynyl group.
  • Examples of the functional group containing a cyclic structure include a monocyclic functional group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, and a cyclooctyl group; a polycyclic functional group such as a norbornyl group and an adamantyl group; pyrrole, furan, A heterocyclic functional group having a thiophene, imidazole, oxazole, thiazole, tetrahydrofuran, dioxane structure; an aromatic hydrocarbon group containing a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring structure.
  • a monocyclic functional group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo
  • the organic group (R 19 ) having 1 to 30 carbon atoms may contain a halogen atom, a hetero atom and a metal atom.
  • halogen atom include fluorine, chlorine, bromine and iodine.
  • oxygen, sulfur, nitrogen, and phosphorus are mentioned as a hetero atom.
  • metal atom include silicon and titanium.
  • R 19 when the organic group (R 19 ) having 1 to 30 carbon atoms contains a hetero atom and / or a metal atom, R 19 may be directly bonded to the bonded hetero atom and / or metal atom. And / or may be bonded via a metal atom.
  • the number of carbon atoms of R 19 in the general formula (7) and the general formula (19), taking into account the flame retardant, 1 to 20 are preferred. Furthermore, from the viewpoint of solvent solubility of the polyimide to be produced, the number of carbon atoms is particularly preferably 1 or more and 10 or less.
  • compounds represented by R 18 : propylene group and R 19 : methyl group include PAM-E (n ⁇ 2), KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.). n ⁇ 10), X-22-161A (n ⁇ 20), BY16-871 (n ⁇ 2), and BY16-853U (n ⁇ 10) manufactured by Toray Dow Corning.
  • Examples of the compound represented by R 18 : propylene group and R 19 : phenyl group include X-22-1660B-3 (n ⁇ 20) manufactured by Shin-Etsu Chemical Co., Ltd.
  • the main chain terminal of the polyimide is not particularly limited as long as it does not affect the performance.
  • the main chain terminal derived from the acid dianhydride and diamine used when producing polyimide may be used, or the main chain terminal may be sealed with another acid anhydride or an amine compound.
  • the weight average molecular weight of the polyimide 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 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. Moreover, it is preferable that it is 1000000 or less from a viewpoint of the viscosity of a polyimide containing resin composition and a moldability.
  • 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.
  • the production method shown in the second embodiment can be used.
  • the resin composition according to the second embodiment using (A) a polyimide structure having a siloxane moiety as a polymer compound and a polyimide having a polyamic acid structure as a structural unit has been described. It is also possible to use the resin composition according to the first aspect by using a polyimide that does not substantially contain a polyamic acid structure as long as the effects of the present invention are achieved.
  • the photosensitive resin composition according to the present embodiment preferably contains a bifunctional hydroxyl group-containing compound and a blocked isocyanate compound. Since the bifunctional hydroxyl group-containing compound does not have a direct bond with polyimide, it is not taken into the skeleton and exists as the second component. Thereby, shrinkage
  • bifunctional hydroxyl group-containing compound the same compounds as those used in the resin composition according to the first embodiment can be used.
  • the polyfunctional hydroxyl-containing compound containing a 2 or more hydroxyl group can also be used in the range with the effect of this invention.
  • the bifunctional hydroxyl group-containing compound is contained in an amount of 1 part by mass to 70 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of achieving both reduction in warpage, solder heat resistance and chemical resistance.
  • the content is preferably 1 part by mass to 60 parts by mass.
  • (C-1) Blocked isocyanate compound As the blocked isocyanate compound, the same compounds as those used for the resin composition according to the first embodiment can be used.
  • the example using a blocked isocyanate compound was demonstrated as (C) polyfunctional crosslinking
  • (D) (Meth) acrylate compound As the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds, 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, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-di ( p-hydroxyphenyl) propane di (meth) acrylate, tris (2-acryloxyethyl) isocyanurate, ⁇ -caprolactone modified tris (acryloxyethyl) isocyanurate, glycerol tri (meth) acrylic , Trimethylolpropane tri (meth) acrylate, polyoxyethylenetrimethylolpropane tri (me
  • the photosensitive resin composition according to the present embodiment contains a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds. From the viewpoint of resolution and HAST resistance, it is preferable to include a (meth) acrylate compound having three or more double bonds.
  • Examples of (meth) acrylate compounds having three or more double bonds include pentaerythritol tri / tetraacrylate (Toagosei Co., Ltd., Aronix M-306), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., A-TMMT) , EO-modified glycerol tri (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-GLY-9E (EO-modified 9 mol)), ditrimethylolpropane tetraacrylate (manufactured by Toagosei Co., Ltd., Aronix M-408), dipentaerythritol penta And hexaacrylate (Aronix M-403, manufactured by Toagosei Co., Ltd.).
  • pentaerythritol tri / tetraacrylate Toagosei Co.
  • the (meth) acrylate compound having three or more double bonds may be a compound represented by the following general formula (10) from the viewpoint of insulation resistance (HAST resistance) and warpage. More preferred. This is because the compound represented by the following general formula (10) is not taken into the skeleton of the polyimide and forms a crosslinked body as the second component, thereby preventing the polyimide skeleton from shrinking at the time of curing and suppressing warpage. It is. In addition, since it does not have a functional group such as a hydroxyl group that reduces electrical insulation, a rigid cross-linked body is formed in the polyimide matrix according to this embodiment, and the Tg and elastic modulus of the cured film are high. Therefore, it is estimated that HAST resistance is improved.
  • HAST resistance insulation resistance
  • R 20 represents a hydrogen atom or a methyl group.
  • a plurality of E each independently represents an alkylene group having 2 to 5 carbon atoms, which may be the same or different.
  • F is an integer from 1 to 10.
  • examples of the alkylene group having 2 to 6 carbon atoms (E) include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, and a neopentyl group.
  • E is more preferably 2 or 3 alkylene groups.
  • f is particularly preferably 1 or more and 5 or less.
  • Examples of the compound represented by the general formula (10) include Aronix M-350 (E: ethylene group, f: 1), M-360 (E: ethylene group, f: 2), M-310 manufactured by Toagosei Co., Ltd. (E: propylene group, f: 1), M-321 (E: propylene group, f: 2), SR502 (E: ethylene group, f: 3), SR9035 (E: ethylene group, f: manufactured by SARTOMER) 5). These may be used alone or in combination.
  • the photosensitive resin composition which concerns on this Embodiment it has the (meth) acrylate compound which has two double bonds, and three or more double bonds from the viewpoint of the curvature after baking and resolution ( It is preferable to use together with a (meth) acrylate compound.
  • (Meth) acrylate compounds having two double bonds are classified into aliphatic di (meth) acrylates and aromatic di (meth) acrylates having a bisphenol structure.
  • aliphatic di (meth) acrylate examples include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and polyethylene / polypropylene glycol di (meth) acrylate.
  • nonaethylene glycol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., 9G
  • heptapropylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., 9PG
  • the like are preferable from the viewpoint of suppressing warpage.
  • examples of the aromatic di (meth) acrylate include compounds represented by the following general formula (20).
  • R 25 and R 26 each represent a hydrogen atom or a methyl group.
  • a plurality of E's each independently represents an alkylene group having 2 to 6 carbon atoms, which may be the same or different. May be.
  • examples of the alkylene group having 2 to 6 carbon atoms (E) include ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentyl group, and the like. It is done.
  • l and k are each an integer of 1 to 10, and 2 ⁇ l + k ⁇ 20. If l and k are 10 or less, flame retardancy and HAST resistance are improved. Further, from the viewpoint of warpage and resolution, l and k in the general formula (20) are more preferably 3 or more and 6 or less and 6 ⁇ l + k ⁇ 12, respectively.
  • Specific examples of the general formula (20) include Aronix M-208 (R 25 , R 26 : hydrogen atom, E: ethylene group, l, k ⁇ 2) manufactured by Toagosei Co., Ltd., Shin-Nakamura Chemical Co., Ltd.
  • AB1206PE the following general formula (21)
  • R 25 hydrogen atom
  • R 26 methyl group
  • E 1 ethylene
  • E 2 propylene group
  • the amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is 5 parts by mass or more and 60 parts by mass or less from the viewpoint of resolution when the amount of polyimide is 100 parts by mass.
  • 10 parts by mass or more and 40 parts by mass or less are more preferable.
  • the resin composition which concerns on this Embodiment when not using as a photosensitive resin, it is not necessarily required to contain the (D) (meth) acrylate compound as a photosensitive agent.
  • (E) Photopolymerization initiator As the photopolymerization initiator, those similar to those shown in the second embodiment can be used.
  • (F) Phosphorus compound As the phosphorus compound, the same compounds as those described in the second embodiment can be used.
  • (H) Photosensitive film Moreover, the photosensitive resin composition which concerns on this Embodiment can be used for formation of a photosensitive film similarly to the photosensitive resin composition which concerns on the said 2nd Embodiment.
  • the present inventors have focused on using a solvent-soluble polyimide having a hydroxyl group and / or a carboxyl group and a siloxane moiety as the polymer compound (A). And, the present inventors have (A) a solvent-soluble polyimide as a polymer compound, (B) a bifunctional hydroxyl group-containing compound as a polyfunctional hydroxyl group-containing compound, and (C) an oxazoline compound as a polyfunctional crosslinkable compound. Can be processed with a solvent or an aqueous alkali solution before the crosslinking reaction, exhibits good through-hole embedding properties, and has an excellent resistance to an aqueous solvent and an aqueous alkali solution after the crosslinking reaction. It was found that can be realized.
  • the fourth embodiment of the present invention will be specifically described.
  • the resin composition according to the fourth embodiment of the present invention includes (a) a polyimide having a hydroxyl group and / or a carboxyl group, (b) a bifunctional hydroxyl group-containing compound, and (c-2) an oxazoline compound.
  • the content of the bifunctional hydroxyl group-containing compound and the oxazoline compound is from 2 parts by mass to 45 parts by mass with respect to 100 parts by mass of the polyimide.
  • the through-hole embedding property is excellent before crosslinking. It is soluble in an ant potassium solution and becomes insoluble in an alkaline solution after crosslinking. Moreover, when a polyimide has a hydroxyl group and / or a carboxyl group, it can react with an oxazoline compound and suppress warpage.
  • the bifunctional hydroxyl group-containing compound is present as the second component without being taken into the polyimide skeleton, shrinkage of the polyimide skeleton during curing can be prevented and warpage can be suppressed.
  • the inclusion of the oxazoline compound inactivates the carboxyl group at a low temperature and enables low-temperature curing, thus preventing shrinkage of the polyimide skeleton during curing and suppressing warpage.
  • the polyimide since the polyimide has a hydroxyl group and / or a carboxyl group, it becomes soluble in an alkaline aqueous solution before curing, becomes insoluble in an alkaline aqueous solution after curing, and has high heat resistance (for example, high solder heat resistance). Is expressed. Moreover, the curvature at the time of hardening can be suppressed by the said structure.
  • the polyimide structure has a hydroxyl group and / or a carboxyl group
  • the presence of a bifunctional hydroxyl group-containing compound in the resin composition can prevent the polyimide skeleton from shrinking during curing. That is, the curvature of the hardened
  • an oxazoline compound insolubility in an alkaline aqueous solution and higher heat resistance can be realized by polymerizing and crosslinking by reaction with a hydroxyl group.
  • the content of the bifunctional hydroxyl group-containing compound and the oxazoline compound is 2 to 45 parts by mass with respect to 100 parts by mass of the polyimide, and the polyimide is excessive with respect to other components.
  • the oxazoline group reacts with a hydroxyl group to form a structure containing a C ⁇ O group or an NH group, but the oxazoline group further reacts with a hydroxyl group and / or carboxylic acid contained in the polyimide remaining after the imidization reaction, An amide structure or a urea structure containing a C ⁇ O group or an NH group is formed.
  • the polyimide used for the resin composition according to the present embodiment has a hydroxyl group and / or a carboxyl group as a structural unit.
  • the polyimide structure part reacts with the crosslinkable functional group of the polyfunctional crosslinkable compound and cures, it shows insolubility in the alkaline aqueous solution after curing.
  • the polyimide used in the resin composition according to the present embodiment has a hydroxyl group and / or a carboxyl group as a structural unit.
  • a hydroxyl group and / or a carboxyl group can be introduced into polyimide by using a diamine having a hydroxyl group and / or a carboxyl group.
  • Such diamines include 2,5-diaminophenol, 3,5-diaminophenol, 4,4 ′-(3,3′-dihydroxy) diaminobiphenyl, 4,4 ′-(2,2 '-Dihydroxy) diaminobiphenyl, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3-hydroxy-4-aminobiphenyl (HAB), 4,4'-(3,3'- Dicarboxy) diphenylamine, methylenebisaminobenzoic acid (MBAA), 2,5-diaminobenzoic acid (DABA), 3,3′-dicarboxy-4,4′-diaminodiphenyl ether, and the like.
  • MBAA methylenebisaminobenzoic acid
  • DABA 2,5-diaminobenzoic acid
  • 3′-dicarboxy-4,4′-diaminodiphenyl ether and the like.
  • the resin composition according to the second aspect using the solvent-soluble polyimide having a hydroxyl group and / or a carboxyl group and a siloxane moiety as the polymer compound (A) has been described. It is also possible to use the resin composition according to the first aspect by using a polyimide that does not substantially contain a polyamic acid structure as long as the effects of the present invention are achieved.
  • the bifunctional hydroxyl group-containing compound used in the resin composition according to the present embodiment refers to a compound containing two hydroxyl groups per molecular chain.
  • the skeleton include those containing hydrocarbon groups such as aliphatic, aromatic, and alicyclic groups.
  • the skeleton is represented by the following formula (14) from the viewpoint of enhancing insulation. Those having a structure in the skeleton are preferred, and compounds containing aliphatic groups are preferred from the viewpoint of warpage suppression.
  • X is aromatic
  • Y is aliphatic having 1 to 10 carbon atoms
  • Z is a functional group selected from an ether group, an ester group, a carbonate group, a urethane group, and a urea group
  • h 0 represents an integer of 0 to 2
  • i represents an integer of 0 to 1
  • j represents an integer of 1 to 1000.
  • a polyphenol-terminated compound is preferable for crosslinking with the oxazoline compound.
  • halogen such as fluorine and chlorine are preferable.
  • bifunctional hydroxyl group-containing compound examples include polytetramethylene diol such as PTMG1000 manufactured by Mitsubishi Chemical Corporation, polybutadiene diol such as G-1000 manufactured by Nippon Soda Co., Ltd., hydrogenated polybutadiene diol such as GI-1000, Asahi Kasei Chemicals Corporation DURANOL T5651, DURANOL T5652, DURANOL T4671, and polycarbonate diols such as Placel CD manufactured by Daicel Chemical Co., Ltd.
  • polytetramethylene diol such as PTMG1000 manufactured by Mitsubishi Chemical Corporation
  • polybutadiene diol such as G-1000 manufactured by Nippon Soda Co., Ltd.
  • hydrogenated polybutadiene diol such as GI-1000, Asahi Kasei Chemicals Corporation DURANOL T5651, DURANOL T5652, DURANOL T4671
  • polycarbonate diols such as Placel CD manufactured by Daice
  • Hydrogenated bisphenols such as HB, phenol-modified silicones at both ends such as X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd., BY16-752 manufactured by Dow Corning, and BY16-799 are listed. It is.
  • a both-ends phenol-modified silicone, polybutadiene diol, hydrogenated polybutadiene diol, and polycarbonate diol are preferable from the viewpoint of improving insulation, and a both-end phenol-modified silicone and polycarbonate diol are preferable from the viewpoint of reducing warpage.
  • the bifunctional hydroxyl group-containing compound is preferably a liquid compound at room temperature from the viewpoint of warpage reduction and solubility in an organic solvent.
  • the number average molecular weight is preferably 500 to 3000, and particularly preferably the number average molecular weight is 500 to 2000.
  • the bifunctional hydroxyl group-containing compound is preferably contained in an amount of 3 parts by mass to 70 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of achieving both warpage reduction, solder heat resistance and chemical resistance. More preferably, it is contained in parts by mass.
  • bifunctional hydroxyl-containing compound containing two hydroxyl groups was demonstrated as (B) polyfunctional hydroxyl-containing compound, it contains two or more hydroxyl groups in the range with the effect of this invention. Polyols can also be used.
  • the oxazoline compound used in the resin composition according to the present embodiment is a compound having two or more oxazoline groups in the molecule.
  • the oxazoline compound one having at least two C ⁇ O groups and / or NH groups in the cross-linking when the cross-linking is formed between the polyimide (polymer compound) and / or the bifunctional hydroxyl group-containing compound is preferable. .
  • oxazoline compound examples include 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, K-2010E, K-2020E, K-2030E, and 2,6-bis (4 -Isopropyl-2-oxazolin-2-yl) pyridine, 2,6-bis (4-phenyl-2-oxazolin-2-yl) pyridine, 2,2'-isopropylidenebis (4-phenyl-2-oxazoline) 2,2′-isopropylidenebis (4-tertiarybutyl-2-oxazoline) and the like. These oxazoline compounds may be used alone or in combination of two or more.
  • a cured product can be obtained by heating the resin composition described above.
  • the mode of heating is not particularly limited, but it is preferable to heat at 50 ° C. to 140 ° C. for 1 minute to 60 minutes in order to make it soluble in an antkari aqueous solution.
  • a crosslinking reaction mainly occurs by heating in a high temperature region (for example, 160 ° C. to 200 ° C.), and becomes insoluble in an alkaline aqueous solution.
  • the maximum temperature is set in the range of 150 ° C. to 220 ° C. with an oven or a hot plate, and air or nitrogen is not used for 5 to 100 minutes. It crosslinks by heating in an active atmosphere.
  • the heating temperature may be constant over the entire processing time or may be gradually raised.
  • the resin composition film can be formed by printing on the surface of a flexible printed circuit board or a semiconductor wafer by known screen printing or a precision dispensing method.
  • the resin composition exhibits excellent heat resistance by thermosetting, the surface cured film of the semiconductor element, the interlayer insulating film, the bonding sheet, the protective insulating film for the printed wiring board, the surface protective film / interlayer insulating of the printed circuit board It is useful as a film and is applied to various electronic components.
  • the resin composition can be applied to copper foil F2-WS (12 ⁇ m) and dried at 95 ° C. for 12 minutes to produce a copper foil with resin having an insulating layer thickness of 15 ⁇ m.
  • Espanex M manufactured by Nippon Steel Chemical Co., Ltd.
  • insulating layer thickness 25 ⁇ m, conductor layer copper foil F2-WS (18 ⁇ m) is used.
  • thermosetting of the resin composition in the present embodiment is performed under relatively low temperature conditions (for example, 160 ° C. to 200 ° C.), copper oxidation does not occur.
  • a circuit board on which double-sided components were mounted was prepared using a double-sided copper-clad board of ESPANEX M (manufactured by Nippon Steel Chemical Co., Ltd., insulation layer thickness 25 ⁇ m, conductor layer copper foil F2-WS (18 ⁇ m)). Even if the resin composition is coated and dried on the substrate, cured after being processed with an alkaline aqueous solution, and the resin composition is used as a surface protective film, good insulating properties are exhibited.
  • the thickness of the surface protective film is preferably 1 ⁇ m to 50 ⁇ m. When the film thickness is 1 ⁇ m or more, the handling becomes easy, and when the film thickness is 50 ⁇ m or less, it is easy to bend and incorporate easily.
  • the resin composition which concerns on this Embodiment can also be used as a photosensitive resin composition by containing the (D) photosensitive agent.
  • the photosensitive film can also be obtained by apply
  • the resin composition according to the present embodiment can be used by containing (F) a phosphorus compound from the viewpoint of improving flame retardancy.
  • a phosphorus compound a phosphate ester compound or a phosphazene compound can be used.
  • the resin composition according to the present embodiment can be suitably used as an interlayer insulating film such as a multilayer flexible wiring board by providing a resin composition on a copper foil and drying it.
  • the resin composition according to the present embodiment can be suitably used as a protective film for a wiring pattern on a wiring board by providing the resin composition so as to cover the wiring pattern formed on the substrate.
  • the resin composition may contain an organic solvent in addition to polyimide, a bifunctional hydroxyl group-containing compound, an oxazoline compound, and the like. It is because it can use preferably as a varnish by setting it as the state melt
  • organic solvents examples include amide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, ⁇ - Lactone solvents such as butyrolactone and ⁇ -valerolactone, sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide and hexamethyl sulfoxide, phenol solvents such as cresol and phenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), Examples include ether solvents such as tetraglyme, dioxane, tetrahydrofuran, butyl benzoate, ethyl benzoate, and methyl benzoate.
  • amide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethyl
  • organic solvents may be used alone or in combination.
  • ⁇ -butyrolactone triglyme, butyl benzoate, and ethyl benzoate.
  • Example 1 The resin composition according to the first embodiment of the present invention will be described with reference to the following Example 1 and Comparative Example 1.
  • Sample 1 to Sample 32 are the resin composition according to the second aspect
  • Sample 33 to Sample 35 are the resin composition according to the first aspect.
  • Example 1 Sample 1 including a cured film of the resin composition was prepared, and its characteristics were confirmed.
  • a resin composition a polyimide varnish having an imidization ratio of 88% (hereinafter referred to as polyimide A), a polycarbonate diol, DURANOL T5651 manufactured by Asahi Kasei Chemicals Co., Ltd. (molecular weight 1000; hereinafter, polyfunctional hydroxyl group-containing compound A) And Duranate SBN-70D (NCO content: 10.2 wt%; hereinafter referred to as isocyanate compound A) manufactured by Asahi Kasei Chemicals, which is a hexamethylene diisocyanate block isocyanate, was used.
  • a method for synthesizing polyimide A, a method for producing a cured film, and a method for evaluating each property will be described.
  • Polyimide A A method for synthesizing polyimide A will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask.
  • the imidation ratio mentioned above was calculated
  • the imidation rate C calculated in the above formula is a value that makes the imidization rate during heat treatment at 220 ° C. for 60 minutes 100%.
  • the warpage was evaluated by lifting the four corners of the sample. Specifically, the sample 1 described above was cut into 5 cm ⁇ 5 cm in an environment of 23 ° C. and a humidity of 50%, and the distance at which the corner was raised relative to the central portion was measured as a warp. Those having a warp of 10 mm or less were evaluated as “good”, those having a warp of 5 mm or less were evaluated as “good”, ⁇ ⁇ being 15 mm or less, “ ⁇ ”, and those exceeding 15 mm were evaluated as “poor”.
  • solder resistance (heat resistance)
  • the solder resistance was evaluated by immersing Sample 1 cut to 3 cm ⁇ 3 cm in a solder bath at 260 ° C. for 60 seconds in accordance with the JPCA-BM02 standard. Visually inspect the external appearance to confirm the presence or absence of changes such as deformation and dissolution traces. If no change is observed in 90% or more of the total area, the circle is marked as ⁇ , and the area is 50% to 90%. The case where no change was observed was indicated by ⁇ , and the case where the region where no change was observed was less than 50% was indicated by ⁇ .
  • the viscosity of 100 ° C. to 220 ° C. was obtained by laminating 27 resin films obtained by etching and removing copper foil from a resin film having a copper foil as a base material using a measuring instrument AR-G2 manufactured by TA Instruments. Using the sample, evaluation was made with a rotor: 8 mm diameter parallel plate, strain: 0.1%, frequency: 1 Hz, and normal stress: 0.1 N (100 g). A case where the viscosity at 100 ° C. to 220 ° C. is in the range of 5000 Pa ⁇ s to 100000 Pa ⁇ s was marked with “ ⁇ ”, and a case where there was a region less than 5000 Pa ⁇ s or exceeded 100,000 Pa ⁇ s was marked with “X”.
  • Interlayer insulation resistance uses Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (insulation layer thickness 25 ⁇ m, conductor layer copper foil F2-WS (18 ⁇ m)) as the base material for flexible printed circuit boards.
  • Espanex M manufactured by Nippon Steel Chemical Co., Ltd.
  • insulation layer thickness 25 ⁇ m, conductor layer copper foil F2-WS (18 ⁇ m) As the base material for flexible printed circuit boards.
  • the insulation resistance between the resin films is 10 9 ⁇ or more. And the case where it did not reach 10 9 ⁇ was marked as x.
  • the through-hole embedding property was evaluated by an optical microscope after embedding the produced four-layer wiring board with an epoxy resin, cutting and polishing the wiring board.
  • the case where resin was embedded in the through hole without a gap was marked with ⁇ , and the case where a gap was observed in the through hole was marked with x.
  • thermal shock test In the thermal shock test, the produced four-layer wiring board was evaluated at ⁇ 40 ° C., 120 ° C. and 1000 cycles according to the JPCA-HD01-2003 standard. The case where the fluctuation of the connection resistance during the cycle was within 10% was marked as ⁇ , and the case where it exceeded 10% was marked as x.
  • the resin flowability was determined by visually checking the resin protrusion at the end of the sample after laminating a 20 cm square resin sheet based on copper foil with copper foil F2-WS (12 ⁇ m) and vacuum press (180 ° C., 20 minutes, 4 MPa). And evaluated. The case where the protrusion of the resin was 1 mm or less was evaluated as “ ⁇ ”, and the case where the resin exceeded 1 mm was evaluated as “X”.
  • Sample 1 The evaluation results of Sample 1 (Sample 1A, Sample 1B) are shown in Table 1 below.
  • Table 1 the cured product using the resin composition according to Sample 1 is sufficiently suppressed in warping during curing and is excellent in solder resistance (that is, heat resistance). Moreover, it turns out that it is excellent also in chemical resistance and the insulation of high temperature, high humidity conditions.
  • the cured product using the resin composition according to Sample 1 has good evaluation results in any of the evaluation of the elastic region and the plastic region, interlayer insulation resistance, through-hole embedding property, thermal shock test, and resin flow property. It was.
  • a cured film was prepared using a resin composition prepared under conditions different from those of Sample 1, and the characteristics of Sample 2 to Sample 21 were confirmed.
  • Samples 2 to 5 were prepared using a resin composition containing polyimide A, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A in the same manner as sample 1.
  • the main difference between Sample 2 to Sample 5 is the content of the polyfunctional hydroxyl group-containing compound A and the isocyanate compound A.
  • Sample 2 was prepared using a resin composition obtained by adding 7.5 parts by mass of polyfunctional hydroxyl group-containing compound A and 7.5 parts by mass of isocyanate compound A to 100 parts by mass of polyimide A.
  • Sample 3 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 10 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A.
  • Sample 4 was prepared using a resin composition in which 15 parts by mass of polyfunctional hydroxyl group-containing compound A and 15 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A.
  • Sample 5 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 15 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. The preparation method and evaluation method of Sample 2 to Sample 5 are the same as Sample 1.
  • Samples 6 to 9 were prepared using a resin composition containing polyimide (hereinafter referred to as polyimide B) having an imidization rate of 28%, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A, which will be described later.
  • the main difference between Samples 6 to 9 is the content of the polyfunctional hydroxyl group-containing compound A and the blocked isocyanate A.
  • Sample 6 was prepared using a resin composition in which polyfunctional hydroxyl group-containing compound A was added by 7.5 parts by mass and isocyanate compound A was added by 7.5 parts by mass with respect to 100 parts by mass of polyimide B.
  • Sample 7 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 10 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B.
  • Sample 8 was prepared using a resin composition in which 30 parts by mass of polyfunctional hydroxyl group-containing compound A and 30 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B.
  • Sample 9 was prepared using a resin composition in which 60 parts by mass of polyfunctional hydroxyl group-containing compound A and 60 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B.
  • the production method and evaluation method of Sample 6 to Sample 9 are the same as those of Sample 1.
  • Polyimide B A method for synthesizing polyimide B is as follows. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. In an ice-water bath at 0 ° C., Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight 1000) 40 g, ⁇ -butyrolactone (GBL) 60 g, ethyl benzoate (BAEE) 60 g, toluene 20 g, ⁇ -valerolactone 12 g, pyridine 18 g And stirred until uniform.
  • GBL ⁇ -butyrolactone
  • BAEE ethyl benzoate
  • Samples 10 to 15 were prepared using a resin composition containing polyimide A and isocyanate compound A.
  • the main difference between samples 10 to 15 is that any one of polyfunctional hydroxyl group-containing compounds B to F is used as the polyfunctional hydroxyl group-containing compound.
  • polyfunctional hydroxyl group-containing compound B polycarbonate diol Duranol T5652 (molecular weight 2000) manufactured by Asahi Kasei Chemicals Corporation was used.
  • polycarbonate diol Duranol T4671 molecular weight 1000 manufactured by Asahi Kasei Chemicals Corporation was used.
  • polyfunctional hydroxyl group-containing compound D polybutadienediol G-1000 (molecular weight 1000) manufactured by Nippon Soda Co., Ltd. was used.
  • polyfunctional hydroxyl group-containing compound E GI-1000 (molecular weight 1000) manufactured by Nippon Soda Co., Ltd., which is a hydrogenated polybutadiene diol, was used.
  • polyfunctional hydroxyl group-containing compound F PTMG1000 (molecular weight 1000) manufactured by Mitsubishi Chemical Corporation, which is polytetramethylene diol, was used.
  • Sample 10 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound B and 5 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A.
  • Sample 11 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound C and 10 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A.
  • Sample 12 was prepared using a resin composition obtained by adding 30 parts by mass of polyfunctional hydroxyl group-containing compound D and 30 parts by mass of isocyanate compound A to 100 parts by mass of polyimide A.
  • Sample 13 was prepared using a resin composition in which 30 parts by mass of polyfunctional hydroxyl group-containing compound E and 30 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A.
  • Sample 14 was prepared using a resin composition in which 30 parts by mass of polyfunctional hydroxyl group-containing compound F and 30 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A.
  • Sample 15 was prepared using a resin composition in which 7.5 parts by mass of polyfunctional hydroxyl group-containing compound B and 7.5 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A.
  • the production method and evaluation method of Sample 10 to Sample 15 are the same as those of Sample 1.
  • Samples 16 and 17 were prepared using a resin composition containing polyimide A and polyfunctional hydroxyl group-containing compound A.
  • the main difference between Sample 16 and Sample 17 is that any of isocyanate compounds B and C is used as the isocyanate compound.
  • Sample 16 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 9 parts by mass of isocyanate compound B were added to 100 parts by mass of polyimide A.
  • Sample 17 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 14 parts by mass of isocyanate compound C were added to 100 parts by mass of polyimide A.
  • the production method and evaluation method of Sample 16 and Sample 17 are the same as Sample 1.
  • Samples 18 and 19 were prepared using a resin composition containing polyimide B, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A.
  • the main differences between Sample 18 and Sample 19 are the content of polyfunctional hydroxyl group-containing compound A and isocyanate compound A, and the heating conditions during curing.
  • Sample 18 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 10 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B.
  • Sample 19 was prepared using a resin composition in which 30 parts by mass of polyfunctional hydroxyl group-containing compound A and 30 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B.
  • the heating conditions for curing were 180 ° C. for 60 minutes, then 180 ° C. for 60 minutes (that is, 180 ° C., 60 minutes ⁇ 2).
  • the production method and evaluation method of Sample 18 and Sample 19 excluding the heating conditions are the same as those of Sample 1.
  • Sample 20 and Sample 21 were prepared using a resin composition containing polyimide A, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A in the same manner as Sample 1.
  • the main difference between Sample 20 and Sample 21 is the content of polyfunctional hydroxyl group-containing compound A and isocyanate compound A.
  • Sample 20 was prepared using a resin composition in which 3 parts by mass of polyfunctional hydroxyl group-containing compound A and 3 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A.
  • Sample 21 was prepared using a resin composition obtained by adding 70 parts by mass of polyfunctional hydroxyl group-containing compound A and 70 parts by mass of isocyanate compound A to 100 parts by mass of polyimide A.
  • the preparation method and evaluation method of the sample 20 and the sample 21 are the same as those of the sample 1.
  • the evaluation results of Sample 2 to Sample 21 are shown in Table 1 below.
  • the cured product using the resin composition in this example has sufficiently suppressed warpage during curing, and is excellent in solder resistance (ie, heat resistance). It also has excellent chemical resistance and insulation under high temperature and high humidity conditions.
  • polybutadiene diol, hydrogenated polybutadiene diol, and polycarbonate diol are preferably used as the polyfunctional hydroxyl group-containing compound from the viewpoint of enhancing the insulation.
  • the heat treatment in the low temperature region (100 to 130 ° C) and the heat treatment in the high temperature region (160 to 200 ° C) are combined from the viewpoint of improving heat resistance and chemical resistance. It can be seen that it is preferable to use them.
  • the heat treatment conditions are not limited to this.
  • a cured film was prepared using a resin composition prepared under conditions different from those of Sample 1 to Sample 21, and the characteristics of Sample 22 to Sample 29 were confirmed.
  • Samples 22 to 25 were prepared in the same manner as Sample 1 using a resin composition containing polyimides C to F, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A.
  • the main difference between sample 22 to sample 25 is the imidization ratio of polyimide.
  • Samples 22 to 25 were prepared using a resin composition in which 15 parts by mass of the polyfunctional hydroxyl group-containing compound A and 15 parts by mass of the isocyanate compound A were added to 100 parts by mass of polyimides C to F. .
  • the preparation method and evaluation method of Samples 22 to 25 are the same as Sample 1.
  • Polyimide C A method for synthesizing polyimide C will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. At room temperature 25 ° C., 15 g of triethylene glycol dimethyl ether, 35 g of ⁇ -butyrolactone, 20.0 g of toluene, and 10.86 g (35.00 mmol) of 4,4′-oxydiphthalic dianhydride (manac, ODPA) Stir until uniform.
  • ODPA 4,4′-oxydiphthalic dianhydride
  • Polyimide D A method for synthesizing polyimide D will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. At room temperature of 25 ° C., 15 g of triethylene glycol dimethyl ether, 35 g of ⁇ -butyrolactone, 20.0 g of toluene, and 10.86 g (35.00 mmol) of ODPA were added and stirred until uniform. Thereafter, the temperature was raised to 80 ° C., 11.30 g (13.78 mmol) of KF-8010 was added, and the mixture was further stirred for 2 hours.
  • Polyimide E A method for synthesizing polyimide E will be described. The polyimide F synthesis method except that the first APB-N is 4.03 g (13.78 mmol) and the second APB-N is 1.97 g (6.73 mmol). Similarly, a polyimide E varnish having an imidization ratio of 80% was obtained.
  • Polyimide F A method for synthesizing polyimide F will be described. The polyimide D synthesis method except that the first APB-N is 4.86 g (16.62 mmol) and the second APB-N is 1.03 g (3.52 mmol). Similarly, a polyimide F varnish having an imidization ratio of 90% was obtained.
  • Sample 26 was prepared in the same manner as Sample 1 using a resin composition containing polyimide C, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A.
  • the main difference between sample 26 and sample 22 is the addition of flame retardant components.
  • 15 parts by mass of polyfunctional hydroxyl group-containing compound A and 15 parts by mass of isocyanate compound A with respect to 100 parts by mass of polyimide C, phosphazene derivative FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd. ) was added using 23 parts by mass of the resin composition.
  • the preparation method and evaluation method of the sample 26 are the same as those of the sample 1.
  • Sample 27 was prepared using the same resin composition as Sample 26. The main difference between the sample 27 and the sample 26 is the substrate used in [Preparation of cured film]. Specifically, in Sample 27, a 12 ⁇ m-thick copper foil F2-WS film manufactured by Furukawa Circuit Foil Co., Ltd. was used as the substrate, and a cured film was formed on the mat surface of the copper foil. The film thickness after drying and curing was about 30 ⁇ m. Other manufacturing methods and evaluation methods of the sample 27 are the same as those of the sample 1.
  • Sample 28 was prepared in the same manner as Sample 1 using a resin composition containing polyimide C, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A.
  • the main difference between the sample 28 and the sample 22 is the addition of a flame retardant component and the addition of a catalyst.
  • Sample 28 is 18 parts by mass of polyfunctional hydroxyl group-containing compound A, 18 parts by mass of isocyanate compound A, and 27 parts by mass of phosphazene derivative FP-300 (flame retardant A) manufactured by Fushimi Pharmaceutical Co., Ltd. with respect to 100 parts by mass of polyimide C.
  • Sample 29 was prepared using the same resin composition as Sample 28. The main difference between sample 29 and sample 29 is only the catalyst species. Specifically, 0.18 parts by mass of U-CAT (registered trademark) 1102 (catalyst B) manufactured by San Apro was used. Other manufacturing methods and evaluation methods of the sample 29 are the same as those of the sample 28.
  • Sample 30 to Sample 32 were prepared using the resin films prepared from Sample 27 to Sample 29, and their characteristics were confirmed.
  • Sample 30 was produced using the resin film obtained in Sample 27.
  • the main difference between the sample 30 and the sample 30 is that a resin film is laminated on a wiring board.
  • Espanex M manufactured by Nippon Steel Chemical Co., Ltd.
  • insulation layer thickness 25 ⁇ m, conductor layer copper foil F2-WS (18 ⁇ m) is used as the base material of the flexible printed wiring board, and the diameter is 0.1 mm.
  • a four-layer wiring board was prepared by copper plating and connecting 25 vias in a daisy chain.
  • Sample 31 was sample 28 and sample 32 was sample 29.
  • a wiring board was prepared by the same method as sample 30 and evaluated by the same method as sample 30.
  • a resin film was prepared using a resin composition prepared under conditions different from those of Sample 1 to Sample 32, and the characteristics of the prepared Sample 33 to Sample 35 were confirmed.
  • Sample 33 is a varnish of polyimide G having an imidization ratio of 100%, polyfunctional hydroxyl group-containing compound A, and Duranate TPA-100 manufactured by Asahi Kasei Chemicals, which is a hexamethylene diisocyanate-based isocyanate (NCO content: 23.1 wt%; What added the isocyanate compound C) was used.
  • Polyfunctional hydroxyl-containing compound A was 10 parts by mass and isocyanate compound C was 4.4 parts by mass with respect to 100 parts by mass of polyimide G.
  • Polyimide G A method for synthesizing polyimide G will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. At room temperature 25 ° C., 15 g of triethylene glycol dimethyl ether, 35 g of ⁇ -butyrolactone, 20.0 g of toluene, and 10.86 g (35.00 mmol) of 4,4′-oxydiphthalic dianhydride (manac, ODPA) Stir until uniform.
  • ODPA 4,4′-oxydiphthalic dianhydride
  • Sample 34 was obtained by adding Polyurethane G varnish to polycarbonate diol, Duranol T5650E (molecular weight 500) manufactured by Asahi Kasei Chemicals, and isocyanate compound D.
  • T5650E was 5 parts by mass and isocyanate compound D was 4.4 parts by mass with respect to 100 parts by mass of polyimide G.
  • the polyimide H might be 30 mass% with respect to the resin composition.
  • a wiring board was produced in the same manner as in Sample 30 and evaluated in the same manner as in Sample 30.
  • Sample 35 was obtained by adding polycarbonate polyol A having an average hydroxyl number of 3.6 as polycarbonate polyol and hexamethylene diisocyanate (hereinafter referred to as isocyanate compound E) to the varnish of polyimide G.
  • the polycarbonate polyol A was 6.2 parts by mass and the hexamethylene diisocyanate was 2 parts by mass with respect to 100 parts by mass of the polyimide G.
  • polyimide G might be 30 mass% with respect to the resin composition.
  • the yield was 1200 g.
  • the resin film using the resin composition according to Sample 30 to Sample 35 is excellent in interlayer insulation resistance, through-hole embedding property, solder resistance (that is, heat resistance), and thermal shock resistance.
  • the same effects as those of the resin compositions according to Sample 1 to Sample 21 shown in Table 1 below were obtained.
  • polyimide with 100% imidization ratio (sample 33 to sample 35)
  • trifunctional or higher polyfunctional hydroxyl group-containing compound (sample 35), using bifunctional isocyanate compound (sample) 35)
  • Comparative Example 1 As a comparative example, a cured film was prepared using a resin composition prepared under conditions different from those of Example 1 described above, and the characteristics of the prepared sample were confirmed. In this comparative example, Comparative Sample 1 to Comparative Sample 8 were prepared and their characteristics were confirmed.
  • Comparative samples 1 to 3 were prepared using a resin composition containing polyimide A.
  • the main differences between Comparative Sample 1 to Comparative Sample 3 are components other than polyimide A.
  • Comparative Sample 1 was prepared using a resin composition not containing polyfunctional hydroxyl group-containing compound A and isocyanate compound A.
  • the comparative sample 2 was produced using the resin composition which added polyfunctional hydroxyl-containing compound A by 5 mass parts with respect to 100 mass parts of polyimide A.
  • the comparative sample 3 was produced using the resin composition which added the isocyanate compound A at 5 mass parts with respect to 100 mass parts of polyimide A.
  • the preparation method and evaluation method of Comparative Sample 1 to Comparative Sample 3 are the same as those in Example 1.
  • Comparative sample 4 and comparative sample 5 were prepared using a resin composition containing polyimide A, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A.
  • the main difference between the comparative samples 4 and 5 is that the content of the isocyanate compound A with respect to the polyfunctional hydroxyl group-containing compound A (that is, the molar ratio between the hydroxyl group contained in the functional hydroxyl group-containing compound and the isocyanate group contained in the isocyanate compound A). It is.
  • the preparation method and evaluation method of the comparative samples 4 and 5 are the same as those in Example 1.
  • Comparative sample 6 was prepared using a resin composition containing polyfunctional hydroxyl group-containing compound A and isocyanate compound A. That is, the comparative sample 6 was produced using the resin composition which does not contain a polyimide. The preparation method and evaluation method of the comparative sample 6 are the same as those in Example 1.
  • Comparative sample 7 was prepared using a resin composition containing a polyfunctional hydroxyl group-containing compound and a polyimide having a imidization ratio of 100% in which a blocked isocyanate was incorporated into the skeleton (polyimide not containing a polyamic acid structure; hereinafter, polyimide H). did. Polyimide H contains a polyfunctional hydroxyl group-containing compound and a blocked isocyanate, and therefore does not contain a polyfunctional hydroxyl group-containing compound and a blocked isocyanate as a component of the resin composition. The preparation method and evaluation method of the comparative sample 7 are the same as those in Example 1.
  • Polyimide H The synthesis method of polyimide H is as follows. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. Asahi Kasei Chemicals Co., Ltd. Duranol T5651 (molecular weight 1000) 78.88 g, hexamethylene diisocyanate 26.91 g, ⁇ -butyrolactone (GBL) 177 g was charged. After stirring at 200 rpm for 15 minutes at room temperature in a nitrogen atmosphere, the temperature was raised to 140 ° C. and stirred for 1 hour.
  • the polyimide H does not contain a polyamic acid structure in the polyimide in the resin composition and incorporates a polyfunctional hydroxyl group-containing compound and a blocked isocyanate into the polyimide skeleton, not as components in the resin composition. It corresponds to.
  • Example 1 and Comparative Example 1 contain a polyimide having a polyimide structure and a polyamic acid structure as structural units, a polyfunctional hydroxyl group-containing compound, and an isocyanate compound.
  • the resin composition according to the second embodiment of the present invention will be described with reference to the following Example 2 to Example 12 and Comparative Example 2 to Comparative Example 6.
  • the following Examples 2 to 12 are resin compositions according to the second aspect.
  • E Photopolymerization initiator: Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (trade name: IRGACURE OXE-02 , Made by Ciba Japan)
  • Phosphorus compound Phosphazene compound (trade name: FP-300, manufactured by Fushimi Pharmaceutical Co., Ltd.)
  • Others Toluene (Wako Pure Chemical Industries, for organic synthesis), ⁇ -butyrolactone (Wako Pure Chemical Industries), sodium carbonate (Wako Pure Chemical Industries)
  • GPC Gel permeation chromatography
  • 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 (Teijin Deyupon Film Co., Ltd., G2) and coated with a clearance of 150 ⁇ m.
  • the coated film was dried at 95 ° C. for 12 minutes using a dryer (manufactured by ESPEC, SPHH-10 l) to obtain a photosensitive film.
  • 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.
  • the obtained photosensitive film was laminated on Kapton (registered trademark) (12 ⁇ m) under the above laminating conditions, and then baked at 180 ° C. for 2 hours. This film was cut into 5 cm squares, and those having a floating height of 5 mm or less at the end were indicated by ⁇ , those having a height of 5 to 10 mm or less were indicated by ⁇ , and those having a floating height higher than that were indicated by ⁇ .
  • Kapton registered trademark
  • IM resistance evaluation> The insulation reliability evaluation was performed as follows. A photosensitive film was laminated on the comb substrate having a line and space of 20 ⁇ m / 20 ⁇ m under the above laminating conditions, then exposed and developed under the above conditions, and baked at 180 ° C. for 2 hours. A migration tester cable was soldered to the film, and an insulation reliability test was conducted under the following conditions.
  • Appearance Comb substrate after IM test is observed with an optical microscope (ECLIPS LV100, manufactured by Nikon Corp.) under the conditions of transmitted light, 200 times. ⁇ .
  • ⁇ Polyimide (1)> In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (255 g), toluene (51.0 g), polyetheramine D-400 (86.8 g (201.9 mmol)), BPDA. (120 g (407.9 mmol)) was 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 40 ° C., APB-N (48.4 g (165.7 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours. Obtained. The weight average molecular weight of the obtained polyimide (1) is shown in Table 5 below.
  • ⁇ Polyimide (3)> In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (99.0 g), toluene (20.0 g), and polyetheramine D-400 (32.0 g (74.42 mmol)). BPDA (30.0 g (102.0 mmol)) was 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 40 ° C., APB-N (5.00 g (17.10 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide (3) solution. Obtained. The weight average molecular weight of the obtained polyimide (3) is shown in Table 5 below.
  • ⁇ Polyimide (5)> In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (107 g), toluene (21.0 g), Jeffamine XTJ-542 (25.7 g (25.70 mmol)), BPDA ( 30.0 g (102.0 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour.
  • ⁇ -butyrolactone 107 g
  • toluene 21.0 g
  • Jeffamine XTJ-542 25.7 g (25.70 mmol)
  • BPDA 30.0 g (102.0 mmol)
  • ⁇ Polyimide (6)> In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with ⁇ -butyrolactone (120 g), toluene (24.0 g), Jeffamine D-2000 (27.4 g (13.70 mmol)), BPDA ( 30.0 g (102.0 mmol)) was 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 40 ° C., APB-N (22.2 g (75.94 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide (6) solution. The weight average molecular weight of the obtained polyimide (6) is shown in Table 5 below.
  • T4671 (6 parts by mass), SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1) with respect to 100 parts by mass of polyimide (1) Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition.
  • the obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film.
  • the photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.
  • Example 4 With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), TPA-B80E (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition.
  • the obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film.
  • the photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.
  • Example 5 With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), SBN-70D (10 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition.
  • the obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film.
  • the photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.
  • Example 7 With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), SBN-70D (6 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 Part by mass) was mixed to prepare a photosensitive resin composition.
  • the obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film.
  • the photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.
  • Example 8 to 12 For each 100 parts by mass of polyimide (2) to (6), T5651 (6 parts by mass), SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition.
  • the obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film.
  • the photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.
  • Examples 2 to 12 have better developability, warpage, and insulation reliability than Comparative Examples 2 to 6.
  • the molar ratio of the hydroxyl group of the bifunctional hydroxyl group-containing compound to the isocyanate group of the isocyanate compound is smaller than 0.5.
  • warping occurred see Comparative Example 5
  • dendrites were generated (see Comparative Example 6).
  • Example 13 to Example 24 are resin compositions according to the second aspect.
  • silicone diamine manufactured by Shin-Etsu Chemical Co., Ltd., KF-8010
  • 1,3-bis (3-aminophenoxy) benzene manufactured by Mitsui Chemicals, APB-N
  • Tetramethylene oxide-di-p-aminobenzoate Ihara Chemical Co., abbreviation PMAB, the following general formula (22)
  • 4,4′-oxydiphthalic dianhydride Manac Co., abbreviation ODPA
  • 3,3 ′ , 4,4'-biphenyltetracarboxylic dianhydride Mitsubishii Chemicals, abbreviation BPDA
  • pyromellitic anhydride Daicel Chemical Industries, abbreviation PMDA
  • ethylene glycol bis trimellitic acid monoester anhydride
  • the insulation reliability evaluation was performed as follows. A photosensitive dry film was laminated on the comb substrate having a line-and-space of 20 ⁇ m / 20 ⁇ m under the above-mentioned laminating conditions, then exposed and developed under the above conditions, and baked at 180 ° C. for 1 hour. A migration tester cable was soldered to the photosensitive dry film, and an insulation reliability test was performed under the following conditions. Insulation deterioration evaluation system: SIR-12 (Enomoto Kasei Co., Ltd.) HAST chamber: EHS-211M (Espec Corp.) Temperature: 110 ° C Humidity: 85% Applied voltage: 2V Application time: 528 hours
  • Insulation resistance 1.0 ⁇ a ⁇ less than 10 6 Omega, less than 1.0 ⁇ 10 6 ⁇ ⁇ 1.0 ⁇ 10 7 ⁇ ⁇ and then, 1.0 ⁇ 10 7 ⁇ ⁇ 1.0 ⁇ 10 8 A value less than ⁇ was rated as ⁇ , and a value of 1.0 ⁇ 10 8 ⁇ or more was rated as ⁇ .
  • Appearance The comb substrate after the HAST test is observed with an optical microscope (ECLIPS LV100, manufactured by Nikon Corp.) under the conditions of transmitted light and 200 times. ⁇ .
  • Appearance (swelling and discoloration): Comb substrate after HAST test is observed with an optical microscope (ECLIPS LV100, manufactured by Nikon), bright field, 100 times condition, swelling and / or swelling of insulating film having a diameter of 50 ⁇ m ⁇ or more Those in which discoloration was observed were evaluated as x, those in which swelling and / or discoloration of an insulating film of 10 ⁇ m ⁇ or more and less than 50 ⁇ m ⁇ were observed were evaluated as ⁇ , and those having swelling and discoloration of 10 ⁇ m ⁇ or less were evaluated as ⁇ .
  • the obtained photosensitive dry film was laminated on Kapton (registered trademark) under the above-mentioned lamination conditions, and then baked at 180 ° C. for 1 hour.
  • a photosensitive dry film was cut out into 5 cm squares, and those with a floating height of less than 5 mm were marked with ⁇ , those with a height of less than 5 to 10 mm were marked with ⁇ , and those with a floating height higher than that were marked with ⁇ .
  • the resolution evaluation was performed as follows. A photosensitive dry film was laminated on the copper clad laminate under the above-mentioned lamination conditions, and then exposed at 30 to 270 mJ / cm 2 . Subsequently, alkaline development with a 1% by mass aqueous sodium carbonate solution and rinsing with water were performed, and the pattern was evaluated with an optical microscope after drying. A 50 ⁇ m to 100 ⁇ m line and space (L / S) pattern was used for the mask. The remaining film ratio of the exposed part (cured part) was 100% by development, and the part where the copper surface of the unexposed part (dissolved part) appeared was read. The case where 70 ⁇ m L / S could be resolved was marked with ⁇ , the case where 100 ⁇ m L / S pattern could be resolved was marked with ⁇ , and the case where 100 ⁇ m could not be resolved was marked with ⁇ .
  • APB-N (6.10 g (20.87 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of polyimide (8).
  • the weight average molecular weight is shown in Table 7 below.
  • APB-N (6.65 g (22.75 mmol) was subsequently added and stirred for 8 hours at 25 ° C. to obtain a solution of polyimide (9).
  • the weight average molecular weight is shown in Table 7 below.
  • polyimide (11) After cooling, APB-N (7.20 g (24.63 mmol) was added and stirred at 25 ° C. for 8 hours to obtain a solution of polyimide (11).
  • the weight average molecular weight of the obtained polyimide (11) was It shows in Table 7 below.
  • Example 13 to 15 BPE-500 (20 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass) with respect to 100 parts by mass of polyimide (7), polyimide (8), polyimide (9), FP-300 (25 parts by mass) and TBXP (15 parts by mass) were mixed to prepare a photosensitive resin composition.
  • the obtained photosensitive resin composition was made into a dry film by the dry film manufacturing method described above to obtain a photosensitive film.
  • This photosensitive film was laminated on a comb-type substrate under the above-mentioned laminating conditions. The insulation reliability of the obtained laminated film was evaluated. The results are shown in Table 8 below. In Examples 13 and 14, the warpage was ⁇ and the resolution was ⁇ , and in Example 15 the warp was ⁇ and the resolution was ⁇ .
  • Example 16 BPE-500 (40 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts by mass) are mixed with 100 parts by mass of polyimide (7).
  • a resin composition was prepared.
  • a laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ⁇ and the resolution was x.
  • Example 17 M-310 (40 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts by mass) are mixed with 100 parts by mass of polyimide (7).
  • a resin composition was prepared.
  • a laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. Further, the warpage was ⁇ , and the resolution was ⁇ .
  • Example 18 BPE-900 (20 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts) with respect to 100 parts by mass of polyimide (7) Part by mass) was mixed to prepare a photosensitive resin composition.
  • a laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ⁇ and the resolution was ⁇ .
  • Example 20 BPE-500 (20 parts by mass), M-350 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts) with respect to 100 parts by mass of polyimide (7) Part by mass) was mixed to prepare a photosensitive resin composition.
  • a laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ⁇ and the resolution was ⁇ .
  • Example 21 BPE-500 (20 parts by mass), M-306 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts) with respect to 100 parts by mass of polyimide (7) Part by mass) was mixed to prepare a photosensitive resin composition.
  • a laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ⁇ and the resolution was ⁇ .
  • Example 22 BPE-500 (20 parts by weight), A-TMMT (20 parts by weight), OXE-02 (1 part by weight), FP-300 (25 parts by weight), TBXP (15 parts per 100 parts by weight of polyimide (7) Part by mass) was mixed to prepare a photosensitive resin composition.
  • a laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ⁇ and the resolution was ⁇ .
  • Example 23 BPE-500 (20 parts by mass), A-GLY-9E (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP with respect to 100 parts by mass of polyimide (7) (15 parts by mass) was mixed to prepare a photosensitive resin composition.
  • a laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ⁇ and the resolution was ⁇ .
  • Example 24 BPE-500 (20 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts) with respect to 100 parts by mass of polyimide (7) Part by mass), T5651 (3 parts by mass), and SBN-70D (3 parts by mass) were mixed to prepare a photosensitive resin composition.
  • a laminated film was produced from the obtained photosensitive resin composition by the same method as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ⁇ and the resolution was ⁇ .
  • Example 13 to 13 using photosensitive resin compositions containing the polyimide structure represented by the general formula (7) and the polyamic acid structure represented by the general formula (8) were used.
  • Example 24 it can be seen that the insulation reliability (HAST resistance) is excellent as compared with Comparative Example 7 and Comparative Example 8.
  • Example 13 and Example 20 are compared with Example 22 and Example 23, resin containing the (meth) acrylate compound which has three or more double bonds of the structure shown by the said General formula (10). It can be seen that the composition has better insulation reliability (HAST resistance).
  • Example 25 and Example 26 are the resin compositions which concern on a 2nd aspect.
  • Example 25 As a resin composition, a varnish of polyimide Z having an imidization ratio of 100%, a bifunctional hydroxyl-containing compound, both-end type phenol-modified silicone X-22-1821 (hydroxyl value 38 mgKOH) manufactured by Shin-Etsu Chemical Co., Ltd. / G), 1,3-bis (4,5-dihydro-2-oxazolyl) benzene (hereinafter referred to as BPO) as an oxazoline compound, and flame retardant A (see Example 1) were used.
  • BPO 1,3-bis (4,5-dihydro-2-oxazolyl) benzene
  • a material obtained by adding 5 parts by mass of double-end type phenol-modified silicone X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd., 13 parts by mass of BPO, and 33 parts by mass of flame retardant A to 100 parts by mass of polyimide Z was used.
  • This resin composition was applied to a copper foil and dried at 95 ° C. for 12 minutes to obtain a resin film having a thickness of 30 ⁇ m.
  • This resin film was used for evaluation of antkari solubility.
  • the resin film was heated at 180 ° C. for 60 minutes to obtain a cured product. This cured product was used for evaluation of alkali resistance.
  • a method for synthesizing polyimide Z will be described.
  • Polyimide Z A method for synthesizing polyimide Z will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. At room temperature 25 ° C., 15 g of triethylene glycol dimethyl ether, 35 g of ⁇ -butyrolactone, 20.0 g of toluene, and 10.86 g (35.00 mmol) of 4,4′-oxydiphthalic dianhydride (manac, ODPA) Stir until uniform.
  • ODPA 4,4′-oxydiphthalic dianhydride
  • the warpage was evaluated by lifting the four corners of the resin film. Specifically, the sample 1 described above was cut into 5 cm ⁇ 5 cm in an environment of 23 ° C. and a humidity of 50%, and the distance at which the corner was raised relative to the central portion was measured as a warp. Those having a warp of 10 mm or less were evaluated as “good”, those having a warp of 5 mm or less were evaluated as “good”, ⁇ ⁇ were determined as 15 mm or less, and those exceeding 15 mm were evaluated as “poor”.
  • solder resistance was evaluated by immersing a cured product cut to 3 cm ⁇ 3 cm in a solder bath at 260 ° C. for 60 seconds in accordance with the JPCA-BM02 standard. Visually inspect the external appearance to confirm the presence or absence of changes such as deformation and dissolution traces. If no change is observed in 90% or more of the total area, the circle is marked as ⁇ , and the area is 50% to 90%. The case where no change was observed was indicated by ⁇ , and the case where the region where no change was observed was less than 50% was indicated by ⁇ .
  • Example 26 As a resin composition, 10 parts by mass of a both-end type phenol-modified silicone X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd. as a bifunctional hydroxyl group-containing compound and 100 parts by mass of polyimide Z as an oxazoline compound A product obtained by adding 20 parts by mass of BPO and 33 parts by mass of flame retardant A was used. Others were produced and evaluated in the same manner as in Example 25 by preparing resin films and cured products.
  • a resin composition 10 parts by mass of a both-end type phenol-modified silicone X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd. as a bifunctional hydroxyl group-containing compound and 100 parts by mass of polyimide Z as an oxazoline compound A product obtained by adding 20 parts by mass of BPO and 33 parts by mass of flame retardant A was used. Others were produced and evaluated in the same manner as in Example 25 by preparing resin films and cured products.
  • Table 9 below shows the evaluation results of Example 25, Example 26, and Comparative Examples 9 to 11.
  • the resin films using the resin compositions according to Example 25 and Example 26 show alkali-solubility while the cured product exhibits alkali resistance, and further has low warpage and excellent solder resistance. The effect similar to the resin composition which concerns on the other Example mentioned above was acquired.
  • Comparative Examples 9 to 11 it can be seen that the evaluation of solder resistance, warpage, and the like deteriorates when any of the polyimide, bifunctional hydroxyl group-containing compound and oxazoline compound is not included.
  • the present invention has an effect that a sufficient warpage reduction during curing and a resin composition capable of realizing excellent heat resistance can be realized, and in particular, a surface protection film for semiconductor elements, an interlayer insulating film, a bonding sheet It can be suitably used as a semiconductor package substrate, a protective layer for circuit boards, a protective insulating film for printed wiring boards, and a protective insulating film for flexible printed boards.

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WO2013108890A1 (ja) * 2012-01-20 2013-07-25 旭化成イーマテリアルズ株式会社 樹脂組成物、積層体、多層プリント配線板及び多層フレキシブル配線板並びにその製造方法
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