WO2011004756A1 - Composition thermodurcissable pour film protecteur pour tableau de connexions - Google Patents

Composition thermodurcissable pour film protecteur pour tableau de connexions Download PDF

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Publication number
WO2011004756A1
WO2011004756A1 PCT/JP2010/061226 JP2010061226W WO2011004756A1 WO 2011004756 A1 WO2011004756 A1 WO 2011004756A1 JP 2010061226 W JP2010061226 W JP 2010061226W WO 2011004756 A1 WO2011004756 A1 WO 2011004756A1
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Prior art keywords
group
component
polyurethane
wiring board
formula
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PCT/JP2010/061226
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English (en)
Japanese (ja)
Inventor
一彦 大賀
律子 東
美奈 大西
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昭和電工株式会社
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Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to CN201080030631.8A priority Critical patent/CN102471460B/zh
Priority to JP2011521896A priority patent/JPWO2011004756A1/ja
Priority to KR1020117024563A priority patent/KR101317259B1/ko
Publication of WO2011004756A1 publication Critical patent/WO2011004756A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions

Definitions

  • the present invention relates to a novel thermosetting composition for a protective film of a wiring board, a protective film for a wiring board obtained by curing the thermosetting composition for the protective film, a flexible wiring board covered with the protective film, and
  • the present invention relates to a method for manufacturing a flexible wiring board covered with the protective film. More specifically, a thermosetting composition for a protective film of a wiring board excellent in low warpage, flexibility, and long-term electrical insulation reliability, and a wiring board obtained by curing the thermosetting composition for a protective film.
  • the present invention relates to a protective film, a flexible wiring board partially or entirely covered with the protective film, and a method for manufacturing a flexible wiring board covered with the protective film.
  • surface protection films for flexible wiring circuits are made by punching out a die that matches the pattern of a polyimide film called a coverlay film, and then pasting it using an adhesive, or UV curing with flexibility.
  • a type or a thermosetting type overcoat agent is applied by a screen printing method, and the latter is particularly useful in terms of workability.
  • resin compositions mainly composed of epoxy resin, acrylic resin, or composites thereof are known. These are often mainly composed of resins that have undergone modification such as introduction of a butadiene skeleton, siloxane skeleton, polycarbonate diol skeleton, long chain aliphatic skeleton, etc.
  • Patent Document 1 JP-A-11-61038 discloses a resin composition using a blocked isocyanate of polybutadiene and a polyol, but the cured product is excellent in terms of flexibility and shrinkage. However, heat resistance is not enough.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-137370 (Patent Document 2) includes a polyamide-imide resin obtained by reacting a polycarbonate diol and a diisocyanate compound and a terminal diisocyanate polyurethane and trimellitic acid, and an amine-type epoxy resin. Although the composition containing this was disclosed, there existed a fault that the long-term reliability of the electrical property of the hardened
  • Patent Document 3 discloses a composition containing a carboxyl group-containing polyurethane polyimide and an epoxidized polybutadiene. This composition is dried to be a solvent. At the time of removal, the carboxyl group-containing polyurethane polyimide and the epoxidized polybutadiene are liable to cause a phase separation structure and have a disadvantage that a uniform film is hardly formed.
  • Patent Document 4 discloses a polyamideimide resin having an organosiloxane skeleton, but the adhesion between the cured product and the substrate is not good. It is necessary to use a special solvent such as methyl-2-pyrrolidone, which may cause a problem because the emulsion may be dissolved particularly during screen printing.
  • Patent Document 5 discloses a carboxyl group-containing polyurethane and an epoxy compound having a polyol unit selected from the group consisting of polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol.
  • a composition comprising is disclosed. For example, looking at the circuit pattern formation method used in the COF (Chip on Film) mounting method, the wiring that is currently widely used in the COF mounting method is produced by the subtractive method. . As an insulating film for wiring produced by these subtractive methods, a cured product obtained from the composition disclosed in Patent Document 5 exhibits sufficient insulating performance.
  • Patent Document 6 discloses a solder resist ink containing a carboxyl group-containing polyurethane having an organic residue derived from dimer diol and an epoxy compound. Regarding the cured product obtained from this composition, the solder resist ink disclosed in Patent Document 6 exhibits sufficient insulating performance as an insulating coating for wiring produced by the subtractive method.
  • An object of the present invention is to provide a thermosetting composition for a protective film of a wiring board, which is flexible and can obtain a protective film having good electrical insulation characteristics even in a semi-additive method, and a wiring board obtained by curing the composition
  • An object of the present invention is to provide a protective wiring film, a flexible wiring board covered with the protective film, and a method of manufacturing the flexible wiring board.
  • the present inventors have used a curable composition containing a polyurethane having a specific structural unit, an epoxy group-containing compound having a specific structure, and a solvent.
  • the present inventors have found that a cured product obtained by curing this curable composition is excellent in flexibility and electrical insulating properties, and the present invention has been completed.
  • the present invention (I) comprises an epoxy group-containing compound having a tricyclodecane structure, a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by formula (1), and a solvent as essential components. It is a thermosetting composition for protective film of a wiring board.
  • R 1 represents an alkylene group having 3 to 18 carbon atoms, and n represents an integer of 1 or more.
  • the present invention (II) is a protective film for a wiring board obtained by curing the thermosetting composition for a protective film for a wiring board of the present invention (I).
  • part or all of the surface of the flexible wiring board in which the wiring is formed on the flexible substrate is covered with the protective film of the wiring board of the present invention (II).
  • This is a flexible wiring board covered with a protective film.
  • a printed film is formed on the pattern by printing the thermosetting composition for the protective film of the wiring board of the present invention (I) on the wiring pattern portion subjected to tin plating of the flexible wiring board.
  • the epoxy group-containing compound having a tricyclodecane structure has a tricyclo [5.2.1.0 2,6 ] decane structure or a tricyclo [3.3.1.1 3,7 ] decane structure
  • the thermosetting composition for a protective film for a wiring board according to [1] which is an epoxy group-containing compound having an aromatic ring structure.
  • thermosetting composition for a protective film of a wiring board according to [2], wherein the epoxy group-containing compound having a tricyclodecane structure is a compound represented by the formula (2).
  • l represents 0 or an integer of 1 or more.
  • the polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) has a functional group capable of reacting with an epoxy group and represented by the formula (1)
  • thermosetting composition for a protective film of a wiring board according to any one of [1] to [4], wherein the functional group capable of reacting with an epoxy group is a carboxyl group.
  • thermosetting composition for a protective film for a wiring board according to any one of [1] to [4], wherein the functional group capable of reacting with an epoxy group is an acid anhydride group.
  • a polyurethane polyimide having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) and further having an imide bond reacts the following components (a) to (d):
  • R 2 and R 3 each independently represents a divalent aliphatic or aromatic hydrocarbon group
  • Y 1 represents a tetravalent organic group derived from a tetracarboxylic acid or an acid anhydride group thereof.
  • X 1 represents a divalent organic group derived from diamine or diisocyanate, and m is an integer of 0 to 20.
  • a polyurethane polyimide having a functional group capable of reacting with an epoxy group, having a structural unit represented by the formula (1), and further having an imide bond is selected from the group consisting of the formulas (4) to (6):
  • a plurality of R 4 are each independently an alkylene group having 3 to 18 carbon atoms
  • a plurality of R 5 are each independently an alkylene group having 3 to 18 carbon atoms
  • a and b are And each independently represents an integer of 1 to 20
  • the plurality of X 2 are each independently a divalent organic group.
  • a plurality of R 6 are each independently an alkylene group having 3 to 18 carbon atoms
  • a plurality of R 7 are each independently an alkylene group having 3 to 18 carbon atoms
  • c and d are And each independently represents an integer of 1 to 20
  • a plurality of X 3 are each independently a divalent organic group
  • Y 2 is CH 2 , SO 2 or O.
  • a plurality of R 8 are each independently an alkylene group having 3 to 18 carbon atoms
  • a plurality of R 9 are each independently an alkylene group having 3 to 18 carbon atoms
  • e and f are: Each independently represents an integer of 1
  • a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) comprises the following component (a), component (b), component (c) and component (e):
  • a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) has a functional group capable of reacting with an epoxy group and represented by the formula (1)
  • the solvent is a mixed solvent containing at least one solvent having a boiling point of 170 ° C. or more and less than 200 ° C. under atmospheric pressure and at least one solvent having a boiling point of 200 ° C. to 220 ° C. under atmospheric pressure.
  • the solvent is a mixed solvent containing at least one solvent selected from the following group A and at least one solvent selected from the following group B as essential components [1] ⁇
  • Group A Diethylene glycol dimethyl ether (boiling point 162 ° C.), diethylene glycol diethyl ether (boiling point 189 ° C.), diethylene glycol ethyl methyl ether (boiling point 176 ° C.), dipropylene glycol dimethyl ether (boiling point 171 ° C.), 3-methoxybutyl acetate (boiling point 171) ° C), ethylene glycol monobutyl ether acetate (boiling point 192 ° C)
  • Group B diethylene glycol butyl methyl ether (boiling point 212 ° C.), tripropylene glycol dimethyl ether (boiling point 215 ° C.), triethylene glycol dimethyl ether (boiling point 216 ° C.), ethylene glycol dibutyl ether (boiling point 203 ° C.), diethylene glycol monoethyl ether acetate (bo
  • thermosetting composition for a protective film for a wiring board obtained by curing the thermosetting composition for a protective film for a wiring board according to any one of [1] to [12].
  • a part of or all of the surface of the flexible wiring board in which the wiring is formed on the flexible substrate is covered with the protective film of the wiring board according to [13].
  • a flexible wiring board covered with a protective film is covered with a protective film.
  • thermosetting composition for a protective film of a wiring board according to any one of [1] to [12] is printed on the wiring pattern portion of the flexible wiring board that has been subjected to tin plating, thereby printing on the pattern
  • a method for producing a flexible wiring board coated with a protective film, comprising forming a film and forming the protective film by heating and curing the printed film at 80 to 130 ° C.
  • the cured product of the present invention has no tack, good handling properties, good flexibility and moisture resistance, long-term electrical insulation reliability at a high level, and low warpage.
  • the adhesiveness to the underfill material is good, and the solvent resistance is also good.
  • the thermosetting composition of the present invention when applying the thermosetting composition of the present invention to a flexible substrate such as a flexible wiring board or a polyimide film, and then creating a cured product (protective film) by a curing reaction, the flexible wiring board with a protective film
  • the warp of the flexible base material with a protective film is small, and thereafter the alignment of the IC chip mounting process is facilitated.
  • the cured product of the present invention has flexibility, it is possible to provide a flexible wiring board with an electrically insulating protective film (for example, a flexible printed wiring board such as COF) that is less prone to cracking.
  • the present invention (I) includes an epoxy group-containing compound having a tricyclodecane structure, a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1), and a wiring containing a solvent as essential components It is a thermosetting composition for the protective film of a board.
  • R 1 represents an alkylene group having 3 to 18 carbon atoms, and n represents an integer of 1 or more.
  • the present invention (II) is a protective film for a wiring board obtained by curing the protective film thermosetting composition for the wiring board of the present invention (I).
  • the epoxy group-containing compound having a tricyclodecane structure which is one of the essential components of the composition of the present invention (I), is not particularly limited as long as it is a compound having a tricyclodecane structure and an epoxy group in the molecule.
  • tricyclodecane structure examples include a tricyclo [5.2.1.0 2,6 ] decane structure or a tricyclo [3.3.1.1 3,7 ] decane structure.
  • Examples of the epoxy group-containing compound having a tricyclo [5.2.1.0 2,6 ] decane structure include compounds represented by the following formula (2) and the following formula (34). (In the formula, l represents 0 or an integer of 1 or more.) (In the formula, g represents 0 or an integer of 1 or more.)
  • examples of the epoxy group-containing compound having a tricyclo [3.3.1.1 3,7 ] decane structure include compounds represented by the following formula (35) to the following formula (38).
  • the compound represented by the formula (2) is particularly preferable.
  • the compound represented by the formula (2) is commercially available from DIC Corporation (grade names: Epicron HP-7200L, Epicron HP-7200, Epicron HP-7200H, Epicron HP-7200HH), and also from Nippon Kayaku Co., Ltd. It is commercially available under the grade names XD-1000-2L and XD-1000, and is easily available.
  • the amount of the epoxy group-containing compound having a tricyclodecane structure, which is an essential component of the present invention (I), has a functional group capable of reacting with an epoxy group, which is an essential component of the present invention (I), which will be described later, and It can be shown by the ratio of the number of functional groups capable of reacting with epoxy groups contained in the polyurethane having the structural unit represented by formula (1) and the number of epoxy groups.
  • the functional group capable of reacting with the epoxy group is a group that reacts 1: 1 with the epoxy group
  • the functional group capable of reacting with the epoxy group contained in the thermosetting composition of the present invention (I)
  • the ratio of the number and the number of epoxy groups of the epoxy group-containing compound having a tricyclodecane structure is preferably in the range of 1/3 to 2/1, more preferably 1 / 2.5 to 1.5 / 1 range. When this ratio is smaller than 1/3, there is a high possibility that many unreacted epoxy groups remain, which is not preferable. On the other hand, if this ratio is larger than 2/1, many functional groups capable of reacting with unreacted epoxy groups remain, which is not preferable in terms of electrical insulation performance. For example, it can be mentioned as a functional group in which a carboxyl group reacts with an epoxy group 1: 1.
  • a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) reacts with an epoxy group in the molecule. If it is a polyurethane which has a functional unit and the structural unit shown by Formula (1), there will be no restriction
  • R 1 represents an alkylene group having 3 to 18 carbon atoms, and n represents an integer of 1 or more.
  • R 1 represents an alkylene group having 3 to 18 carbon atoms.
  • the water resistance of the resulting polyurethane cannot be kept sufficiently, which is not preferable.
  • the type of solvent capable of dissolving the generated polyurethane may be extremely reduced, or adhesion to polyimide may be lowered, which is not preferable.
  • n is preferably an integer of 1 to 20.
  • the structural unit of the formula (1) is a structural unit derived from a (poly) carbonate diol raw material having a diol structural unit having 3 to 18 carbon atoms. Further, in order to increase water resistance, dimer diol is combined with an epoxy group. It can be preferably used as one component when producing a polyurethane having a functional group capable of reacting and having a structural unit represented by the formula (1).
  • the raw material (poly) carbonate diol having a number average molecular weight of 400 to 10,000 can be used.
  • (poly) carbonate in the (poly) carbonate diol described in this specification means that the molecule has one or more carbonate bonds.
  • (poly) carbonate means both monocarbonate and polycarbonate. Therefore, “(poly) carbonate diol” described in the present specification means a compound having one or more carbonate bonds in the molecule and two alcoholic hydroxyl groups.
  • the raw material diol component may remain and be included.
  • the remaining diol component is referred to as “(poly) carbonate diol”. It is defined as not included.
  • (poly) carbonate diol is produced by transesterification using 1,9-nonanediol and diethyl carbonate as raw materials in the presence of a catalyst
  • the raw material 1,9-nonanediol is a product.
  • 5 mass% remains in a certain (poly) carbonate diol, it means that the remaining 1,9-nonanediol is not included in the “(poly) carbonate diol”.
  • Examples of the functional group capable of reacting with the epoxy group include functional groups such as amino group, carboxyl group, carboxylic anhydride group, mercapto group, isocyanato group and hydroxyl group.
  • the reaction rate with the epoxy group-containing compound having a tricyclodecane structure is preferably within a certain range. From this, a carboxyl group and a carboxylic anhydride group are preferable. Further, it is desirable in use that the functional group is stable in the odor of the compound or in a normal atmosphere in a normal temperature atmosphere. In view of this, a carboxyl group is most desirable.
  • the increase in the crosslinking density during curing should be smaller unless the solvent resistance, long-term electrical insulation properties, and heat resistance of the cured product are impaired. desirable.
  • it has a functional group that can react with an epoxy group and is represented by the formula (1
  • the polyurethane having the structural unit represented by () preferably has at least one structure in the molecule among the following three structures.
  • a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) further has an imide structure. That is, a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) has a functional unit capable of reacting with an epoxy group and represented by the formula (1). It is desirable to be a polyurethane polyimide having an imide bond.
  • the following one structure desirably has a certain branched structure in the molecule as long as it is soluble in the solvent.
  • Another structure is a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1), and further containing an organic residue derived from dimer diol. desirable.
  • a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by formula (1) has a functional unit capable of reacting with an epoxy group and represented by formula (1).
  • a case of polyurethane polyimide having an imide bond is described.
  • polyurethane polyimide having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) and further having an imide bond examples include, for example, JP-A-2003-198105 and JP-A-2006. Examples thereof include a polyurethane polyimide having a functional group capable of reacting with an epoxy group described in Japanese Patent No. -307183, a structural unit represented by the formula (1), and further having an imide bond.
  • a polyurethane polyimide having a functional group capable of reacting with an epoxy group described in JP-A No. 2003-198105 and having a structural unit represented by the formula (1) and further having an imide bond is represented by the following formula ( 4)
  • a plurality of R 4 are each independently an alkylene group having 3 to 18 carbon atoms
  • a plurality of R 5 are each independently an alkylene group having 3 to 18 carbon atoms
  • a and b are And each independently represents an integer of 1 to 20, and the plurality of X 2 are each independently a divalent organic group.
  • a plurality of R 6 are each independently an alkylene group having 3 to 18 carbon atoms
  • a plurality of R 7 are each independently an alkylene group having 3 to 18 carbon atoms
  • c and d are: Each independently represents an integer of 1 to 20, a plurality of X 3 are each independently a divalent organic group, and Y 2 is CH 2 , SO 2 or O.
  • a plurality of R 8 are each independently an alkylene group having 3 to 18 carbon atoms
  • a plurality of R 9 are each independently an alkylene group having 3 to 18 carbon atoms
  • e and f are:
  • a plurality of X 4 are each independently a divalent organic group
  • Y 3 is any one of the following formulas (7) to (33): .
  • the polyurethane polyimide having the structure represented by formula (4) or formula (5) is usually one or more compounds selected from trivalent polycarboxylic acids having acid anhydride groups and derivatives thereof, and isocyanate compounds or amines. Obtained by reacting with a compound.
  • the trivalent polycarboxylic acid having an acid anhydride group and its derivative are not particularly limited.
  • a compound represented by the formula (39) is used.
  • Trimellitic anhydride is particularly preferable from the viewpoints of heat resistance and cost.
  • R 14 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.
  • the compound shown by Formula (40) can be used.
  • R 15 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group
  • Y 2 represents CH 2 , CO, SO 2 , or O.
  • a compound represented by the formula (41) can be used.
  • Y 3 is any one of the above formulas (7) to (33).
  • tetracarboxylic dianhydrides may be used alone or in combination of two or more.
  • an aliphatic dicarboxylic acid succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc.
  • Aromatic dicarboxylic acids isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.
  • an amide bond is also formed in the molecular chain.
  • a diisocyanate compound represented by the formula (42) can be used.
  • a plurality of R 16 are each independently an alkylene group having 3 to 18 carbon atoms
  • a plurality of R 17 are each independently an alkylene group having 3 to 18 carbon atoms
  • h and i are And each independently represents an integer of 1 to 20
  • a plurality of X 5 are each independently a divalent organic group.
  • the diisocyanate compound of the formula (42) can be obtained by reacting the (poly) carbonate diol represented by the formula (43) with the diisocyanate represented by the formula (44).
  • a plurality of R 18 are each independently an alkylene group having 3 to 18 carbon atoms, and j is an integer of 1 to 20
  • X 6 is a divalent organic group.
  • X 6 of the diisocyanate represented by the formula (44) is, for example, an alkylene group having 1 to 20 carbon atoms or a phenylene group that is unsubstituted or substituted with a lower alkyl group having 1 to 5 carbon atoms such as a methyl group.
  • An arylene group is mentioned.
  • the number of carbon atoms of the alkylene group is more preferably 1-18.
  • a group having two aromatic rings such as diphenylmethane-4,4′-diyl group and diphenylsulfone-4,4′-diyl group is also preferable.
  • Examples of the (poly) carbonate diol represented by the above formula (43) include ⁇ , ⁇ -poly (1,6-hexylene carbonate) diol, ⁇ , ⁇ -poly (3-methyl-1,5-pentyl). Lencarbonate) diol, ⁇ , ⁇ -poly [(1,6-hexylene: 3-methyl-pentamethylene) carbonate] diol, ⁇ , ⁇ -poly [(1,9-nonylene: 2-methyl-1,8- Octylene) carbonate] diol and the like, and commercially available products are trade names PLACEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL, manufactured by Daicel Chemical Industries, Ltd. Kuraray Polyol C-590, C-1065N, C-1015N, C-2015N etc. I can get lost. These can be used alone or in combination of two or more.
  • the diol component as a raw material may be left and contained, but in the present specification, the remaining diol component is referred to as “(poly). It is defined as not included in “carbonate diol”. Accordingly, trade names PLACEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL, manufactured by Daicel Chemical Industries, Ltd., and trade names Kuraray polyol C-590, C-1065N, manufactured by Kuraray Co., Ltd.
  • Raw material diols contained in commercially available (poly) carbonate diols such as C-1015N and C-2015N are not included in “(poly) carbonate diols”. These raw material diol components are included in (w) described later.
  • diisocyanate represented by the formula (44) examples include diphenylmethane-2,4'-diisocyanate;3,2'-,3,3'-,4,2'-,4,3'-5, , 2'-, 5,3'-, 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate;3,2'-,3,3'-,4,2'-,4,3'-,5,2'-,5,3'-,6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate;3,2'-,3,3'-4,2'-,4,3'-,5,2'-,5,3'-,6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate; diphenylmethane-4, 4'-diisocyanate;diphenylmethane-3,3'-diisocyan
  • hexamethylene diisocyanate 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, trans Aliphatic or alicyclic isocyanates such as cyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and lysine diisocyanate, or trifunctional or higher polyisocyanates can be used.
  • the diisocyanate represented by the formula (44) may be stabilized with a blocking agent necessary to avoid changes over time.
  • a blocking agent include alcohol, phenol and oxime, but there is no particular limitation.
  • component (w) a diol component other than the (poly) carbonate diol represented by the formula (43) (hereinafter referred to as component (w)) can be used as necessary.
  • component (w) examples include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
  • the raw material diol contained in the above-mentioned commercially available (poly) carbonate diol is contained in this component (w).
  • the reaction between the (poly) carbonate diol represented by the above formula (43) and the component (w) and the diisocyanate represented by the formula (44) can be carried out without solvent or in the presence of an organic solvent.
  • the reaction temperature is preferably 60 to 200 ° C, more preferably 80 to 180 ° C.
  • the reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like. For example, it can be 2 to 5 hours on a 1 to 5 L flask scale.
  • the number average molecular weight of the diisocyanate compound represented by the formula (42) thus obtained is preferably 500 to 10,000, more preferably 1,000 to 9,500, and 1,500 to Particularly preferred is 9,000.
  • the number average molecular weight is less than 500, the warping property tends to be deteriorated.
  • the number average molecular weight exceeds 10,000, the reactivity of the isocyanate compound is lowered, and it tends to be difficult to obtain a polyimide resin.
  • the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
  • Polyisocyanate compounds other than the diisocyanate compound represented by the formula (42) can also be used as the isocyanate compound as the raw material component of the polyurethane polyimide represented by the formulas (4) to (6). These compounds are not particularly limited as long as they are polyisocyanate compounds other than the diisocyanate compound represented by the formula (42), and examples thereof include diisocyanates represented by the formula (44) and trivalent or higher polyisocyanates. These can be used alone or in combination of two or more.
  • the preferred range of the number average molecular weight of the polyisocyanate compound other than the diisocyanate compound represented by the formula (42) is the same as that of the diisocyanate compound represented by the formula (42).
  • a diisocyanate compound represented by the formula (42) and a polyisocyanate compound other than the diisocyanate compound represented by the formula (42) in combination are preferable to use.
  • a diisocyanate compound represented by the formula (42) and a polyisocyanate compound other than the diisocyanate compound represented by the formula (42) in combination are preferable to use.
  • polyisocyanate compound other than the diisocyanate compound represented by the formula (42) 50 to 100% by mass of the total amount is preferably an aromatic polyisocyanate, and a balance of heat resistance, solubility, mechanical properties, cost, etc. , 4,4'-diphenylmethane diisocyanate is particularly preferred.
  • a diisocyanate compound represented by the formula (42) and a polyisocyanate compound other than the diisocyanate compound represented by the formula (42) are used in combination, a diisocyanate compound represented by the formula (42) / a compound other than the diisocyanate compound represented by the formula (42)
  • the equivalent ratio of the polyisocyanate compound is preferably 0.1 / 0.9 to 0.9 / 0.1, more preferably 0.2 / 0.8 to 0.8 / 0.2, Particularly preferred is 0.3 / 0.7 to 0.7 / 0.3.
  • Examples of the amine compound as a raw material component of the polyurethane polyimide having the structural units represented by the formulas (4) to (6) include compounds obtained by converting the isocyanato group into an amino group in the isocyanate compound. Conversion of the isocyanato group to an amino group can be performed by a known method. A preferred range of the number average molecular weight of the amine compound is the same as that of the diisocyanate compound represented by the formula (42).
  • a trivalent polycarboxylic acid having an acid anhydride group as a raw material component of a polyurethane polyimide having a structural unit represented by formulas (4) to (6) or a derivative thereof and / or a tetravalent having an acid anhydride group.
  • the blending ratio of the polycarboxylic acid is such that the carboxyl group and the acid anhydride are based on the total number of isocyanate groups of the isocyanate compound (the diisocyanate compound represented by the formula (42) and the polyisocyanate compound other than the diisocyanate compound represented by the formula (42)).
  • the ratio of the total number of physical groups is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, and more preferably 0.8 to 1.2. It is particularly preferable to do so. When this ratio is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the resin containing polyimide bonds.
  • a trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and / or a tetravalent polycarboxylic acid having an acid anhydride group is a compound represented by the formula (39), and an isocyanate compound is represented by the formula (42).
  • an isocyanate compound is represented by the formula (42).
  • a polyamideimide having a structural unit represented by the formula (5) can be obtained.
  • a polyamideimide having a structural unit represented by the formula (6) can be obtained.
  • the reaction of one or more compounds selected from acids with an isocyanate compound or an amine compound can be carried out by heat condensation in the presence of a solvent while removing the carbon dioxide gas that is generated free from the reaction system. .
  • a polyurethane polyimide having a carboxyl group, an acid anhydride or an isocyanate group at the terminal can be produced.
  • the terminal group is preferably a carboxyl group and / or an acid anhydride in consideration of reactivity with the epoxy group.
  • a solvent having a boiling point of 150 ° C. to 250 ° C. under atmospheric pressure is generally used.
  • 2 solvents having a boiling point of 150 ° C. to 250 ° C. under atmospheric pressure are used. More than one type can be used in combination and is preferred. More preferably, a solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C. under atmospheric pressure and a solvent having a boiling point of 200 ° C. to 220 ° C. under atmospheric pressure are used in combination.
  • Examples of the solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C. under atmospheric pressure include diethylene glycol dimethyl ether (boiling point 162 ° C.), diethylene glycol diethyl ether (boiling point 189 ° C.), diethylene glycol ethyl methyl ether (boiling point 176 ° C.), dipropylene glycol. -Ludimethyl ether (boiling point 171 ° C.), 3-methoxybutyl acetate (boiling point 171 ° C.), ethylene glycol monobutyl ether acetate (boiling point 192 ° C.) and the like.
  • Examples of the solvent having a boiling point of 200 ° C. to 220 ° C. under atmospheric pressure include diethylene glycol butyl methyl ether (boiling point 212 ° C.), tripropylene glycol dimethyl ether (boiling point 215 ° C.), triethylene glycol dimethyl ether (boiling point 216 ° C.), ethylene Examples include glycol dibutyl ether (boiling point 203 ° C.), diethylene glycol monoethyl ether acetate (boiling point 217 ° C.), and ⁇ -butyrolactone (boiling point 204 ° C.).
  • a suitable solvent for the thermosetting composition of the present invention As it is preferable to use a suitable solvent for the thermosetting composition of the present invention as it is.
  • the following combinations of solvents are preferable. Specifically, as a solvent having a boiling point of 170 ° C. to 200 ° C. under atmospheric pressure, diethylene glycol diethyl ether (boiling point 189 ° C.), diethylene glycol ethyl methyl ether (boiling point 176 ° C.), dipropylene glycol dimethyl ether (boiling point 171 ° C.) ) And a solvent having a boiling point of 200 ° C. to 220 ° C.
  • ⁇ -butyrolactone (boiling point 204 ° C.), and most preferable combination is atmospheric pressure.
  • ⁇ -butyrolactone (boiling point 204 ° C.)
  • ⁇ -butyrolactone (boiling point 204 ° C.)
  • the ratio of the solvent having a boiling point of 170 ° C. to 200 ° C. under atmospheric pressure and the solvent having a boiling point of 200 ° C. to 220 ° C. under atmospheric pressure is a mass ratio, The range is from 5:95 to 80:20, and more preferably from 10:90 to 60:40.
  • a solvent having a boiling point of 170 ° C. to 200 ° C. under atmospheric pressure and a solvent other than a solvent having a boiling point of 200 ° C. to 220 ° C. under atmospheric pressure are used in a range that does not impair the solubility of the polyurethane polyimide. can do.
  • Reactive monomers and reactive diluents can also be used as solvents.
  • the amount of solvent used is preferably 0.8 to 5.0 times (mass ratio) of the polyurethane polyimide to be produced. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to the inability to stir. If it exceeds 5.0 times, the reaction rate tends to decrease.
  • the reaction temperature is preferably 80 to 210 ° C, more preferably 100 to 190 ° C, and particularly preferably 120 to 180 ° C. If it is less than 80 ° C., the reaction time becomes too long, and if it exceeds 210 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur.
  • the reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
  • the number average molecular weight of the polyurethane polyimide thus obtained is preferably 4,000 to 40,000, more preferably 5,000 to 38,000, and 6,000 to 36,000. It is particularly preferred. When the number average molecular weight is less than 4,000, film properties such as heat resistance tend to be lowered. In addition, workability tends to be inferior. In addition, the isocyanate group at the end of the resin can be blocked with a blocking agent such as alcohols, lactams or oximes after completion of the synthesis.
  • JP-A 2006-307183 discloses a polyurethane polyimide having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1), and further having an imide bond. ), The component (b), the component (c ′) and the component (d). Component (a) diisocyanate, Component (b) (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, Component (c ′) A diol compound having a functional group capable of reacting with an epoxy group, and Component (d) a bifunctional hydroxyl-terminated imide represented by the formula (3).
  • R 2 and R 3 each independently represents a divalent aliphatic or aromatic hydrocarbon group
  • Y 1 represents a tetravalent organic group derived from a tetracarboxylic acid or an acid anhydride group thereof.
  • X 1 represents a divalent organic group derived from diamine or diisocyanate, and m is an integer of 0 to 20.
  • any diisocyanate may be used as long as it has two isocyanate groups in one molecule.
  • an aliphatic, alicyclic or aromatic diisocyanate preferably an aliphatic, alicyclic or aromatic diisocyanate having 2 to 30 carbon atoms excluding an isocyanate group, specifically 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene Diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanate methyl) -Cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,4'-diphenylme
  • a blocked diisocyanate obtained by blocking an isocyanate group with a blocking agent can be used.
  • the blocking agent include alcohols, phenols, active methylenes, mercaptans, acid amides, acid imides, imidazoles, ureas, oximes, amines, imines, There are bisulfite type, pyridine type and the like, and these may be used alone or in combination.
  • Specific blocking agents include alcohols such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, Cyclohexanol, etc., phenolic, phenol, cresol, ethyl phenol, butyl phenol, nonyl phenol, dinonyl phenol, styrenated phenol, hydroxybenzoate, etc., active methylene As systems, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc., as mercaptans, as butyl mercaptan, dodecyl mercaptan, etc., as acid amides, as acetanilide, acetate amide, ⁇ -caprolactam, ⁇ -valero Lactam, ⁇ -Buti
  • Poly carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms has a function of imparting flexibility to a target polyurethane polyimide.
  • the (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms preferably has a number average molecular weight of preferably 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight is less than 500, it is difficult to obtain suitable flexibility, and when the number average molecular weight exceeds 10,000, the heat resistance and solvent resistance may be deteriorated.
  • the (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms is specifically UH-CARB, UN-CARB, UD-CARB, UC-CARB, Daicel manufactured by Ube Industries, Ltd.
  • Preferred examples include PLACEL CD-PL, PLACEL CD-H manufactured by Chemical Industry Co., Ltd., and Kuraray polyol C series manufactured by Kuraray Co., Ltd. These polycarbonate polyols are used alone or in combination of two or more.
  • the polyol component that is a raw material may remain and be included.
  • the remaining polyol component is referred to as “(poly) carbonate polyol”. It is defined as not included.
  • (poly) carbonate polyol is produced by transesterification using 1,9-nonanediol and diethyl carbonate as raw materials in the presence of a catalyst
  • the raw material, 1,9-nonanediol is a product.
  • the remaining 1,9-nonanediol is not included in the “(poly) carbonate polyol”, but the component (x ).
  • a (poly) carbonate polyol having an organic residue derived from one kind of diol having 3 to 18 carbon atoms may be used, or two or more kinds may be used in combination.
  • the diol compound having a functional group capable of reacting with such an epoxy group is not particularly limited, but a diol compound having an active hydrogen as a substituent, for example, a diol compound having a carboxyl group or a phenolic hydroxyl group is preferable. In particular, a diol compound having a carboxyl group is preferred.
  • a diol compound having 1 to 30 carbon atoms is preferred, and a diol compound having 2 to 20 carbon atoms is more preferred.
  • examples of the diol compound having a phenolic hydroxyl group include 2,6-bis (hydroxymethyl) -phenol and 2,6-bis (hydroxymethyl) -p-cresol, which have a carboxyl group.
  • examples of the diol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolbutyric acid.
  • the bifunctional hydroxyl-terminated imide can be represented by the following formula (3).
  • R 2 and R 3 each independently represents a divalent aliphatic or aromatic hydrocarbon group
  • Y 1 represents a tetravalent organic group derived from a tetracarboxylic acid or an acid anhydride group thereof.
  • X 1 represents a divalent organic group derived from diamine or diisocyanate, and m is an integer of 0 to 20.
  • This bifunctional hydroxyl-terminated imide is obtained from a tetracarboxylic acid component and an amine component composed of a diamine compound and a monoamine compound having one hydroxyl group.
  • m represents an integer of 0 to 20, preferably 0 to 10, more preferably 0 to 5, and particularly preferably 1 to 5. When m is 20 or more, the bending resistance of the obtained insulating film may be deteriorated.
  • the tetracarboxylic acid component that is a raw material component of the bifunctional hydroxyl-terminated imide is an aromatic tetracarboxylic acid, or an esterified product of an acid dianhydride or lower alcohol thereof, and the resulting polyurethane polyimide has excellent heat resistance. Therefore, it is preferable.
  • 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, and 2,2 ′, 3,3′-biphenyl are particularly preferred.
  • Tetracarboxylic acids or their acid dianhydrides or esterified products of lower alcohols are preferred because they have excellent solubility in solvents when used as polyurethane polyimides.
  • the tetracarboxylic acid component is preferably a tetracarboxylic dianhydride that can be easily reacted with a diamine.
  • the diamine compound in the amine component used as a raw material for the bifunctional hydroxyl-terminated imide is not particularly limited, and aromatic, alicyclic and aliphatic diamines can be used.
  • the aromatic diamine is one benzene ring such as 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 1,4-diamino-2,5-dihalogenobenzene.
  • the alicyclic diamine is preferably an alicyclic diamine having 5 to 30 carbon atoms having one or more aliphatic rings in the molecule, such as isophorone diamine, norbornene diamine, 1,2-diaminocyclohexane, 1,3-diamino. Examples include cyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, and the like.
  • the aliphatic diamine is preferably an aliphatic diamine having 2 to 30 carbon atoms, and examples thereof include hexamethylene diamine and diaminododecane.
  • a bifunctional hydroxyl-terminated imide using an alicyclic diamine has high solubility in a solvent. Therefore, even when R 18 in the formula (43) is combined with a (poly) carbonate polyol composed of a long chain methylene group having 9 to 18 carbon atoms, the polyurethane polyimide is uniformly distributed in the solvent. It is particularly suitable because it is easily dissolved and has good heat resistance.
  • the monoamine compound having one hydroxyl group in the amine component of the bifunctional hydroxyl-terminated imide is not particularly limited as long as it is a compound having one hydroxyl group and one amino group in the molecule.
  • Aliphatic monoamine compounds having a hydroxyl group such as propanol and aminobutanol, in particular aliphatic monoamine compounds having a hydroxyl group having 1 to 10 carbon atoms, and alicyclic monoamine compounds having a hydroxyl group such as aminocyclohexanol, particularly having 3 to 3 carbon atoms
  • Fragrance having a hydroxyl group such as an alicyclic monoamine compound having 20 hydroxyl groups, aminophenol, aminocresol, 4-hydroxy-4'-aminodiphenyl ether, 4-hydroxy-4'-aminobiphenyl, aminobenzyl alcohol, aminophenethyl alcohol, etc.
  • Group monoamination Objects can be particularly carbon atoms suitably include aromatic monoamine compound having 6-20 hydroxyl groups.
  • the bifunctional hydroxyl-terminated imide comprises a tetracarboxylic acid component and an amine component composed of a diamine compound and a monoamine compound having one hydroxyl group, an acid anhydride group of the tetracarboxylic acid component (or two adjacent carboxyl groups, etc. ) And the number of equivalents of the amino group of the amine component so as to be substantially equal to each other, polymerization and imidization reaction can be performed in a solvent.
  • a tetracarboxylic acid component (particularly tetracarboxylic dianhydride), an amine component composed of a diamine compound and a monoamine compound having a hydroxyl group, an acid anhydride group (or an adjacent dicarboxylic acid group) and an amine component.
  • the oligomer having an amide-acid bond is obtained by reacting each component in an organic polar solvent at a reaction temperature of about 100 ° C. or less, particularly 80 ° C. or less. Then, the amide-acid oligomer (also referred to as an amic acid oligomer) is added with an imidizing agent at a low temperature of about 0 ° C. to 140 ° C.
  • toluene or xylene may be added and reacted while removing condensed water by azeotropy.
  • Examples of the solvent used in producing the bifunctional hydroxyl-terminated imide include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam.
  • Solvents dimethyl sulfoxide, hexamethylphosphamide, dimethylsulfone, tetramethylenesulfone, dimethyltetramethylenesulfone-containing solvents such as sulfur atoms, cresol, phenol, xylenol and other phenolic solvents, diethylene glycol dimethyl ether (diglyme), triethylene Glycol solvents such as glycol dimethyl ether (triglyme) and tetraglyme, lactone solvents such as ⁇ -butyrolactone, isophorone, cyclohexanone, 3,3,5-trimethylcyclo Ketones solvents such as cyclohexanone, pyridine, ethylene glycol, dioxane, and other solvents such as tetramethylurea and benzene optionally toluene, aromatic hydrocarbon solvents such as xylene. These organic solvents may be used alone or in combination of two or more.
  • the bifunctional hydroxyl-terminated imide produced as described above may be a mixture of a plurality of bifunctional hydroxyl-terminated imides having different m in the formula (3).
  • a mixture of a plurality of bifunctional hydroxyl-terminated imide oligomers having different m may be used separately for each polyimide, but can be suitably used as it is without being separated.
  • m (average value of m in the case of a mixture) of bifunctional hydroxyl-terminated imides can be controlled by the charging ratio (molar ratio) of the diamine compound and the monoamine compound in the amine component at the time of production.
  • the bifunctional hydroxyl-terminated imide produced as described above may be used as a modified imide oligomer solution by directly or concentrating or diluting the reaction solution.
  • the reaction solution may be poured into a non-soluble solvent such as water and isolated as a powdered product, and the powder product may be dissolved in a solvent and used when necessary.
  • This polyurethane polyimide as mentioned above, Component (a) diisocyanate, Component (b) (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, Component (c ′) A diol compound having a functional group capable of reacting with an epoxy group, and component (d) are obtained by reacting a composition having a bifunctional hydroxyl-terminated imide represented by the formula (3) as essential components.
  • a polyol that does not belong to any of the component (b), the component (c ′) and the component (d) can be used in combination (hereinafter, this component will be referred to as a component (x)).
  • component (x) examples include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
  • the polyol component as a raw material may be left and contained, but in this specification, the remaining polyol component is “(poly) It is not included in “carbonate polyol” but included in component (x).
  • the composition ratio of each component of component (a), component (b), component (c ′), and component (d) is the total number of hydroxyl groups / isocyanate groups.
  • the molar ratio of component (c ′) + component (d) + component (x)] / component (a) is 0.5 to 3.0, preferably 0.8 to 2.5, particularly 0.9 to 2. A ratio of 0.0 is preferred.
  • a polymerization liquid may thicken and it is unpreferable.
  • the molar ratio of [component (b) + component (c ′) + component (x)] / component (d) is 0.01 to 100, preferably 0.1 to 10. This is because too much [component (b) + component (c ′) + component (x)] is inferior in heat resistance, and too much component (d) is inferior in flexibility.
  • the combination of the component (b) and the component (c ′), which are raw material components in producing this polyurethane polyimide is an organic residue derived from a diol having 3 to 18 carbon atoms having a number average molecular weight of 500 to 10,000.
  • component (b) and component (c ′) When comprising a combination of a (poly) carbonate polyol having a group (component (b)) and component (c ′), component (a), [component (b) + component (c ′) + component (x)], Has a molar ratio of [component (b) + component (c ′) + component (x)] / component (a) of 0.5 to 2.5, preferably 0.8 to 2.5,
  • the component (b) and component (c ′) have a molar ratio of component (c ′) / component (b) of 0.1 to 10, preferably 0.1 to 5. .
  • component (x) is preferably used in a smaller amount than component (b) or component (c ′), and more preferably only the polyol component remaining during the synthesis of component (b) is used.
  • the resulting polyurethane polyimide preferably contains structural units of the following formulas (45) to (47).
  • X 6 is a divalent group obtained by removing an isocyanate group from diisocyanate
  • a plurality of R 20 are each independently a divalent group obtained by removing a hydroxyl group from a diol having 3 to 18 carbon atoms
  • t is 1 (An integer of ⁇ 40, u represents an integer of 1 to 100)
  • W represents a divalent group obtained by removing a hydroxyl group from a diol having a functional group capable of reacting with an epoxy group
  • v represents 1 to 40
  • X 6 is a divalent group obtained by removing an isocyanate group from diisocyanate
  • a plurality of R 21 and R 22 are each independently a divalent aliphatic or
  • Polyurethane polyimide is a copolymer of (poly) carbonate unit derived from a diol having 3 to 18 carbon atoms, a diol unit having a functional group capable of reacting with an epoxy group, and a bifunctional hydroxyl-terminated imide unit via a urethane bond.
  • U, v, and x represent the degree of polymerization and the composition ratio of these units. However, this does not restrictively indicate that the above units are block copolymerized.
  • the (poly) carbonate unit derived from a diol having 3 to 18 carbon atoms, the diol unit having a functional group capable of reacting with an epoxy group, and the bifunctional hydroxyl-terminated imide unit may be block copolymerized or random copolymerized.
  • the terminal is not specified, it is an isocyanate group or a hydroxyl group by the diisocyanate compound or each unit located at the terminal.
  • a diisocyanate compound and a (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms or a diol having a functional group capable of reacting with an epoxy group The reaction with can be carried out without solvent or dissolved in a solvent.
  • the reaction temperature is 30 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., and the reaction time is usually 1 to 10 hours.
  • This reaction is preferably performed in a nitrogen atmosphere in order to prevent the isocyanate from being deactivated by moisture.
  • the reaction with the functional hydroxyl-terminated imide can be suitably carried out in a solvent in a nitrogen atmosphere at a reaction temperature of 30 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., for a reaction time of 1 to 15 hours.
  • the ratio of the number of hydroxyl groups of the bifunctional hydroxyl-terminated imide to the number of isocyanate groups of the diisocyanate compound is 0.5 to 2.5, preferably 1.5 to 2.5. Preferably it is. If it is 0.5 or less, the heat resistance of the resulting polyurethane polyimide resin is low, and if it is 2.5 or more, it becomes too hard when it is used as a cured film.
  • Examples of the solvent that can be suitably used in the reaction for producing the polyurethane polyimide include the paragraph [4] as a solvent that can be used in the synthesis of the polyurethane polyimide having the structural unit represented by the formulas (4) to (6).
  • the solvents described in [0191] to [0197] can be used.
  • the polyurethane polyimide can be dissolved in a solvent at a high concentration of at least 3% by mass, preferably about 5 to 60% by mass. It is preferable that the solution viscosity at 25 ° C. (E-type rotational viscometer) is about 1000 to 10000000 mPa ⁇ s, particularly about 1000 to 600000 mPa ⁇ s.
  • the number average molecular weight of the polyurethane polyimide constituting the resin composition of the present invention is preferably 3000 to 50000, more preferably 4000 to 40000, and particularly preferably 4000 to 30000. When the number average molecular weight is less than 3000, the heat resistance and mechanical properties of the resulting cured insulating film tend to be reduced.
  • the acid value of the polyurethane imide is preferably 5 to 120 mgKOH / g, more preferably 10 to 50 mg KOH / g.
  • the acid value is less than 5 mgKOH / g, the reactivity with the epoxy group-containing compound having a tricyclodecane structure is lowered, and the heat resistance of the protective film of the wiring board obtained by curing the thermosetting composition described later is low. May be.
  • the protective film may be too hard and brittle.
  • This polyurethane preferably has a number average molecular weight of 3,000 to 50,000 and an acid value of 5 to 120 mgKOH / g, more preferably a number average molecular weight of 4,000 to 30,000 and an acid value of 10 to 50 mg KOH / g.
  • a polyurethane polyimide obtained by reacting raw materials essentially comprising the following (a), (b), (c) and (d).
  • Component (a) diisocyanate Component (b) (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, Component (c) a diol having a carboxyl group, Component (d) A bifunctional hydroxyl-terminated imide represented by the formula (3).
  • a polyurethane having a certain branched structure in the molecule within a range that dissolves in a solvent, a functional group capable of reacting with an epoxy group, and a structural unit represented by the formula (1) includes the following component (a) and component: It can be obtained by reacting raw material components essentially comprising (b), component (c) and component (e). Component (a) diisocyanate, Component (b) (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, Component (c) a diol having a carboxyl group, Component (e) A compound having 3 or more hydroxyl groups in one molecule.
  • any diisocyanate may be used as long as it has two isocyanate groups in one molecule.
  • an aliphatic, alicyclic or aromatic diisocyanate preferably an aliphatic, alicyclic or aromatic diisocyanate having 2 to 30 carbon atoms excluding an isocyanate group, specifically 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine diisocyanate,
  • the (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms as component (b) preferably has a number average molecular weight of 400 to 10,000, more preferably 450 to 5000, most preferably 500. ⁇ 3000.
  • the number average molecular weight is less than 400, it is difficult to obtain suitable flexibility, and when the number average molecular weight exceeds 10,000, the heat resistance and solvent resistance may be deteriorated.
  • the (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms is specifically UH-CARB, UN-CARB, UD-CARB, UC-CARB, Daicel manufactured by Ube Industries, Ltd.
  • the polyol component as a raw material may be left and contained, but in this specification, the remaining polyol component is “(poly) It is defined as not included in “carbonate polyol”.
  • diol having a carboxyl group as the component (c) examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bis (hydroxyethyl) glycine, N, N-bis ( Hydroxyethyl) glycine and the like can be mentioned.
  • 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferable from the viewpoint of solubility in a solvent.
  • These diols having a carboxyl group may be used alone or in combination of two or more.
  • Examples of the compound having 3 or more hydroxyl groups in one molecule of component (e) include glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, sorbitol, and the like. Can be mentioned. Of these, trimethylolethane, trimethylolpropane, and tris (2-hydroxyethyl) isocyanurate are particularly preferable in view of ease of synthesis.
  • the polyol component as a raw material may be left and contained, but the remaining polyol component has a compound having three or more hydroxyl groups in one molecule. Is included in the component (e).
  • component (y) a diol component not included in any of component (b), component (c) and component (e) (below) , Described as component (y)).
  • component (y) examples include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
  • the polyol component as a raw material may be left and contained, but the remaining polyol component has a compound having two hydroxyl groups in one molecule ( That is, when it is a diol), it means that it is contained in the component (y) described later.
  • the polyurethane having a functional group capable of reacting with an epoxy group which is a component of the thermosetting composition of the present invention and having a structural unit represented by the formula (1) the above component (a), component (b),
  • the polyurethane obtained by reacting the raw material component which makes component (c) and component (e) essential, as a manufacturing method of this polyurethane it can manufacture with the following method, for example.
  • a raw material component which essentially comprises component (a), component (b), component (c) and component (e) using a solvent in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate (If necessary, the component (y)) can be reacted. It is preferable to carry out this reaction without a catalyst because the physical property value of the protective film for the wiring board of the present invention (II) to be described later is improved.
  • a known urethanization catalyst such as dibutyltin dilaurate
  • a component (b), a component (c), a component (e), and a component (y) as needed are prepared first, and it melt
  • the starting molar ratio of the raw materials is the molecular weight and acid value of the polyurethane obtained by reacting the desired raw material components essentially comprising component (a), component (b), component (c) and component (e). Adjust accordingly.
  • the molecular weight of the polyurethane can also be adjusted by using a monohydroxyl compound. That is, when the target number average molecular weight is reached (or when the target number average molecular weight is approached), a monohydroxyl compound is added for the purpose of blocking the terminal isocyanate group and further suppressing the increase in the number average molecular weight. .
  • the number of isocyanate groups in the polyisocyanate compound may be less than or equal to the number of total hydroxyl groups in component (b), component (c), component (e) and component (y). Or even if it increases, there is no problem.
  • the excess monohydroxyl compound may be used as a part of the solvent as it is. Alternatively, it may be removed by distillation or the like.
  • the introduction of the monohydroxyl compound into the polyurethane obtained by reacting the raw material components essentially comprising component (a), component (b), component (c) and component (e) increases the molecular weight of this polyurethane.
  • the monohydroxyl compound is dropped into the solution at 20 to 150 ° C, more preferably at 70 to 140 ° C. Thereafter, the reaction is completed by maintaining at the same temperature.
  • the amount of the component (e) used is preferably 0.1 to 5.0% by mass of the total raw material components, more preferably 0.2 to 2.0% by mass, and most preferably 0.3 to 1.5% by mass. If it is less than 0.1% by mass, the added effect may not be exhibited, which is not preferable. Moreover, when more than 5.0 mass%, molecular weight adjustment at the time of a synthesis
  • the number average molecular weight of the polyurethane obtained by reacting the raw material components essentially comprising the component (a), the component (b), the component (c) and the component (e) is 1,000 to 100,000. Is more preferable, 3000 to 50000 is more preferable, and 5000 to 30000 is particularly preferable.
  • the “number average molecular weight” described in the present specification is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC). If the number average molecular weight is less than 1,000, the elongation, flexibility, and strength of the cured film may be impaired. If the number average molecular weight exceeds 100,000, the solubility in a solvent becomes low, and the viscosity even if dissolved. Becomes higher, and there may be restrictions in terms of use. In this specification, unless otherwise specified, the GPC measurement conditions are as follows.
  • the acid value of this polyurethane is preferably 5 to 120 mgKOH / g, more preferably 10 to 50 mgKOH / g.
  • the acid value is less than 5 mgKOH / g, the reactivity with the epoxy group-containing compound having a tricyclodecane structure is lowered, and the heat resistance of the protective film of the wiring board obtained by curing the protective film thermosetting composition is low. May be.
  • the protective film may be too hard and brittle.
  • a polyurethane having a number average molecular weight of 1,000 to 100,000 and an acid value of 5 to 120 mgKOH / g and having a functional group capable of curing reaction and a carbonate bond is preferred, and more preferably, the number average molecular weight is 3000. And an acid value of 10 to 50 mgKOH / g.
  • the acid value of polyurethane is a value of acid value measured by potentiometric titration method of JIS K0070.
  • Examples of the solvent that can be suitably used in the reaction for producing the polyurethane include those described in paragraph [0191] as a solvent that can be used in the synthesis of the polyurethane polyimide having the structural unit represented by the formulas (4) to (6). ] To [0197] can be used.
  • the “dimer diol” means that a dimer acid and / or a lower alcohol ester thereof is reduced in the presence of a catalyst, and a diol having 36 carbon atoms having a carboxylic acid portion of the dimer acid as an alcohol as a main component. It is a thing.
  • the main component means that 50% by mass or more is present.
  • a hydrogenated dimer diol obtained by hydrogenating a carbon-carbon double bond derived from dimer acid is particularly preferable.
  • dimer diols examples include PRIPOL (registered trademark) 2033 (manufactured by Croda) and Sovermol (registered trademark) 908 (manufactured by Cognis).
  • PRIPOL (registered trademark) 2033 is mainly composed of a mixture of compounds represented by the following formulas (48) and (49).
  • the “dimer acid” is an acid obtained by an intermolecular dimerization reaction of an unsaturated fatty acid, and an unsaturated fatty acid having 11 to 22 carbon atoms forms a dimer having 36 carbon atoms.
  • a dibasic acid obtained by dimerization by blending is a main component.
  • Examples of commercially available products include PRIPOL (registered trademark) 1006, 1009, 1015, and 1025 (manufactured by Croda), and EMPOL (registered trademark) 1062 (Cognis).
  • PRIPOL registered trademark
  • EMPOL registered trademark
  • R 10 and R 11 are both alkyl groups
  • p and q are integers of 0 or more, and the number of carbon atoms contained in R 10 and R 11 and the sum of p and q are 30
  • R 12 and R 13 are all alkyl groups
  • r and s are integers of 0 or more, and the total number of carbon atoms contained in R 12 and R 13 and r and s is 34. .
  • the “organic residue derived from dimer diol” in the present invention means a structure excluding hydrogen of at least one alcoholic hydroxyl group of the dimer diol.
  • the “organic residue derived from a diol having 3 to 18 carbon atoms” means a structure in which hydrogen of at least one alcoholic hydroxyl group of the diol having 3 to 18 carbon atoms is removed.
  • a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) and further containing an organic residue derived from dimer diol includes, for example, the following component (a), It can synthesize
  • any diisocyanate may be used as long as it has two isocyanate groups in one molecule.
  • an aliphatic, alicyclic or aromatic diisocyanate preferably an aliphatic, alicyclic or aromatic diisocyanate having 2 to 30 carbon atoms excluding an isocyanate group, specifically 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine diisocyanate,
  • the (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms as component (b) preferably has a number average molecular weight of 400 to 10,000, more preferably 450 to 5000, most preferably 500. ⁇ 3000.
  • the number average molecular weight is less than 400, it is difficult to obtain suitable flexibility, and when the number average molecular weight exceeds 10,000, the heat resistance and solvent resistance may be deteriorated.
  • the (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms is specifically UH-CARB, UN-CARB, UD-CARB, UC-CARB, Daicel manufactured by Ube Industries, Ltd.
  • the polyol component as a raw material may be left and contained, but in this specification, the remaining polyol component is “(poly) It is defined as not included in “carbonate polyol”.
  • the raw material, 1,9-nonanediol is a product.
  • the remaining 1,9-nonanediol is not included in the “(poly) carbonate polyol”, but the component (z ).
  • diol having a carboxyl group as the component (c) examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bis (hydroxyethyl) glycine, N, N-bis ( Hydroxyethyl) glycine and the like can be mentioned.
  • 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferable from the viewpoint of solubility in a solvent.
  • These polyols having a carboxyl group may be used alone or in combination of two or more.
  • the dimer diol of component (l) is mainly a diol having 36 carbon atoms in which dimer acid and / or its lower alcohol ester is reduced in the presence of a catalyst, and the carboxylic acid portion of dimer acid is alcohol.
  • the main component means that 50% by mass or more is present.
  • the dimer diol in the present specification a hydrogenated dimer diol obtained by hydrogenating a carbon-carbon double bond derived from dimer acid is particularly preferable. Examples of commercially available dimer diols include PRIPOL 2033 (manufactured by Croda) and Sovermol 908 (manufactured by Cognis).
  • the component (a), the component (b), the component (c) and the component (l) as necessary, the component (a), the component (b), the component (c) and the component (l) A diol component (component (z)) not included in any of them can be used in combination.
  • the component (z) include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
  • the polyol component as a raw material may remain and be included, but the remaining polyol component is not included in the component (b) but included in the component (z).
  • a polyurethane having a functional group capable of reacting with an epoxy group which is a component of the thermosetting composition of the present invention and having a structural unit represented by the formula (1) has a functional group capable of reacting with an epoxy group and
  • the polyurethane may be produced, for example, by the following method. Can do.
  • a raw material component which essentially comprises component (a), component (b), component (c) and component (l) using a solvent in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate It can synthesize
  • a known urethanization catalyst such as dibutyltin dilaurate
  • a component (b), a component (c), a component (l), and a component (z) are prepared first, and it melt
  • the starting molar ratio of the raw materials is the molecular weight and acid value of the polyurethane obtained by reacting the desired raw material components essentially comprising component (a), component (b), component (c) and component (l). Adjust accordingly.
  • the molecular weight of the polyurethane can also be adjusted by using a monohydroxyl compound. That is, when the target number average molecular weight is reached (or when the target number average molecular weight is approached), a monohydroxyl compound is added for the purpose of blocking the terminal isocyanate group and further suppressing the increase in the number average molecular weight. .
  • component (a) When using a monohydroxyl compound, the same is true even if the number of isocyanate groups in component (a) is less than the total number of hydroxyl groups in component (b), component (c), component (l) and component (z). But it doesn't matter if you increase it or not.
  • the excess monohydroxyl compound may be used as a part of the solvent as it is. Alternatively, it may be removed by distillation or the like.
  • the introduction of the monohydroxyl compound into the polyurethane obtained by reacting the raw material components essential to the component (a), the component (b), the component (c) and the component (l) increases the molecular weight of the polyurethane.
  • the monohydroxyl compound is dropped into the solution at 20 to 150 ° C, more preferably at 70 to 140 ° C. Thereafter, the reaction is completed by maintaining at the same temperature.
  • the amount of component (l) used is preferably 5 to 50% by mass, more preferably the total amount of component (b), component (c), component (l) and component (z). It is 10 to 45% by mass, and most preferably 15 to 40% by mass. When the amount is less than 5% by mass, the added effect may not be exhibited, which is not preferable. Moreover, when more than 50 mass%, the adhesiveness to the polyimide substrate of the protective film mentioned later may fall, and it is unpreferable.
  • the number average molecular weight of the polyurethane obtained by reacting the raw material components essentially comprising the component (a), the component (b), the component (c) and the component (l) is 1,000 to 100,000. Is more preferable, 3000 to 50000 is more preferable, and 5000 to 30000 is particularly preferable. If the number average molecular weight is less than 1000, the elongation, flexibility, and strength of the cured film may be impaired. If the number average molecular weight exceeds 100000, the solubility in a solvent becomes low, and the viscosity increases even if dissolved. There may be restrictions on usage.
  • the acid value of this polyurethane is preferably 5 to 120 mgKOH / g, more preferably 10 to 50 mgKOH / g.
  • the acid value is less than 5 mgKOH / g, the reactivity with the epoxy group-containing compound having a tricyclodecane structure is lowered, and the heat resistance of the protective film of the wiring board obtained by curing the protective film thermosetting composition is low. May be.
  • the protective film may be too hard and brittle.
  • a polyurethane having a number average molecular weight of 1,000 to 100,000 and an acid value of 5 to 120 mgKOH / g and having a functional group capable of curing reaction and a carbonate bond is preferred, and more preferably, the number average molecular weight is 3000. And an acid value of 10 to 50 mgKOH / g.
  • Examples of the solvent that can be suitably used in the reaction for producing the polyurethane include those described in paragraph [0191] as a solvent that can be used in the synthesis of the polyurethane polyimide having the structural unit represented by the formulas (4) to (6). ] To [0197] can be used.
  • the solvent which is an essential component of the thermosetting composition of the present invention (I) was used for the synthesis of a polyurethane having a functional group capable of reacting with the aforementioned epoxy group and having a structural unit represented by the formula (1). It is economically preferable to use the solvent as it is as the solvent of the thermosetting composition of the present invention (I). Moreover, you may add a solvent further in the meaning which adjusts a viscosity.
  • the concentration of the solvent in the thermosetting composition of the present invention (I) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass.
  • the thermosetting composition of the present invention (I) can further preferably contain a curing accelerator.
  • the curing accelerator is not particularly limited as long as it is a compound that promotes the reaction between an epoxy group and a carboxyl group.
  • melamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyloxyethyl-s -Triazines such as triazine, 2,4-methacryloyloxyethyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid adducts
  • imidazole 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methyl
  • melamine in view of achieving both a curing accelerating action and electrical insulation performance, preferred are melamine, imidazole compounds, cycloamidine compounds and derivatives thereof, phosphine compounds, and amine compounds. More preferred are melamine, 1,5-diazabicyclo (4.3.0) nonene-5 and salts thereof, and 1,8-diazabicyclo (5.4.0) undecene-7 and salts thereof.
  • the blending amount of these curing accelerators is not particularly limited as long as the curing acceleration effect can be achieved.
  • the present invention Of the epoxy group-containing compound having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) and a tricyclodecane structure contained in the thermosetting composition of (I) It is preferably blended in the range of 0.05 to 5 parts by mass, more preferably 0.1 to 3.0 parts by mass with respect to the total amount of 100 parts by mass.
  • the blending amount is less than 0.05 parts by mass, it is difficult to cure in a short time, and when it exceeds 5 parts by mass, the electrical insulation characteristics and water resistance of the cured product obtained by curing the composition are deteriorated. There is.
  • thermosetting composition of the present invention inorganic fine particles and / or organic fine particles can be blended and preferably blended for the purpose of adjusting fluidity.
  • inorganic fine particles and / or organic fine particles means not only inorganic fine particles and organic fine particles, but also a powdery inorganic compound physically coated with an organic compound or chemically surfaced with an organic compound. It is defined to include organic / inorganic composite fine particles that have been treated.
  • Inorganic fine particles and / or organic fine particles that may be used for the purpose of blending in the thermosetting composition of the present invention (I) contain an epoxy group having a tricyclodecane structure, which is an essential component of the present invention (I).
  • the paste is dispersed in a composition containing a compound, a polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1), and a solvent.
  • inorganic fine particles examples include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and silicon nitride (Si 3 N 4 ).
  • the organic fine particles are preferably heat-resistant resin fine particles having an amide bond, an imide bond, an ester bond or an ether bond.
  • the resin is preferably a polyimide resin or a precursor thereof, a polyamideimide resin or a precursor thereof, or a polyamide resin from the viewpoint of heat resistance and mechanical properties.
  • the average particle size of these inorganic fine particles and / or organic fine particles is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • the blending amount of the inorganic fine particles and / or organic fine particles is 1 to 150 parts by mass, preferably 1 with respect to 100 parts by mass of the total amount of the carboxyl group-containing polyurethane, solvent and curing agent contained in the curable resin composition. It is ⁇ 120 parts by mass, more preferably 1 to 60 parts by mass.
  • thermosetting composition for a protective film of a wiring board of the present invention is, for example, a heat for a protective film of a wiring board for Chip On Film (hereinafter referred to as COF) patterned by a screen printing method. It can be used as a curable composition.
  • COF described in this specification means a mounting method in which a bare chip is mounted on a flexible wiring board and connected.
  • thermosetting composition of the present invention (I) When the thermosetting composition of the present invention (I) is used as a thermosetting composition for a protective film of a wiring board for COF patterned by a screen printing method, generation of bubbles during printing
  • An antifoaming agent can be used and preferably used for the purpose of eliminating or suppressing the odor.
  • the antifoaming agent is not particularly limited as long as it literally has an action of eliminating or suppressing bubbles generated when the thermosetting composition of the present invention (I) is printed.
  • the antifoaming agent used in the thermosetting composition of the present invention (I) include, for example, BYK-077 (manufactured by Big Chemie Japan), SN deformer 470 (manufactured by San Nopco), TSA750S (momentive Performance Materials, Inc.), silicone-based antifoaming agents such as silicone oil SH-203 (Toray Dow Corning), Dappo SN-348 (San Nopco), Dappo SN-354 (San Nopco), Acrylic polymer antifoaming agents such as Dappo SN-368 (manufactured by San Nopco), Disparon 230HF (manufactured by Enomoto Kasei Co., Ltd.), Surfynol DF-110D (manufactured by Nissin Chemical Industry Co., Ltd.), Surfynol DF-37 (Nissan) Acetylene diol type antifoaming agent such as Shin-Chemical Industry Co.,
  • thermosetting composition of the present invention (I) includes surfactants such as a leveling agent, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, kustal violet, carbon as necessary.
  • surfactants such as a leveling agent, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, kustal violet, carbon as necessary.
  • Known colorants such as black and naphthalene black can be added.
  • an antioxidant such as a phenolic antioxidant, a phosphite antioxidant, or a thioether antioxidant. And preferably added.
  • phenolic antioxidants include compounds represented by the following formulas (50) to (60).
  • Examples of the phosphite antioxidant include compounds represented by the following formulas (61) to (71).
  • Examples of the thioether-based antioxidant include compounds represented by the following formulas (72) to (77).
  • flame retardants and lubricants can be added as necessary.
  • thermosetting composition of the present invention (I) can be obtained by uniformly kneading and mixing part or all of the blending components with a roll mill, a bead mill or the like. When a part of the blending components is mixed, the remaining components can be mixed when actually used.
  • thermosetting composition of the present invention (I) is used as a thermosetting composition for a protective film of a wiring board for COF patterned by a screen printing method
  • the heat of the present invention (I) In order to improve the printability of the curable composition, it is desirable to have a certain range of thixotropy index.
  • the “thixotropy index” described in the present specification is a cone / plate viscometer (Brookfield's model: DV-II + Pro spindle model number: CPE-52), measured at 1 rpm at 25 ° C. It is defined as the ratio of the viscosity at the time of 10 to the viscosity at a rotation speed of 10 rpm at 25 ° C.
  • thermosetting composition of the present invention (I) When the thermosetting composition of the present invention (I) is used as a thermosetting composition for a protective film patterned by a screen printing method, the printability of the thermosetting composition of the present invention (I) is good. Therefore, the thixotropy index at 25 ° C. of the composition is preferably in the range of 1.1 to 3.0, more preferably in the range of 1.1 to 2.5.
  • the thermosetting composition of this invention (I) as a soldering resist ink composition
  • the thixotropy index in 25 degreeC of a thermosetting composition became less than 1.1, the thermosetting composition was printed. Later, the composition may flow, so that the film thickness may not be constant or the printed pattern may not be maintained.
  • the thixotropy index at 25 ° C. of the thermosetting composition is larger than 3.0, the defoaming property of the coating film of the printed composition may be deteriorated.
  • the present invention (II) is a protective film for a wiring board obtained by curing the thermosetting composition for a protective film for a wiring board according to the present invention (I).
  • the protective film of the wiring board of the present invention (II) removes part or all of the solvent in the thermosetting composition for the protective film of the wiring board of the present invention (I), and then proceeds with the curing reaction by heating. In general, a cured product is obtained.
  • the protective film can be obtained through the following first to third steps. 1st process The process of printing the thermosetting composition of this invention (I) and obtaining a coating film. Second Step A step of obtaining a coating film from which a part or all of the solvent has been removed by evaporating the solvent from the coating film obtained in the first step in an atmosphere of 20 ° C. to 100 ° C. Third step A step of obtaining a heat-cured coating film (that is, a cured coating film) by thermally curing the coating film obtained in the second process in an atmosphere of 100 ° C. to 250 ° C.
  • the first step is a step of printing the thermosetting composition of the present invention (I) to obtain a coating film
  • a coating film can be obtained by coating by a screen printing method, a roll coater method, a spray method, a curtain coater method or the like, and most preferably a screen printing method.
  • the second step is a step of obtaining a coating film from which a part or all of the solvent has been removed by evaporating the solvent from the coating film obtained in the first step in an atmosphere of 20 ° C. to 100 ° C.
  • the time for removing the solvent is preferably 4 hours or less, more preferably 2 hours or less.
  • the third step is a step in which the coating film obtained in the second step is thermally cured in an atmosphere of 100 ° C. to 250 ° C. to obtain a thermally cured coating film (that is, a cured coating film).
  • the heat curing time is preferably in the range of 20 minutes to 4 hours, and more preferably in the range of 30 minutes to 2 hours.
  • a part or all of the surface of the flexible wiring board in which the wiring is formed on the flexible substrate is covered with the protective film for the wiring board described in the present invention (II).
  • This is a flexible wiring board covered with a protective film.
  • a printed film is formed on the pattern by printing the thermosetting composition for the protective film of the wiring board of the present invention (I) on the wiring pattern portion subjected to tin plating of the flexible wiring board.
  • thermosetting composition of the present invention (I) can be used, for example, as a protective film for a wiring board for COF by covering the entire surface or a part of the wiring of a flexible wiring board for COF.
  • the protective film for the flexible wiring board can be formed through the following steps A to C.
  • Process A The process of screen-printing the thermosetting composition of this invention (I) on the wiring pattern part by which the tin plating process of the flexible wiring board was carried out previously, and obtaining a coating film.
  • Process B A step of evaporating the solvent from the coating film obtained in the step A in an atmosphere of 20 to 100 ° C. to obtain a coating film from which a part or all of the solvent has been removed.
  • Process C A step of obtaining a protective film for a flexible printed wiring board by thermosetting the coating film obtained in the step B in an atmosphere of 80 to 130 ° C.
  • the temperature for evaporating the solvent in Step B is 20 to 100 ° C., preferably 60 to 100 ° C., more preferably, considering the evaporation rate of the solvent and the quick transition to the next step (Step C). 70 to 90 ° C.
  • the time for evaporating the solvent in Step B is not particularly limited, but is preferably 10 to 120 minutes, and more preferably 20 to 100 minutes.
  • the operation of the step B is an operation performed as necessary.
  • the operation of the step C may be performed immediately after the operation of the step A, and the curing reaction and the removal of the solvent may be performed together.
  • the conditions for thermosetting performed in Step C are in the range of 80 to 130 ° C. from the viewpoint of preventing the plating layer from diffusing and obtaining warpage and flexibility suitable as a protective film.
  • the temperature is preferably 90 to 130 ° C, and 110 to 130 ° C.
  • the time for thermosetting performed in step C is not particularly limited, but is preferably 20 to 150 minutes, and more preferably 30 to 120 minutes.
  • the polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1), which is an essential component of the present invention (I), has a carboxyl group as a functional group capable of reacting with an epoxy group.
  • the acid value was measured by the following method.
  • the solvent in the polyurethane solution having a carboxyl group was distilled off under reduced pressure under heating to obtain a polyurethane having a carboxyl group.
  • the acid value was measured according to the potentiometric titration method of JIS K0070.
  • the apparatus used in the potentiometric titration method is described below. Apparatus name: Kyoto Denshi Kogyo Co., Ltd. potentiometric automatic titrator AT-510 Electrode: Composite glass electrode C-173 manufactured by Kyoto Electronics Industry Co., Ltd.
  • ⁇ Measurement of hydroxyl value> The hydroxyl value was measured according to the neutralization titration method of JIS K0070.
  • the viscosity of the carboxyl group-containing polyurethane solution was measured by the following method. About 0.8 g of a carboxyl group-containing polyurethane solution was used, and a cone / plate viscometer (Brookfield model: DV-II + Pro spindle model number: CPE-52) was used at a temperature of 25.0 ° C. and a rotational speed of 5 rpm. Under the conditions, the viscosity after 7 minutes from the start of measurement was measured.
  • bifunctional hydroxyl-terminated imide (A) a bifunctional hydroxyl-terminated imide having m (average value) of 1 in the formula (3) (hereinafter referred to as bifunctional hydroxyl-terminated imide (A)). It was confirmed that.
  • bifunctional hydroxyl-terminated imide (B) a bifunctional hydroxyl-terminated imide having m (average value) of 3 in the formula (3) (hereinafter referred to as bifunctional hydroxyl-terminated imide (B)). It was confirmed that.
  • IR infrared absorption
  • the materials were heated to 100 ° C..
  • the temperature of the reaction solution was lowered to 90 ° C., and 133.7 g (0.510 mol) of methylenebis (4-cyclohexylisocyanate) was added dropwise over 30 minutes with a dropping funnel.
  • 133.7 g (0.510 mol) of methylenebis (4-cyclohexylisocyanate) was added dropwise over 30 minutes with a dropping funnel.
  • 1.3 g (28.2 mmol) of ethanol was added dropwise, and further reacted at 80 ° C. for 3 hours to have a carboxyl group and a carbonate bond.
  • a solution containing polyurethane (hereinafter referred to as polyurethane (1)) was obtained.
  • the viscosity of the solution containing the obtained polyurethane (1) was 101 Pa ⁇ s.
  • the number average molecular weight of the polyurethane (1) contained in the solution containing the polyurethane (1) was 14,000, and the acid value of the polyurethane (1) was 40.0 mg-KOH / g. Moreover, the solid content concentration in the solution containing this polyurethane (1) was 40.0% by mass.
  • polyurethane (2) a solution containing a polyurethane having a carboxyl group and a carbonate bond and having a structural unit derived from dimer diol.
  • the viscosity of the solution containing the obtained polyurethane (2) was 78 Pa ⁇ s.
  • the number average molecular weight of the polyurethane (2) contained in the solution containing the polyurethane (2) was 13,000, and the acid value of the polyurethane (2) was 40.0 mg-KOH / g.
  • the solid content concentration in the solution containing this polyurethane (2) was 45.0% by mass.
  • the temperature of the reaction solution was lowered to 90 ° C., and 136.0 g (0.518 mol) of methylenebis (4-cyclohexylisocyanate) was added dropwise over 30 minutes with a dropping funnel. After reacting at 120 ° C. for 9 hours and confirming that the isocyanate almost disappeared, 3.6 g (0.049 mol) of isobutanol (manufactured by Kyowa Hakko Chemical Co., Ltd.) was added dropwise, and the reaction was further performed at 120 ° C. for 4 hours.
  • polyurethane (3) a solution containing a polyurethane having a carboxyl group and a carbonate bond and having a structural unit derived from dimer diol.
  • the viscosity of the solution containing the obtained polyurethane (3) was 84 Pa ⁇ s.
  • the number average molecular weight of the polyurethane (3) contained in the solution containing the polyurethane (3) was 12,000, and the acid value of the polyurethane (3) was 30.0 mg-KOH / g.
  • the solid content concentration in the solution containing this polyurethane (3) was 45.0% by mass.
  • the number average molecular weight of the polyurethane (4) contained in the solution containing the polyurethane (4) was 12,000, and the acid value of the polyurethane (4) was 39.8 mg-KOH / g. Moreover, the solid content concentration in the solution containing this polyurethane (4) was 50.3% by mass.
  • the number average molecular weight of the polyurethane (5) contained in the solution containing the polyurethane (5) was 19,000, and the acid value of the polyurethane (5) was 0 mg-KOH / g. Moreover, the solid content concentration in the solution containing this polyurethane (5) was 50.1% by mass.
  • Example formulation 1 1,8-diazabicyclo (4.5.0) undecene-7 (hereinafter referred to as DBU) as a curing accelerator with respect to 100 parts by mass of polyurethane polyimide (1) in a solution containing polyurethane polyimide (1) ( 1 part by mass of San Apro Co., Ltd.) was added and stirred and mixed uniformly. Further, 7 parts by mass of silica powder (Nippon Aerosil Co., Ltd., trade name: Aerosil R972) and 5 parts by mass of talc (Nippon Talc Co., Ltd., trade name: SG2000) were added, first roughly kneaded, and then triple roll mill (Inoue Co.
  • DBU 1,8-diazabicyclo (4.5.0) undecene-7
  • a composition (hereinafter referred to as a main agent composition A1) containing polyurethane polyimide (1) uniformly mixed by repeating this kneading three times using a model manufactured by Seisakusho: S-43 / 4 ⁇ 11). .) Further, in a container equipped with a stirrer, a thermometer, and a condenser, 300 g of an epoxy resin having a structure represented by the following formula (2) (DIC Corporation grade name; HP-7200H epoxy equivalent 278 g / eq), 180 g of ⁇ -butyrolactone and 120 g of diethylene glycol diethyl ether was added and stirring was started. While continuing stirring, the temperature in the container was raised to 70 ° C. using an oil bath.
  • dissolved completely it cooled to room temperature, and the HP-7200H containing solution (henceforth hardening agent solution B1) with a density
  • l represents 0 or an integer of 1 or more.
  • 100 parts by mass of the main agent composition A1 and 9,65 parts by mass of the curing agent solution B1 and 0.5 part by mass of an antifoaming agent (product name: TSA750S manufactured by Momentive Performance Materials) are mixed, and a spatula is used. , Mixed well with stirring.
  • Example of formulation 2 In a solution containing polyurethane polyimide (2), 7.9 parts by mass of Aerosil 380 (manufactured by Nippon Aerosil Co., Ltd.) and 1 part by weight of DBU (manufactured by Sun Apro Co., Ltd.) with respect to 100 parts by mass of polyurethane polyimide (2) Part is first roughly kneaded, then, using a three roll mill (manufactured by Inoue Seisakusho Co., Ltd. Model: S-43 / 4 ⁇ 11), this kneading is repeated three times to perform main kneading, and polyurethane polyimide (2) is obtained.
  • main agent composition A2 A composition containing the composition (hereinafter referred to as main agent composition A2) was obtained.
  • a curing agent solution B1 and 0.5 part by mass of an antifoaming agent (trade name: TSA750S manufactured by Momentive Performance Materials) are added, and ⁇ -butyrolactone:
  • Example formulation 3 111.1 parts by mass of the solution containing the polyurethane (1), 5.0 parts by mass of silica powder (trade name; Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.), and melamine (manufactured by Nissan Chemical Industries, Ltd.) as a curing accelerator 36 parts by mass were mixed, and using a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd. Model: S-43 / 4 ⁇ 11), kneading was repeated three times to perform main kneading, and a composition containing polyurethane (1) ( Hereinafter, referred to as main agent composition A3).
  • silica powder trade name
  • Aerosil R974 manufactured by Nippon Aerosil Co., Ltd.
  • melamine manufactured by Nissan Chemical Industries, Ltd.
  • Example of formulation 4 111.1 parts by mass of the solution containing the polyurethane (2), 5.0 parts by mass of silica powder (trade name; Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.), and melamine (manufactured by Nissan Chemical Industries, Ltd.) as a curing accelerator 36 parts by mass were mixed, and using a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd. Model: S-43 / 4 ⁇ 11), kneading was repeated three times to perform main kneading, and a composition containing polyurethane (2) ( Hereinafter, referred to as main agent composition A4).
  • silica powder trade name
  • Aerosil R974 manufactured by Nippon Aerosil Co., Ltd.
  • melamine manufactured by Nissan Chemical Industries, Ltd.
  • Example formulation 5 111.1 parts by mass of the solution containing the polyurethane (3), 5.0 parts by mass of silica powder (trade name; Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.), and melamine (manufactured by Nissan Chemical Industries, Ltd.) as a curing accelerator 36 parts by mass were mixed, using a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd. Model: S-43 / 4 ⁇ 11), kneading was repeated three times to perform main kneading, and a composition containing polyurethane (3) ( Hereinafter, referred to as main agent composition A5).
  • silica powder trade name
  • Aerosil R974 manufactured by Nippon Aerosil Co., Ltd.
  • melamine manufactured by Nissan Chemical Industries, Ltd.
  • Spatula is mixed with 19.1 parts by weight of the curing agent solution B1 and 0.60 parts by weight of an antifoaming agent (product name: TSA750S, manufactured by Momentive Performance Materials) with respect to 100 parts by weight of the main agent composition A5.
  • an antifoaming agent product name: TSA750S, manufactured by Momentive Performance Materials
  • thermosetting composition H1 (Comparative Formulation Example 1) With respect to 100 parts by mass of the main agent composition A1, Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., (3 ′, 4′-epoxycyclohexane) methyl-3,4-epoxycyclohexanecarboxylate, epoxy equivalent 126 g / eq) 4 .2 parts by mass and an antifoaming agent (product name: TSA750S, manufactured by Momentive Performance Materials) 0.5 part by mass is uniformly mixed with the composition containing the polyurethane polyimide (1), and the polyurethane polyimide (1) A thermosetting composition (hereinafter referred to as thermosetting composition H1) was obtained.
  • thermosetting composition H2 For 100 parts by mass of the main agent composition A2, 10 parts by mass of YH-434 (trade name of amine-type epoxy resin manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 120 g / eq) and TSA750S (manufactured by Momentive Performance Materials) Anti-foaming agent name) 0.5 parts by mass, diluted with ⁇ -butyrolactone, thermosetting including polyurethane polyimide (2) having a viscosity of 35 Pa ⁇ s, a thixotropy index of 2.4, and a nonvolatile content of 40% by mass A composition (hereinafter referred to as a thermosetting composition H2) was obtained.
  • main agent composition A6 111.1 parts by mass of the solution containing the polyurethane (4), 5.0 parts by mass of silica powder (trade name; Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.), and melamine (manufactured by Nissan Chemical Industries, Ltd.) as a curing accelerator 36 parts by mass are mixed, using a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd. Model: S-43 / 4 ⁇ 11), the kneading is repeated three times to perform the main kneading, and a composition containing polyurethane (4) ( Hereinafter, referred to as main agent composition A6).
  • Comparative Formulation Example 4 88.9 parts by mass of the solution containing the polyurethane (5), 5.0 parts by mass of silica powder (trade name; Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.), and melamine (manufactured by Nissan Chemical Industries, Ltd.) as a curing accelerator 0. 36 parts by mass are mixed, using a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd. Model: S-43 / 4 ⁇ 11), the kneading is repeated three times to perform main kneading, and a composition containing polyurethane (5) ( Hereinafter, referred to as main agent composition A7).
  • silica powder trade name; Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.
  • melamine manufactured by Nissan Chemical Industries, Ltd.
  • thermosetting composition G1 thermosetting composition G8
  • thermosetting composition H1 thermosetting composition H4, respectively.
  • Evaluation of adhesion to copper subjected to, evaluation of warpage and long-term electrical insulation reliability were performed. The results are shown in Table 1.
  • thermosetting composition G1 The polyimide film (Kapton (registered trademark) 300H, manufactured by Toray DuPont Co., Ltd.) is coated with the thermosetting composition G1 by a screen printing method so that the thickness of the thermosetting composition is 15 ⁇ m (the thickness after drying). ) And placed in an 80 ° C. hot air circulation dryer for 30 minutes, and then placed in a 120 ° C. hot air circulation dryer for 120 minutes for curing.
  • thermosetting composition G1 was applied to a substrate by screen printing, placed in an 80 ° C hot air circulating dryer for 30 minutes, and then placed in a 120 ° C hot air circulating dryer for 60 minutes to cure. I let you. A 38 ⁇ m-thick polyimide film [Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.] was used as the substrate. About the coating film which apply
  • the test piece After leaving the test piece at a temperature of 23 ⁇ 0.5 ° C. and a humidity of 60 ⁇ 5% RH for 12 hours or more, the test piece is left in a convex state, and the part that is most warped from the plane and a circle
  • the height of the warp from the plane was measured using a length meter and averaged at two locations that were symmetric with respect to the center of.
  • the sign represents the direction of warping, and when left in a downwardly convex state, the case where the cured film is on the upper side with respect to the polyimide film is “+”, and the case where the cured film is on the lower side is “ ⁇ ”.
  • Table 1 The results are shown in Table 1.
  • the same evaluation was performed using the thermosetting composition G2 to the thermosetting composition G8 and the thermosetting composition H1 to the thermosetting composition H4. The results are also shown in Table 1.
  • thermosetting composition G1 was applied by clean printing so that the thickness of the coating film was 15 ⁇ m, held at room temperature for 10 minutes, and cured by placing it in a 120 ° C. hot air circulating dryer for 60 minutes.
  • the PET film on the back of the prepared test piece was peeled off, cut into a strip shape having a width of 10 mm with a cutter knife, bent about 180 degrees so that the coating surface was on the outside, and 0.5 ⁇ 0 using a compressor.
  • thermosetting composition G2 Compressed at 2 MPa for 3 seconds.
  • the bent part was bent and observed with a 30-fold microscope to confirm the presence or absence of cracks.
  • the results are shown in Table 1.
  • the same evaluation was performed using the thermosetting composition G2 to the thermosetting composition G8 and the thermosetting composition H1 to the thermosetting composition H4.
  • the results are also shown in Table 1.
  • a substrate having a fine comb pattern shape described in JPCA-ET01, manufactured by etching a flexible copper-clad laminate (Sumitomo Metal Mining Co., Ltd. grade name; Esperflex copper thickness; 8 ⁇ m, polyimide thickness: 38 ⁇ m) Width / width between copper wirings 15 ⁇ m / 15 ⁇ m)
  • thermosetting composition G2 to the thermosetting composition G8 and the thermosetting composition H1 to the thermosetting composition H4. The results are also shown in Table 1.
  • thermosetting composition G2 to the thermosetting composition G8 and the thermosetting composition H1 to the thermosetting composition H4. The results are also shown in Table 1.
  • thermosetting composition of the present invention (I) a novel composition capable of expressing long-term electrical insulation characteristics while maintaining a high level of resistance value and the composition were cured.
  • cured material obtained can be provided.
  • thermosetting composition for a protective film of a wiring board of the present invention is suitably used for the production of a flexible wiring board.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention a pour objet une composition thermodurcissable pour un film protecteur destiné à un tableau de connexions, qui possède d’excellentes propriétés de faible gauchissement, une excellente flexibilité, et une excellente fiabilité d’isolation à long terme. La composition thermodurcissable pour un film protecteur destiné à un tableau de connexions comprend, en tant que composants essentiels, un composé contenant un groupe époxy ayant une structure tricyclodécane, un polyuréthane ayant une unité structurale représentée par la formule (1) et ayant un groupe fonctionnel qui peut réagir avec un groupe époxy, et un solvant. Dans la formule (1), R1 représente un groupe alkylène ayant de 3 à 18 atomes de carbone, et n représente un nombre entier égal à 1 ou plus. En tant que composé contenant un groupe époxy ayant une structure tricyclodécane, un composé représenté par la formule (2) est de préférence utilisé.
PCT/JP2010/061226 2009-07-06 2010-06-24 Composition thermodurcissable pour film protecteur pour tableau de connexions WO2011004756A1 (fr)

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JP2015147940A (ja) * 2009-10-07 2015-08-20 日立化成株式会社 熱硬化性樹脂組成物及び硬化膜
WO2016129541A1 (fr) * 2015-02-09 2016-08-18 味の素株式会社 Composition de résine thermodurcissable
JP2019068062A (ja) * 2017-09-29 2019-04-25 昭和電工株式会社 レジストインキ並びに配線の保護膜及びその製造方法、半導体基板及びその保護膜の製造方法

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KR20140097248A (ko) * 2011-10-28 2014-08-06 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 전기화학 전지를 위한 폴리우레탄-기반 전극 바인더 조성물 및 이의 전극
KR102016675B1 (ko) * 2011-10-28 2019-08-30 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 전기화학 전지를 위한 폴리우레탄-기반 전극 바인더 조성물 및 이의 전극
WO2016129541A1 (fr) * 2015-02-09 2016-08-18 味の素株式会社 Composition de résine thermodurcissable
JPWO2016129541A1 (ja) * 2015-02-09 2017-11-16 味の素株式会社 熱硬化性樹脂組成物
JP2019068062A (ja) * 2017-09-29 2019-04-25 昭和電工株式会社 レジストインキ並びに配線の保護膜及びその製造方法、半導体基板及びその保護膜の製造方法

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KR20120022784A (ko) 2012-03-12
TWI495662B (zh) 2015-08-11
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CN102471460A (zh) 2012-05-23
TW201113312A (en) 2011-04-16
JPWO2011004756A1 (ja) 2012-12-20

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