WO2011004756A1 - Thermosetting composition for protective film for wiring board - Google Patents
Thermosetting composition for protective film for wiring board Download PDFInfo
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- 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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- polyurethane
- wiring board
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- 0 CC(CC1)C(C)C(**)C1O* Chemical compound CC(CC1)C(C)C(**)C1O* 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- 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
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- 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
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- 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
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- 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.
Abstract
Description
しかしながら、近年、電子機器の軽量小型化に伴いフレキシブル基板も軽薄化が進み、これに伴い、オーバーコートする樹脂組成物の柔軟性や硬化収縮の影響が、より顕著に現れるようになってきている。このため、硬化タイプのオーバーコート剤では、柔軟性や硬化収縮による反りの点で、要求性能を満足できなくなっているのが現状である。 Conventionally, 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. As these curing type overcoat agents, 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. In addition, while suppressing the deterioration of chemical resistance and electrical insulation as much as possible, improvement of flexibility and suppression of warpage due to curing shrinkage have been performed.
However, in recent years, flexible substrates have become lighter and thinner as electronic devices become lighter and smaller, and accordingly, the effects of flexibility and curing shrinkage of the resin composition to be overcoated are becoming more prominent. . For this reason, in the present situation, the curing type overcoat agent cannot satisfy the required performance in terms of warpage due to flexibility and curing shrinkage.
この更なる狭ピッチ化に伴い、更なる電気絶縁性能の良好な樹脂の開発が求められている。
本発明の目的は、柔軟で、セミアディティブ法においても電気絶縁特性の良好な保護膜を得ることができる配線板の保護膜用熱硬化性組成物、該組成物を硬化して得られる配線板の保護膜、該保護膜によって被覆されたフレキシブル配線板、およびフレキシブル配線板の製造方法を提供することを目的とする。 However, with the development of the semi-additive method, the distance between wirings of the flexible wiring board is expected to be further narrowed (for example, 20 μm pitch or less).
With this further narrowing of the pitch, development of a resin having further excellent electrical insulation performance is required.
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.
(式中、R1は、炭素数3~18のアルキレン基を表し、nは1以上の整数を表す。) That is, 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.
(In the formula, R 1 represents an alkylene group having 3 to 18 carbon atoms, and n represents an integer of 1 or more.)
(式中、lは、0または1以上の整数を表す。) [3] The 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).
(In the formula, l represents 0 or an integer of 1 or more.)
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c) カルボキシル基を有するジオール、および
成分(d) 式(3)で示される2官能性水酸基末端イミド。
(式中、R2、R3は、それぞれ独立に、2価の脂肪族または芳香族炭化水素基を示し、Y1はテトラカルボン酸またはその酸無水物基から誘導される4価の有機基を示し、X1はジアミン或いはジイソシアネートから誘導される2価の有機基を示し、mは、0~20の整数である。) [7] 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): The thermosetting composition for a protective film for a wiring board according to [4] or [5], which is a polyurethane polyimide obtained by the above process.
Component (a) diisocyanate,
Component (b) (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms,
Component (c) Diol having a carboxyl group, and Component (d) A bifunctional hydroxyl-terminated imide represented by the formula (3).
Wherein R 2 and R 3 each independently represents a divalent aliphatic or aromatic hydrocarbon group, and 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.)
(式中、複数個のR4は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR5は、それぞれ独立に炭素数3~18のアルキレン基であり、a及びbは、それぞれ独立に1~20の整数であり、複数個のX2は、それぞれ独立に2価の有機基である。)
(式中、複数個のR6は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR7は、それぞれ独立に炭素数3~18のアルキレン基であり、c及びdは、それぞれ独立に1~20の整数であり、複数個のX3は、それぞれ独立に2価の有機基であり、Y2は、CH2、SO2またはOである。)
式中、複数個のR8は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR9は、それぞれ独立に炭素数3~18のアルキレン基であり、e及びfは、それぞれ独立に1~20の整数であり、複数個のX4は、それぞれ独立に2価の有機基であり、Y3は、式(7)~式(33)のいずれかの基である。
[8] 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): The thermosetting composition for a protective film of a wiring board according to [4] or [6], which is a polyurethane polyimide having at least one selected structural unit.
(Wherein 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, and 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.)
(Wherein 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, and 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, and Y 2 is CH 2 , SO 2 or O.)
In the formula, 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, and e and f are: Each independently represents an integer of 1 to 20, a plurality of X 4 are each independently a divalent organic group, and Y 3 is any group of formulas (7) to (33).
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c) カルボキシル基を有するジオール、
成分(e) 1分子中に水酸基を3個以上有する化合物。 [9] 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): The thermosetting composition for a protective film of a wiring board according to any one of [1] to [3], which is a polyurethane obtained by reaction.
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.
[12]溶剤が、下記A群の中から選ばれる少なくとも1種の溶剤と下記B群の中から選ばれる少なくとも1種の溶剤を必須成分とする混合溶剤であることを特徴とする[1]~[11]のいずれかに記載の配線板の保護膜用熱硬化性組成物。
A群:ジエチレングリコールジメチルエーテル(沸点162℃)、ジエチレングリコールジエチルエーテル(沸点189℃)、ジエチレングリコールエチルメチルエーテル(沸点176℃)、ジプロピレングリコ−ルジメチルエーテル(沸点171℃)、3−メトキシブチルアセテート(沸点171℃)、エチレングリコールモノブチルエーテルアセテート(沸点192℃)
B群:ジエチレングリコールブチルメチルエーテル(沸点212℃)、トリプロピレングリコールジメチルエーテル(沸点215℃)、トリエチレングリコールジメチルエーテル(沸点216℃)、エチレングリコールジブチルエーテル(沸点203℃)、ジエチレングリコールモノエチルエーテルアセテート(沸点217℃)、γ−ブチロラクトン(沸点204℃) [11] 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 thermosetting composition for a protective film of a wiring board according to any one of [1] to [10], wherein
[12] 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] ~ The thermosetting composition for a protective film of a wiring board according to any one of [11].
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 (boiling point) 217 ° C.), γ-butyrolactone (boiling point 204 ° C.)
また、本発明の硬化物は可撓性を有するので、クラックの生じにくい電気絶縁保護膜付きのフレキシブル配線板(例えば、COF等のフレキシブルプリント配線板)を提供することができる。 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. In addition, the adhesiveness to the underfill material is good, and the solvent resistance is also good. For this reason, 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 In addition, 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.
In addition, since 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.
まず、本発明(I)について説明する。
本発明(I)は、トリシクロデカン構造を有するエポキシ基含有化合物、エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有するポリウレタン及び溶剤を必須成分とする配線板の保護膜用熱硬化性組成物である。
(式中、R1は、炭素数3~18のアルキレン基を表し、nは1以上の整数を表す。) Hereinafter, the present invention will be specifically described.
First, the present invention (I) will be described.
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.
(In the formula, R 1 represents an alkylene group having 3 to 18 carbon atoms, and n represents an integer of 1 or more.)
(式中、lは、0または1以上の整数を表す。)
(式中、gは、0または1以上の整数を表す。) 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.)
In addition, 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).
上記の式(2)及び式(34)~(38)の中では、式(2)及び式(35)~式(38)で示される化合物が当てはまる。 Among these compounds having a tricyclo [5.2.1.0 2,6 ] decane structure or a tricyclo [3.3.1.1 3,7 ] decane structure and an epoxy group, it is preferable to reduce the water absorption rate. Specifically, an epoxy group containing a tricyclo [5.2.1.0 2,6 ] decane structure or a tricyclo [3.3.1.1 3,7 ] decane structure and having an aromatic ring structure Compounds are preferred.
Among the formulas (2) and (34) to (38), the compounds represented by the formulas (2) and (35) to (38) are applicable.
式(2)で示される化合物は、DIC株式会社から市販され(グレード名:エピクロンHP−7200L、エピクロンHP−7200、エピクロンHP−7200H、エピクロンHP−7200HH)、また、日本化薬株式会社からもXD−1000−2L、XD−1000のグレード名で市販されており、容易に入手可能である。 Among epoxy group-containing compounds having a tricyclo [5.2.1.0 2,6 ] decane structure or a tricyclo [3.3.1.1 3,7 ] decane structure and having an aromatic ring structure In view of the ease, 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.
前記エポキシ基と反応可能な官能基がエポキシ基と1:1で反応する基の場合には、本発明(I)の熱硬化性組成物中に含まれる、エポキシ基と反応可能な官能基の数とトリシクロデカン構造を有するエポキシ基含有化合物のエポキシ基の数の比は、1/3~2/1の範囲であることが好ましく、さらに好ましくは、1/2.5~1.5/1の範囲である。この比が1/3より小さくなると、未反応のエポキシ基が多く残存する可能性が高くなり好ましいことではない。また、この比が2/1よりも大きくなると、未反応のエポキシ基と反応可能な官能基が多く残存することになり、電気絶縁性能上好ましいこととは言えない。例えば、カルボキシル基がエポキシ基1:1で反応する官能基として挙げることができる。 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.
When 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.
(式中、R1は、炭素数3~18のアルキレン基を表し、nは1以上の整数を表す。) One of the essential components of the composition of the present invention (I), 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 | limiting in particular.
(In the formula, R 1 represents an alkylene group having 3 to 18 carbon atoms, and n represents an integer of 1 or more.)
nは、1~20の整数であることが好ましい。 In formula (1), R 1 represents an alkylene group having 3 to 18 carbon atoms. In the case of an alkylene group having 2 or less carbon atoms, the water resistance of the resulting polyurethane cannot be kept sufficiently, which is not preferable. Further, in the case of an alkylene group having 19 or more carbon atoms, 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.
例えば、1,9−ノナンジオールおよびジエチルカーボネートを原料に用いて、触媒の存在下、エステル交換反応によって(ポリ)カーボネートジオールを製造する際に、原料である1,9−ノナンジオールが生成物である(ポリ)カーボネートジオール中に5質量%残存していた場合には、この残存している1,9−ノナンジオールは、「(ポリ)カーボネートジオール」には含まれないことを意味する。 In addition, when the (poly) carbonate diol is produced, the raw material diol component may remain and be included. In the present specification, the remaining diol component is referred to as “(poly) carbonate diol”. It is defined as not included.
For example, when (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. When 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”.
次の1つの構造は、溶剤に溶解する範囲で分子中に一定の分岐構造を有することが望ましい。
もう1つの構造は、エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有し、さらに、ダイマージオールから誘導された有機残基を含有するポリウレタンであることが望ましい。 First, one of them is that 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.
(式中、複数個のR4は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR5は、それぞれ独立に炭素数3~18のアルキレン基であり、a及びbは、それぞれ独立に1~20の整数であり、複数個のX2は、それぞれ独立に2価の有機基である。)
(式中、複数個のR6は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR7は、それぞれ独立に炭素数3~18アルキレン基であり、c及びdは、それぞれ独立に1~20の整数であり、複数個のX3は、それぞれ独立に2価の有機基であり、Y2は、CH2、SO2またはOである。)
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) Polyurethane polyimide having in its molecule a structural unit represented by formula (6).
(Wherein 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, and 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.)
(Wherein 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, and 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.)
In the formula, 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, and e and f are: Each independently represents an integer of 1 to 20, a plurality of X 4 are each independently a divalent organic group, and Y 3 is any one of the following formulas (7) to (33): .
(式中、R14は、水素、炭素数1~10のアルキル基又はフェニル基を示す。) The trivalent polycarboxylic acid having an acid anhydride group and its derivative are not particularly limited. For example, in the case of a polyurethane polyimide having a structure represented by the formula (4), a compound represented by the formula (39) is used. Can be used. Trimellitic anhydride is particularly preferable from the viewpoints of heat resistance and cost.
(In the formula, R 14 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.)
(式中、R15は、水素、炭素数1~10のアルキル基又はフェニル基を示し、Y2は、CH2、CO、SO2、またはOである。) Moreover, in the case of the polyurethane polyimide which has a structure shown by Formula (5), the compound shown by Formula (40) can be used.
(Wherein R 15 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and Y 2 represents CH 2 , CO, SO 2 , or O.)
(式中、Y3は、前記の式(7)~式(33)のいずれかの基である。) Furthermore, in the case of polyurethane polyimide having a structure represented by the formula (6), a compound represented by the formula (41) can be used.
(In the formula, Y 3 is any one of the above formulas (7) to (33).)
(式中、複数個のR16は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR17は、それぞれ独立に炭素数3~18のアルキレン基であり、h及びiは、それぞれ独立に1~20の整数であり、複数個のX5は、それぞれ独立に2価の有機基である。) As the isocyanate compound, for example, a diisocyanate compound represented by the formula (42) can be used.
(Wherein 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, and h and i are And each independently represents an integer of 1 to 20, and a plurality of X 5 are each independently a divalent organic group.)
(式中、複数個のR18は、それぞれ独立に炭素数3~18のアルキレン基であり、jは、1~20の整数である。)
(式中、X6は、2価の有機基である。) 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).
(Wherein 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)
(In the formula, X 6 is a divalent organic group.)
従って、ダイセル化学工業株式会社製の商品名PLACCEL、CD−205、205PL、205HL、210、210PL、210HL、220、220PL、220HL、株式会社クラレ製の商品名クラレポリオールC−590、C−1065N、C−1015N、C−2015N等の市販の(ポリ)カーボネートジオール中に含まれる原料ジオールは、「(ポリ)カーボネートジオール」には含まれない。これらの原料ジオール成分は、後述の(w)に含まれる。 As described above, when the (poly) carbonate diol is produced, 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.
また、前述の市販の(ポリ)カーボネートジオール中に含まれる原料ジオールは、この成分(w)に含まれる。 Examples of the component (w) include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2 -Methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethylpropanediol, 1, Examples include 3-cyclohexanedimethanol, 1,3-xylylene glycol, and 1,4-xylylene glycol.
Moreover, the raw material diol contained in the above-mentioned commercially available (poly) carbonate diol is contained in this component (w).
これらの化合物としては、式(42)で示されるジイソシアネート化合物以外のポリイソシアネート化合物であれば特に限定されず、例えば、式(44)で示されるジイソシアネート、3価以上のポリイソシアネート等が挙げられる。これらは、単独で又は2種類以上を組み合わせて使用することができる。式(42)で示されるジイソシアネート化合物以外のポリイソシアネート化合物の数平均分子量の好ましい範囲は、式(42)で示されるジイソシアネート化合物と同様である。 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).
(式中、R4、R5、a、b、X2は、前記のとおりである。) In addition, 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). When the diisocyanate compound shown is used, a polyamideimide having a structural unit represented by the formula (4) can be obtained.
(Wherein R 4 , R 5 , a, b, and X 2 are as described above.)
(式中、R6、R7、c、d、X3、Y2は、前記のとおりである。) Further, a trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and / or a tetravalent polycarboxylic acid having an acid anhydride group as a compound represented by the formula (40), an isocyanate compound represented by the formula (42) When the diisocyanate compound shown is used, a polyamideimide having a structural unit represented by the formula (5) can be obtained.
(Wherein R 6 , R 7 , c, d, X 3 and Y 2 are as described above.)
(式中、R8、R9、e、f、X4、Y3は、前記のとおりである。) Further, a trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and / or a tetravalent polycarboxylic acid having an acid anhydride group as a compound represented by the formula (41), an isocyanate compound represented by the formula (42) When the diisocyanate compound shown is used, a polyamideimide having a structural unit represented by the formula (6) can be obtained.
(In the formula, R 8 , R 9 , e, f, X 4 , and Y 3 are as described above.)
この方法によって、末端にカルボキシル基、酸無水物或いはイソシアネート基を有するポリウレタンポリイミドが製造できる。末端基としては、エポキシ基との反応性を考慮すると、カルボキシル基及び/または酸無水物であることが好ましい。 A trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof, and a tetravalent polycarboxylic acid having an acid anhydride group in a process for producing a polyurethane polyimide having a structural unit represented by formula (4) to formula (6) 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. .
By this method, 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.
具体的には、大気圧下で170℃~200℃の沸点を有する溶剤として、ジエチレングリコールジエチルエーテル(沸点189℃)、ジエチレングリコールエチルメチルエーテル(沸点176℃)、ジプロピレングリコ−ルジメチルエーテル(沸点171℃)の中から選ばれる少なくとも1種と、大気圧下で200℃~220℃の沸点を有する溶剤として、γ−ブチロラクトン(沸点204℃)との組み合わせることが好ましく、最も好ましい組み合わせとしては、大気圧下で170℃~200℃の沸点を有する溶剤としてジエチレングリコールジエチルエーテル(沸点189℃)と、大気圧下で200℃~220℃の沸点を有する溶剤としてγ−ブチロラクトン(沸点204℃)とを組み合わせることである。 After synthesis, it is preferable to use a suitable solvent for the thermosetting composition of the present invention as it is. In order to carry out the reaction in a homogeneous system with high volatility and low temperature curability, 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. under atmospheric pressure, preferably γ-butyrolactone (boiling point 204 ° C.), and most preferable combination is atmospheric pressure. Combining diethylene glycol diethyl ether (boiling point 189 ° C.) as a solvent having a boiling point of 170 ° C. to 200 ° C. and γ-butyrolactone (boiling point 204 ° C.) as a solvent having a boiling point of 200 ° C. to 220 ° C. under atmospheric pressure. It is.
また、合成終了後に樹脂末端のイソシアネート基をアルコール類、ラクタム類、オキシム類等のブロック剤でブロックすることもできる。 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.
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c′) エポキシ基と反応可能な官能基を有するジオール化合物、および
成分(d) 式(3)で示される2官能性水酸基末端イミド。
(式中、R2、R3は、それぞれ独立に、2価の脂肪族または芳香族炭化水素基を示し、Y1はテトラカルボン酸またはその酸無水物基から誘導される4価の有機基を示し、X1はジアミン或いはジイソシアネートから誘導される2価の有機基を示し、mは、0~20の整数である。) 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).
Wherein R 2 and R 3 each independently represents a divalent aliphatic or aromatic hydrocarbon group, and 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.)
前記ブロック化剤としては、例えばアルコ−ル系、フェノ−ル系、活性メチレン系、メルカプタン系、酸アミド系、酸イミド系、イミダゾ−ル系、尿素系、オキシム系、アミン系、イミン系、重亜硫酸塩系、ピリジン系等があり、これらを単独あるいは混合して使用してもよい。具体的なブロック化剤としては、アルコ−ル系としてメタノ−ル、エタノ−ル、プロパノ−ル、ブタノ−ル、2−エチルヘキサノ−ル、メチルセロソルブ、ブチルセロソルブ、メチルカルビト−ル、ベンジルアルコ−ル、シクロヘキサノ−ル等、フェノ−ル系として、フェノ−ル、クレゾ−ル、エチルフェノ−ル、ブチルフェノ−ル、ノニルフェノ−ル、ジノニルフェノ−ル、スチレン化フェノ−ル、ヒドロキシ安息香酸エステル等、活性メチレン系として、マロン酸ジメチル、マロン酸ジエチル、アセト酢酸メチル、アセト酢酸エチル、アセチルアセトン等、メルカプタン系として、ブチルメルカプタン、ドデシルメルカプタン等、酸アミド系として、アセトアニリド、酢酸アミド、ε−カプロラクタム、δ−バレロラクタム、γ−ブチロラクタム等、酸イミド系として、コハク酸イミド、マレイン酸イミド、イミダゾ−ル系として、イミダゾ−ル、2−メチルイミダゾ−ル、尿素系として、尿素、チオ尿素、エチレン尿素等、オキシム系として、ホルムアルドオキシム、アセトアルドオキシム、アセトオキシム、メチルエチルケトオキシム、シクロヘキサノンオキシム等、アミン系として、ジフェニルアミン、アニリン、カルバゾール等、イミン系として、エチレンイミン、ポリエチレンイミン等、重亜硫酸塩系として、重亜硫酸ソ−ダ等、ピリジン系として、2−ヒドロキシピリジン、2−ヒドロキシキノリン等が挙げられる。 As the diisocyanate, a blocked diisocyanate obtained by blocking an isocyanate group with a blocking agent can be used.
Examples of 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, ε-caprolactam, δ-valero Lactam, γ-Butirola Tam, etc., acid imide, succinimide, maleic imide, imidazole, imidazole, 2-methylimidazole, urea, urea, thiourea, ethylene urea, etc., oxime, Formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc., amine type, diphenylamine, aniline, carbazole, etc., imine type, ethyleneimine, polyethyleneimine, etc., bisulfite type, bisulfite type Examples of pyridines such as 2-hydroxypyridine and 2-hydroxyquinoline.
例えば、1,9−ノナンジオールおよびジエチルカーボネートを原料に用いて、触媒の存在下、エステル交換反応によって(ポリ)カーボネートポリオールを製造する際に、原料である1,9−ノナンジオールが生成物である(ポリ)カーボネートポリオール中に5質量%残存していた場合には、この残存している1,9−ノナンジオールは、「(ポリ)カーボネートポリオール」には含まれずに、後述の成分(x)に含まれることを意味する。 In addition, when the (poly) carbonate polyol is produced, the polyol component that is a raw material may remain and be included. In the present specification, the remaining polyol component is referred to as “(poly) carbonate polyol”. It is defined as not included.
For example, when (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. When 5% by mass remains in a certain (poly) carbonate polyol, the remaining 1,9-nonanediol is not included in the “(poly) carbonate polyol”, but the component (x ).
(式中、R2、R3は、それぞれ独立に、2価の脂肪族または芳香族炭化水素基を示し、Y1はテトラカルボン酸またはその酸無水物基から誘導される4価の有機基を示し、X1はジアミン或いはジイソシアネートから誘導される2価の有機基を示し、mは、0~20の整数である。) Used when synthesizing 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 described in JP-A-2006-307183. The bifunctional hydroxyl-terminated imide can be represented by the following formula (3).
Wherein R 2 and R 3 each independently represents a divalent aliphatic or aromatic hydrocarbon group, and 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.)
テトラカルボン酸成分は、ジアミンと反応させることが容易なテトラカルボン酸二無水物を用いることが好ましい。 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. Specifically, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2 , 2-bis (3,4-benzenedicarboxylic acid) hexafluoropropane, pyromellitic acid, 1,4-bis (3,4-benzenedicarboxylic acid) benzene, 2,2-bis [4- (3,4- Phenoxydicarboxylic acid) phenyl] propane, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1, , 5,8-naphthalenetetracarboxylic acid, aromatic tetracarboxylic acids such as 1,1-bis (2,3-dicarboxyphenyl) ethane, or esterified products of their acid dianhydrides and lower alcohols, and Cycloaliphatic tetracarboxylic acids such as cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3-methylcyclohexane-1,2,4,5-tetracarboxylic acid, or their acids Preferable examples include anhydrides and esterified products of lower alcohols. Of these, 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.
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c′) エポキシ基と反応可能な官能基を有するジオール化合物、および
成分(d) 式(3)で示される2官能性水酸基末端イミド
を必須成分とする組成物を反応して得られる。 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.
(式中、X6はジイソシアネートからイソシアネート基を除いた2価の基、複数個のR20は、それぞれ独立に、炭素数3~18のジオールから水酸基を除いた2価の基、tは1~40の整数、uは1~100の整数を表す。)
(式中、X6はジイソシアネートからイソシアネート基を除いた2価の基、Wは、エポキシ基と反応可能な官能基を有するジオールから水酸基を除いた2価の基を表し、vは1~40の整数を表す。)
(式中、X6はジイソシアネートからイソシアネート基を除いた2価の基、複数個のR21、R22はそれぞれ独立に2価の脂肪族または芳香族炭化水素基、Y4はテトラカルボン酸のカルボキシル基を除いた4価の基、X7はジアミンのアミノ基を除いた2価の基を表し、wは0~20の整数、xは1~100の整数を表す。) The resulting polyurethane polyimide preferably contains structural units of the following formulas (45) to (47).
(In the formula, 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)
(Wherein X 6 represents a divalent group obtained by removing an isocyanate group from diisocyanate, 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, and v represents 1 to 40) Represents an integer.)
(In the formula, 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 aromatic hydrocarbon group, and Y 4 is a tetracarboxylic acid. A tetravalent group excluding a carboxyl group, X 7 represents a divalent group excluding an amino group of diamine, w represents an integer of 0 to 20, and x represents an integer of 1 to 100.)
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c) カルボキシル基を有するジオール、
成分(d) 式(3)で示される2官能性水酸基末端イミド。 When the stability of the synthesized polyimide polyurethane is regarded as important among polyurethane polyimides having a functional group capable of reacting with an epoxy group and the structural unit represented by the formula (1) and further having an imide bond Than the 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, as described in JP-A-2003-198105. Polyurethane polyimide having a functional group capable of reacting with an epoxy group described in JP-A-2006-307183, a structural unit represented by the formula (1), and further having an imide bond is preferable. Particularly preferred is 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).
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c) カルボキシル基を有するジオール、
成分(e) 1分子中に水酸基を3個以上有する化合物。 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.
例えば、トリメチロールプロパンと1,9−ノナンジオールおよびジエチルカーボネートを原料に用いて、触媒の存在下、エステル交換反応によって(ポリ)カーボネートポリオールを製造する際に、原料であるトリメチロールプロパンと1,9−ノナンジオールが生成物である(ポリ)カーボネートポリオール中にそれぞれ5質量%ずつ残存していた場合には、この残存しているトリメチロールプロパンおよび1,9−ノナンジオールは、「(ポリ)カーボネートポリオール」には含まれずに、ポリオールが1分子中に水酸基を3個以上有する化合物(この場合には、トリメチロールプロパン)である場合には、このポリオールは成分(e)に属することを意味し、ポリオールが1分子中に水酸基を2個有する化合物(この場合には、1,9−ノナンジオール)である場合には、後述の成分(y)に含まれることを意味する。 As described above, when the (poly) carbonate polyol is produced, 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”.
For example, when a (poly) carbonate polyol is produced by transesterification using trimethylolpropane, 1,9-nonanediol and diethyl carbonate as raw materials in the presence of a catalyst, When 5% by mass of 9-nonanediol remained in the (poly) carbonate polyol as a product, the remaining trimethylolpropane and 1,9-nonanediol were “(poly) When the polyol is a compound (in this case, trimethylolpropane) that is not included in the “carbonate polyol” and has 3 or more hydroxyl groups in one molecule, this means that the polyol belongs to the component (e). And a compound having two hydroxyl groups in one molecule (in this case, 1, - in the case of nonanediol) is meant to be included in the components described below (y).
成分(y)としては、例えば、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、1,8−オクタンジオール、1,3−シクロヘキサンジメタノール、1,4−シクロヘキサンジメタノール、1,9−ノナンジオール、2−メチル−1,8−オクタンジオール、1,10−デカメチレングリコール、1,2−テトラデカンジオール、2,4−ジエチル−1,5−ペンタンジオール、2−ブチル−2−エチルプロパンジオール、1,3−シクロヘキサンジメタノール、1,3−キシリレングリコール、1,4−キシリレングリコール等を挙げることができる。 If necessary, in addition to component (b), component (c) and component (e), a diol component not included in any of component (b), component (c) and component (e) (below) , Described as component (y)).
Examples of the component (y) include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2 -Methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethylpropanediol, 1, Examples include 3-cyclohexanedimethanol, 1,3-xylylene glycol, and 1,4-xylylene glycol.
なお、本明細書においては、特に断りのない限り、GPCの測定条件は以下のとおりである。
装置名:日本分光株式会社製HPLCユニット HSS−2000
カラム:ShodexカラムLF−804(3本直列)
移動相:テトラヒドロフラン
流速:1.0mL/min
検出器:日本分光株式会社製RI−2031Plus
温度:40.0℃
試料量:サンプルループ 100μリットル
試料濃度:0.1質量%前後に調製。 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.
Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation
Column: Shodex column LF-804 (3 in series)
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: JASCO Corporation RI-2031Plus
Temperature: 40.0 ° C
Sample amount: 100 μl of sample loop Sample concentration: prepared at around 0.1% by mass.
なお、本明細書において、ポリウレタンの酸価は、JIS K0070の電位差滴定法で測定された酸価の値である。 As this polyurethane, 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.
In this specification, the acid value of polyurethane is a value of acid value measured by potentiometric titration method of JIS K0070.
(式中、R10およびR11は何れもアルキル基であり、pおよびqは0以上の整数であり、かつR10およびR11に含まれる各炭素数ならびにpおよびqの合計は30である。)
(式中、R12およびR13は何れもアルキル基であり、rおよびsは0以上の整数であり、かつR12およびR13に含まれる各炭素数ならびにrおよびsの合計は34である。) In the present specification, 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. Here, the main component means that 50% by mass or more is present. In addition to the diol having 36 carbon atoms, there may be a diol having 22 to 44 carbon atoms and not 36 carbon atoms. As 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 (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).
(Wherein 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) .)
(Wherein 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. .)
また、本発明における「炭素数3~18のジオールから誘導された有機残基」とは、炭素数3~18のジオールの少なくとも1つのアルコール性水酸基の水素を除いた構造を意味する。 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.
In the present invention, 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.
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c) カルボキシル基を有するジオール、
成分(l) ダイマージオール
成分(z) 成分(b)、成分(c)及び成分(l)の群から選ばれるポリオール以外のポリオール 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 | combine by making the raw material component (component (z) as needed) which makes component (b), a component (c), and a component (l) essential.
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 (l) Dimer diol Component (z) Polyol other than polyol selected from the group consisting of component (b), component (c) and component (l)
例えば、1,9−ノナンジオールおよびジエチルカーボネートを原料に用いて、触媒の存在下、エステル交換反応によって(ポリ)カーボネートポリオールを製造する際に、原料である1,9−ノナンジオールが生成物である(ポリ)カーボネートポリオール中に5質量%残存していた場合には、この残存している1,9−ノナンジオールは、「(ポリ)カーボネートポリオール」には含まれずに、後述の成分(z)に含まれることを意味する。 As described above, when the (poly) carbonate polyol is produced, 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”.
For example, when (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. When 5% by mass remains in a certain (poly) carbonate polyol, the remaining 1,9-nonanediol is not included in the “(poly) carbonate polyol”, but the component (z ).
成分(z)としては、例えば、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、1,8−オクタンジオール、1,3−シクロヘキサンジメタノール、1,4−シクロヘキサンジメタノール、1,9−ノナンジオール、2−メチル−1,8−オクタンジオール、1,10−デカメチレングリコール、1,2−テトラデカンジオール、2,4−ジエチル−1,5−ペンタンジオール、2−ブチル−2−エチルプロパンジオール、1,3−シクロヘキサンジメタノール、1,3−キシリレングリコール、1,4−キシリレングリコール等を挙げることができる。 Further, in addition to 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.
Examples of the component (z) include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2 -Methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethylpropanediol, 1, Examples include 3-cyclohexanedimethanol, 1,3-xylylene glycol, and 1,4-xylylene glycol.
数平均分子量が1000未満では、硬化膜の伸度、可撓性、並びに強度を損なうことがあり、100000を超えると溶剤への溶解性が低くなる上に、溶解しても粘度が高くなり、使用面で制約が生じることがある。 As described above, 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.
これらの硬化促進剤を単独で使用しても、或いは2種類以上を併用しても良い。 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. For example, 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 Compounds, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4- Methylimidazole, 1-cyanoethyl-2 Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1- (cyanoethylaminoethyl) -2-methyl Imidazole, N- [2- (2-Methyl-1-imidazolyl) ethyl] urea, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenyl Imidazolium trimellitate, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2'-methyl Imidazolyl- (1 ′)]-ethyl-s-triazine 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ′)]-Ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N, N′-bis ( 2-methyl-1-imidazolylethyl) adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4.5-dihydroxymethylimidazole, 2-methylimidazole isocyanuric acid adduct, 2-phenyl Imidazole-isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-tria Gin isocyanuric acid adduct, 2-methyl-4-formylimidazole, 2-ethyl-4-methyl-5-formylimidazole, 2-phenyl-4-methylformylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1- (2-hydroxyethyl) imidazole, vinylimidazole, 1-methylimidazole, 1-allylimidazole, 2-ethylimidazole, 2-butylimidazole, 2-butyl-5-hydroxymethylimidazole, Imidazoles such as 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-benzyl-2-phenylimidazole hydrobromide, 1-dodecyl-2-methyl-3-benzylimidazolium chloride Compound, 1,5-diazabicyclo 4.3.0) Nonamen-5 and salts thereof, cycloamidine compounds such as diazabicycloalkenes such as 1,8-diazabicyclo (5.4.0) undecene-7 and salts thereof, and derivatives thereof, triethylenediamine, benzyl Tertiary amino group-containing compounds such as dimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) ) Phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxypheny) ) Phosphine, tris (tri-alkoxyphenyl) phosphine, tris (tetra-alkoxyphenyl) phosphine, trialkyl phosphine, dialkyl aryl phosphines, organic phosphine compounds such as an alkyl diaryl phosphines, can be given Jishianjiajido like.
These curing accelerators may be used alone or in combination of two or more.
なお、本明細書においては、「無機微粒子および/または有機微粒子」とは、無機微粒子、有機微粒子のみならず、粉末状の無機化合物に有機化合物で物理的に被覆或いは有機化合物で化学的に表面処理したような有機・無機の複合物系微粒子も含まれるものと定義する。 In the thermosetting composition of the present invention (I), inorganic fine particles and / or organic fine particles can be blended and preferably blended for the purpose of adjusting fluidity.
In the present specification, “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.
なお、本明細書で記載の「COF」とは、ベアチップをフレキシブル配線板に搭載し、接続する実装方式を意味する。 The thermosetting composition for a protective film of a wiring board of the present invention (I) 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.
Note that “COF” described in this specification means a mounting method in which a bare chip is mounted on a flexible wiring board and connected.
上記の消泡剤は、文字通り、本発明(I)の熱硬化性組成物を印刷する際に、発生する気泡を消す或いは抑制する作用を有するものであれば、特に制限はない。
本発明(I)の熱硬化性組成物に使用される消泡剤の具体例としては、例えば、BYK−077(ビックケミー・ジャパン社製)、SNデフォーマー470(サンノプコ社製)、TSA750S(モメンティブ・パフォーマンス・マテリアルズ社製)、シリコーンオイルSH−203(東レ・ダウコーニング株式会社製)等のシリコーン系消泡剤、ダッポーSN−348(サンノプコ社製)、ダッポーSN−354(サンノプコ社製)、ダッポーSN−368(サンノプコ社製)、ディスパロン230HF(楠本化成株式会社製)等のアクリル重合体系消泡剤、サーフィノールDF−110D(日信化学工業株式会社製)、サーフィノールDF−37(日信化学工業株式会社製)等のアセチレンジオール系消泡剤、FA−630等のフッ素含有シリコーン系消泡剤等を挙げることができる。 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.
Specific examples of 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., Ltd., and fluorine-containing FA-630 etc. Mention may be made of a silicone-based anti-foaming agents, and the like.
Examples of 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).
本発明(II)は、本発明(I)に記載の配線板の保護膜用熱硬化性組成物を硬化して得られる配線板の保護膜である。 Next, the protective film of the wiring board of the present invention (II) will be described.
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).
第一工程
本発明(I)の熱硬化性組成物を印刷して塗膜を得る工程。
第二工程
第一工程で得られた塗膜を20℃~100℃の雰囲気下で溶媒を蒸発させ、一部或いは全量の溶媒が除去された塗膜を得る工程。
第三工程
第二工程で得られた塗膜を、100℃~250℃の雰囲気下で熱硬化を行い、熱硬化された塗膜(即ち、硬化塗膜)を得る工程。 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. For example, when obtaining the protective film for the wiring board of the present invention (II), 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.
工程A
本発明(I)の熱硬化性組成物を、フレキシブル配線板の予め錫メッキ処理された配線パターン部にスクリーン印刷し、塗膜を得る工程。
工程B
工程Aで得られた塗膜を20~100℃の雰囲気下で溶媒を蒸発させ、一部或いは全量の溶媒が除去された塗膜を得る工程。
工程C
工程Bで得られた塗膜を、80~130℃の雰囲気下で熱硬化を行い、熱硬化されたフレキシブル配線板の保護膜を得る工程。 Below, the specific process of the manufacturing method of this invention (IV) is described. For example, 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.
本発明(I)の必須成分である、エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有するポリウレタンが、エポキシ基と反応可能な官能基としてカルボキシル基を有する場合に、以下の方法によって酸価の測定を行った。
前記のカルボキシル基を有するポリウレタン溶液中の溶媒を加熱下で、減圧留去してカルボキシル基を有するポリウレタンを得た。
このカルボキシル基を有するポリウレタンを用いて、JIS K0070の電位差滴定法に準拠して酸価を測定した。
なお、電位差滴定法で用いた装置を以下に記す。
装置名:京都電子工業株式会社製 電位差自動滴定装置 AT−510
電極:京都電子工業株式会社製 複合ガラス電極C−173 <Measurement of acid value>
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. In some cases, 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.
Using this 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.
JIS K0070の中和滴定法に従い、水酸基価を測定した。 <Measurement of hydroxyl value>
The hydroxyl value was measured according to the neutralization titration method of JIS K0070.
GPCで測定したポリスチレン換算の値であり、GPCの測定条件は以下のとおりである。
装置名:日本分光(株)製HPLCユニット HSS−2000
カラム:ShodexカラムLF−804を3本連結(直列)
移動相:テトラヒドロフラン
流速:1.0mL/min
検出器:日本分光株式会社製 RI−2031Plus
温度:40.0℃
試料量:サンプルループ 100μl
試料濃度:0.1質量%前後に調製 <Measurement of number average molecular weight of polyurethane>
It is a value in terms of polystyrene measured by GPC, and GPC measurement conditions are as follows.
Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation
Column: Three Shodex columns LF-804 connected (in series)
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI-2031Plus manufactured by JASCO Corporation
Temperature: 40.0 ° C
Sample volume: Sample loop 100 μl
Sample concentration: adjusted to around 0.1% by mass
カルボキシル基含有ポリウレタン溶液の粘度を以下の方法により測定した。
カルボキシル基含有ポリウレタン溶液約0.8gを使用して、コーン/プレート型粘度計(Brookfield社製 型式;DV−II+Pro スピンドルの型番;CPE−52)を用いて、温度25.0℃、回転数5rpmの条件で測定開始から7分経過後の粘度を測定した。 <Measurement of viscosity of polyurethane solution>
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.
熱硬化性組成物のチクソトロピー指数を以下の方法により測定した。
熱硬化性組成物約0.6gを使用して、チクソトロピー指数をコーン/プレート型粘度計(Brookfield社製 型式;DV−II+Pro スピンドルの型番;CPE−52)を用いて、温度25.0℃、回転数10rpmの条件で測定開始から7分経過後の粘度を測定した。その後、温度25.0℃、回転数1rpmの条件で測定開始から7分経過後の粘度を測定した。
なお、チクソトロピー指数の計算は以下の方法により求めた。
チクソトロピー指数の求め方:
チクソトロピー指数=[1rpmの粘度]÷[10rpmの粘度] <Measurement of thixotropy index>
The thixotropy index of the thermosetting composition was measured by the following method.
Using a thermosetting composition of about 0.6 g, a thixotropy index was determined using a cone / plate viscometer (Brookfield model: DV-II + Pro spindle model number: CPE-52) at a temperature of 25.0 ° C. The viscosity was measured after 7 minutes from the start of measurement under the condition of 10 rpm. Thereafter, the viscosity was measured after 7 minutes from the start of measurement under the conditions of a temperature of 25.0 ° C. and a rotation speed of 1 rpm.
The thixotropy index was calculated by the following method.
How to find the thixotropy index:
Thixotropic index = [viscosity at 1 rpm] ÷ [viscosity at 10 rpm]
(参考合成例1)2官能性水酸基末端イミド(A)の製造
窒素導入管、ディーンスタークレシバー、冷却管を備えた容量500mLのガラス製セパラブルフラスコに、2,3,3′,4′−ビフェニルテトラカルボン酸二無水物58.8g(0.20mol)、イソホロンジアミン17.0g(0.10mol)、3−アミノプロパノール15.0g(0.20mol)、及びジメチルアセトアミド200mLを仕込み、窒素雰囲気下、100℃で1時間撹拌した。次いで、トルエン50mLを加え、180℃4時間加熱し、イミド化反応により生じた水をトルエンと共沸により除いた。反応溶液を水2Lに投入して、生じた沈殿を濾取し、水洗後減圧乾燥し、粉末78.8gを得た。この化合物の1H−NMRの結果より、この化合物は式(3)のm(平均値)が1である2官能性水酸基末端イミド(以下、2官能性水酸基末端イミド(A)と記す。)であることが確認された。 <Synthesis of bifunctional hydroxyl-terminated imide>
(Reference Synthesis Example 1) Production of bifunctional hydroxyl-terminated imide (A) In a 500-mL glass separable flask equipped with a nitrogen introduction tube, a Dean Star crusher, and a cooling tube, 2, 3, 3 ', 4'- In a nitrogen atmosphere, 58.8 g (0.20 mol) of biphenyltetracarboxylic dianhydride, 17.0 g (0.10 mol) of isophoronediamine, 15.0 g (0.20 mol) of 3-aminopropanol, and 200 mL of dimethylacetamide were charged. , And stirred at 100 ° C. for 1 hour. Subsequently, 50 mL of toluene was added and heated at 180 ° C. for 4 hours, and water generated by the imidization reaction was removed azeotropically with toluene. The reaction solution was poured into 2 L of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 78.8 g of powder. From the result of 1 H-NMR of this compound, this compound is 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.
窒素導入管、ディーンスタークレシバー、冷却管を備えた容量500mLのガラス製セパラブルフラスコに、2,3,3′,4′−ビフェニルテトラカルボン酸二無水物58.8g(0.20mol)、イソホロンジアミン25.55g(0.15mol)、3−アミノプロパノール7.51g(0.1mol)、及びジメチルアセトアミド200mLを仕込み、窒素雰囲気下、100℃で1時間撹拌した。次いで、トルエン50mLを加え、180℃4時間加熱し、イミド化反応により生じた水をトルエンと共沸により除いた。反応溶液を水2Lに投入して、生じた沈殿を濾取し、水洗後減圧乾燥し、粉末72.0gを得た。この化合物の1H−NMRの結果より、この化合物は式(3)のm(平均値)が3である2官能性水酸基末端イミド(以下、2官能性水酸基末端イミド(B)と記す。)であることが確認された。 (Reference Synthesis Example 2) Production of bifunctional hydroxyl-terminated imide (B) In a 500 mL glass separable flask equipped with a nitrogen introduction tube, a Dean Star cleaver and a cooling tube, 2,3,3 ', 4'- In a nitrogen atmosphere, 58.8 g (0.20 mol) of biphenyltetracarboxylic dianhydride, 25.55 g (0.15 mol) of isophoronediamine, 7.51 g (0.1 mol) of 3-aminopropanol, and 200 mL of dimethylacetamide were charged. , And stirred at 100 ° C. for 1 hour. Subsequently, 50 mL of toluene was added and heated at 180 ° C. for 4 hours, and water generated by the imidization reaction was removed azeotropically with toluene. The reaction solution was poured into 2 L of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 72.0 g of powder. From the result of 1 H-NMR of this compound, this compound is 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.
(実施合成例1)
ポリウレタンポリイミド(1)の合成
窒素導入管を備えた容量300mLのガラス製フラスコに、クラレポリオールC−2015((ポリ)カーボネートジオールと原料ジオール(即ち、1,6−ヘキサンジオール及び3−メチル−1,5−ペンタンジオール)の混合物、原料ジオールの仕込みモル比;1,6−ヘキサンジオール:3−メチル−1,5−ペンタンジオール=85:15、水酸基価56.1mgKOH/g、1,6−ペキサンジオールの残存濃度1.5質量%、3−メチル−1,5−ペンタンジオールの残存濃度0.5質量%)50.00g(25mmol)、2,2−ジメチロールプロピオン酸3.35g(25mmol)、4,4′−ジフェニルメタンジイソシアネート15.64g(62.5mmol)、γ−ブチロラクトン69.76gを仕込み、窒素雰囲気下、60℃で3.5時間撹拌した。次いで、参考例2で調製した2官能性水酸基末端イミド(A)20.92g(25mmol)、γ−ブチロラクトン20.92gを加え、80℃で10時間撹拌した。このポリウレタンポリイミド(以下、ポリウレタンポリイミド(1)と記す。)溶液のGPCから求めた数平均分子量は6800であった。このポリウレタンポリイミド(1)の溶液にγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=27.7:72.3(質量比)の混合溶媒23.75gを加え、固形分濃度44質量%に調整した。この溶液の粘度は、40Pa・sであった。また、ポリウレタンポリイミド(1)の酸価は15.6mg−KOH/gであった。 <Synthesis of polyurethane polyimide>
(Execution synthesis example 1)
Synthesis of Polyurethane Polyimide (1) Into a glass flask having a capacity of 300 mL equipped with a nitrogen introduction tube, Kuraray polyol C-2015 ((poly) carbonate diol and raw material diol (ie 1,6-hexanediol and 3-methyl-1) , 5-pentanediol), feed molar ratio of raw material diol; 1,6-hexanediol: 3-methyl-1,5-pentanediol = 85: 15, hydroxyl value 56.1 mgKOH / g, 1,6- Pexanediol residual concentration of 1.5 mass%, 3-methyl-1,5-pentanediol residual concentration of 0.5 mass%) 50.00 g (25 mmol), 2,2-dimethylolpropionic acid 3.35 g ( 25 mmol), 4,4′-diphenylmethane diisocyanate 15.64 g (62.5 mmol), γ-butyro G of tons 69.76G, under a nitrogen atmosphere and stirred 3.5 hours at 60 ° C.. Next, 20.92 g (25 mmol) of the bifunctional hydroxyl-terminated imide (A) prepared in Reference Example 2 and 20.92 g of γ-butyrolactone were added and stirred at 80 ° C. for 10 hours. The number average molecular weight determined from GPC of this polyurethane polyimide (hereinafter referred to as polyurethane polyimide (1)) solution was 6800. 23.75 g of a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 27.7: 72.3 (mass ratio) was added to the polyurethane polyimide (1) solution to adjust the solid content concentration to 44 mass%. The viscosity of this solution was 40 Pa · s. Moreover, the acid value of polyurethane polyimide (1) was 15.6 mg-KOH / g.
ポリウレタンポリイミド(2)の合成
窒素導入管を備えた5リットルのガラス製容器に、1,6−ヘキサン系ポリカーボネートジオールであるPLACCELCD−220((ポリ)カーボネートジオールと原料ジオール(即ち、1,6−ヘキサンジオール)の混合物、水酸基価56.1mgKOH/g、1,6−ヘキサンジオールの残存濃度3.0質量%)1000.0g(0.50mol)及び4,4′−ジフェニルメタンジイソシアネート250.27g(1.00mol)、γ−ブチロラクトン833.15gを仕込み、140℃に昇温し、5時間反応させた。更に、この反応混合物に、3,3′,4,4′−ジフェニルスルホンテトラカルボン酸二無水物358.29g(1.00mol)、4,4′−ジフェニルメタンジイソシアネート125.14g(0.50mol)、及びγ−ブチロラクトン584.97gを加えて、160℃で5時間反応させた。得られたポリウレタンポリイミド(以下、ポリウレタンポリイミド(2)と記す。)をγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=67:33(質量比)の混合溶媒で希釈し、粘度40Pa・s、固形分濃度40質量%のポリウレタンポリイミド(2)の溶液を得た。GPCから求めたこのポリウレタンポリイミド(2)の数平均分子量は14000であった。
ポリウレタンポリイミド(2)は、赤外吸収(IR)スペクトルを測定して、カルボン酸無水物の吸収が確認された。
このポリウレタンポリイミド(2)の溶液は合成後その日の内に下記の評価に使用された。 (Execution synthesis example 2)
Synthesis of Polyurethane Polyimide (2) In a 5 liter glass container equipped with a nitrogen introduction tube, a 1,6-hexane polycarbonate diol, PLACELCD-220 ((poly) carbonate diol and raw material diol (ie, 1,6- Hexanediol), hydroxyl value 56.1 mgKOH / g, 1,6-hexanediol residual concentration 3.0 mass%) 1000.0 g (0.50 mol) and 4,4'-diphenylmethane diisocyanate 250.27 g (1 0.003 mol) and 833.15 g of γ-butyrolactone were charged, and the temperature was raised to 140 ° C. and reacted for 5 hours. Further, to this reaction mixture, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 358.29 g (1.00 mol), 4,4′-diphenylmethane diisocyanate 125.14 g (0.50 mol), And 58.497 g of γ-butyrolactone were added and reacted at 160 ° C. for 5 hours. The obtained polyurethane polyimide (hereinafter referred to as polyurethane polyimide (2)) is diluted with a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 67: 33 (mass ratio), and has a viscosity of 40 Pa · s and a solid content concentration of 40 mass. % Polyurethane polyimide (2) solution was obtained. The number average molecular weight of this polyurethane polyimide (2) obtained from GPC was 14,000.
The polyurethane polyimide (2) was measured for infrared absorption (IR) spectrum, and absorption of carboxylic acid anhydride was confirmed.
This polyurethane polyimide (2) solution was used for the following evaluation within the day after synthesis.
(実施合成例3)
ポリウレタン(1)の合成
攪拌装置、温度計およびコンデンサーを備えた反応容器に、C−1015N(株式会社クラレ製(ポリ)カーボネートジオールと原料ジオール(即ち、1,9−ノナンジオール及び2−メチル−1,8−オクタンジオール)の混合物、原料ジオールの仕込みモル比;1,9−ノナンジオール:2−メチル−1,8−オクタンジオール=15:85、水酸基価112.3mgKOH/g、1,9−ノナンジオールの残存濃度2.1質量%、2−メチル−1,8−オクタンジオールの残存濃度9.3質量%)220.4g(0.221mol)、2,2−ジメチロールブタン酸(日本化成株式会社製)42.2g(0.285mol)、トリメチロールプロパン2.7g(20.1mmol)、γ−ブチロラクトン510.0gとジエチレングリコールジエチルエーテル90.0gを仕込み、100℃に加熱してすべての原料を溶解した。反応液の温度を90℃まで下げ、滴下ロートにより、メチレンビス(4−シクロヘキシルイソシアネート)133.7g(0.510mol)を30分かけて滴下した。120℃で9時間反応を行い、ほぼイソシアネートが消失したことを確認した後、エタノール1.3g(28.2mmol)を滴下し、さらに80℃で3時間反応を行い、カルボキシル基及びカーボネート結合を有するポリウレタン(以下、ポリウレタン(1)と記す。)を含む溶液を得た。
得られたポリウレタン(1)を含む溶液の粘度は101Pa・sであった。また、ポリウレタン(1)を含む溶液中に含まれるポリウレタン(1)の数平均分子量は14,000であり、ポリウレタン(1)の酸価は40.0mg−KOH/gであった。
また、このポリウレタン(1)を含む溶液中の固形分濃度は40.0質量%であった。 <Synthesis of branched polyurethane having carboxyl group and carbonate bond>
(Execution synthesis example 3)
Synthesis of polyurethane (1) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, C-1015N (Kuraray Co., Ltd. (poly) carbonate diol and raw diol (ie, 1,9-nonanediol and 2-methyl- 1,8-octanediol), feed molar ratio of raw material diol; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15: 85, hydroxyl value 112.3 mgKOH / g, 1,9 -Residual concentration of nonanediol of 2.1 mass%, residual concentration of 2-methyl-1,8-octanediol of 9.3 mass%) 220.4 g (0.221 mol), 2,2-dimethylolbutanoic acid (Japan) 42.2 g (0.285 mol), 2.7 g (20.1 mmol) trimethylolpropane, γ-butyrolactone 51 Were charged .0g and diethylene glycol diethyl ether 90.0 g, was dissolved. 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. After reacting at 120 ° C. for 9 hours and confirming that the isocyanate almost disappeared, 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.
(実施合成例4)
ポリウレタン(2)の合成
攪拌装置、温度計およびコンデンサーを備えた反応容器に、C−2015N(株式会社クラレ製(ポリ)カーボネートジオールと原料ジオール(即ち、1,9−ノナンジオール及び2−メチル−1,8−オクタンジオール)の混合物、原料ジオールの仕込みモル比;1,9−ノナンジオール:2−メチル−1,8−オクタンジオール=15:85、水酸基価56.5mgKOH/g、1,9−ノナンジオールの残存濃度1.0質量%、2−メチル−1,8−オクタンジオールの残存濃度3.6質量%)107.9g(0.054mol)、2,2−ジメチロールブタン酸(日本化成株式会社製)32.3g(0.218mol)、PRIPOL2033(ダイマージオール98.2質量%、モノオール0.6質量%、トリマートリオール1.2質量%、水酸基価;205mgKOH/g)107.9g(0.194mol)、トリシクロ[5.2.1.02,6]デカンジメタノール(東京化成工業株式会社製)14.8g(0.075mol)、γ−ブチロラクトン297.0gとジエチレングリコールジエチルエーテル198.0gを仕込み、100℃に加熱してすべての原料を溶解した。反応液の温度を90℃まで下げ、滴下ロートにより、メチレンビス(4−シクロヘキシルイソシアネート)142.1g(0.542mol)を30分かけて滴下した。120℃で9時間反応を行い、ほぼイソシアネートが消失したことを確認した後、イソブタノール(協和発酵ケミカル株式会社製)3.6g(0.049mol)を滴下し、さらに120℃で4時間反応を行い、カルボキシル基及びカーボネート結合を有しかつダイマージオールから誘導される構造単位を有するポリウレタン(以下、ポリウレタン(2)と記す。)を含む溶液を得た。
得られたポリウレタン(2)を含む溶液の粘度は78Pa・sであった。また、ポリウレタン(2)を含む溶液中に含まれるポリウレタン(2)の数平均分子量は13,000であり、ポリウレタン(2)の酸価は40.0mg−KOH/gであった。
また、このポリウレタン(2)を含む溶液中の固形分濃度は45.0質量%であった。 <Synthesis of polyurethane having a carboxyl group and a carbonate bond and having a structural unit derived from dimer diol>
(Execution synthesis example 4)
Synthesis of polyurethane (2) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, C-2015N (Kuraray Co., Ltd. (poly) carbonate diol and raw diol (ie 1,9-nonanediol and 2-methyl- 1,8-octanediol), feed molar ratio of raw material diol; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15: 85, hydroxyl value 56.5 mgKOH / g, 1,9 -Residual concentration of nonanediol of 1.0 mass%, residual concentration of 2-methyl-1,8-octanediol of 3.6 mass%) 107.9 g (0.054 mol), 2,2-dimethylolbutanoic acid (Japan) (Made by Kasei Co., Ltd.) 32.3 g (0.218 mol), PRIPOL 2033 (98.2% by weight of dimer diol, 0.6% by weight of monool) Trimertriol 1.2 mass%, hydroxyl value; 205 mg KOH / g) 107.9 g (0.194 mol), tricyclo [5.2.1.0 2,6 ] decanedimethanol (Tokyo Chemical Industry Co., Ltd.) 14 .8 g (0.075 mol), 297.0 g of γ-butyrolactone and 198.0 g of diethylene glycol diethyl ether were charged and heated to 100 ° C. to dissolve all the raw materials. The temperature of the reaction solution was lowered to 90 ° C., and 142.1 g (0.542 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. Then, a solution containing a polyurethane having a carboxyl group and a carbonate bond and having a structural unit derived from dimer diol (hereinafter referred to as polyurethane (2)) was obtained.
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.
Moreover, the solid content concentration in the solution containing this polyurethane (2) was 45.0% by mass.
ポリウレタン(3)の合成
攪拌装置、温度計およびコンデンサーを備えた反応容器に、C−2015N(株式会社クラレ製(ポリ)カーボネートジオールと原料ジオール(即ち、1,9−ノナンジオール及び2−メチル−1,8−オクタンジオール)の混合物、原料ジオールの仕込みモル比;1,9−ノナンジオール:2−メチル−1,8−オクタンジオール=15:85、水酸基価56.5mgKOH/g、1,9−ノナンジオールの残存濃度1.0質量%、2−メチル−1,8−オクタンジオールの残存濃度3.6質量%)46.7g(0.024mol)、2,2−ジメチロールブタン酸(日本化成株式会社製)32.1g(0.217mol)、PRIPOL2033(ダイマージオール98.2質量%、モノオール0.6質量%、トリマートリオール1.2質量%、水酸基価;205mgKOH/g)116.7g(0.210mol)、UM−90(1/1)(宇部興産株式会社製(ポリ)カーボネートジオールと原料ジオール(即ち、1,6−ヘキサンジオール及びシクロヘキサンジメタノール)の混合物、原料ジオールの仕込みモル比;1,6−ヘキサンジオール:シクロヘキサンジメタノール=1/1、水酸基価122.7mgKOH/g、1,6−ヘキサンジオールの残存濃度3.9質量%、シクロヘキサンジメタノールの残存濃度4.7質量%)70.0g(0.077mol)、γ−ブチロラクトン297.0gとジエチレングリコールジエチルエーテル198.0gを仕込み、100℃に加熱してすべての原料を溶解した。反応液の温度を90℃まで下げ、滴下ロートにより、メチレンビス(4−シクロヘキシルイソシアネート)136.0g(0.518mol)を30分かけて滴下した。120℃で9時間反応を行い、ほぼイソシアネートが消失したことを確認した後、イソブタノール(協和発酵ケミカル株式会社製)3.6g(0.049mol)を滴下し、さらに120℃で4時間反応を行い、カルボキシル基及びカーボネート結合を有しかつダイマージオールから誘導される構造単位を有するポリウレタン(以下、ポリウレタン(3)と記す。)を含む溶液を得た。
得られたポリウレタン(3)を含む溶液の粘度は84Pa・sであった。また、ポリウレタン(3)を含む溶液中に含まれるポリウレタン(3)の数平均分子量は12,000であり、ポリウレタン(3)の酸価は30.0mg−KOH/gであった。
また、このポリウレタン(3)を含む溶液中の固形分濃度は45.0質量%であった。 (Execution synthesis example 5)
Synthesis of polyurethane (3) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, C-2015N (Kuraray Co., Ltd. (poly) carbonate diol and raw diol (ie, 1,9-nonanediol and 2-methyl- 1,8-octanediol), feed molar ratio of raw material diol; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15: 85, hydroxyl value 56.5 mgKOH / g, 1,9 -Residual concentration of nonanediol of 1.0 mass%, residual concentration of 2-methyl-1,8-octanediol of 3.6 mass%) 46.7 g (0.024 mol), 2,2-dimethylolbutanoic acid (Japan) 32.1 g (0.217 mol) manufactured by Kasei Co., Ltd., PRIPOL 2033 (98.2% by weight of dimer diol, 0.6% by weight of monool, Trimer triol 1.2% by mass, hydroxyl value; 205 mg KOH / g) 116.7 g (0.210 mol), UM-90 (1/1) (Ube Industries, Ltd. (poly) carbonate diol and raw diol (ie, 1 , 6-hexanediol and cyclohexanedimethanol), feed molar ratio of raw material diol; 1,6-hexanediol: cyclohexanedimethanol = 1/1, hydroxyl value 122.7 mgKOH / g, 1,6-hexanediol 70.0 g (0.077 mol) of residual concentration 3.9% by mass, residual concentration of cyclohexanedimethanol 4.7% by mass), 297.0 g of γ-butyrolactone and 198.0 g of diethylene glycol diethyl ether were charged and heated to 100 ° C. All the ingredients were dissolved. 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. Then, a solution containing a polyurethane having a carboxyl group and a carbonate bond and having a structural unit derived from dimer diol (hereinafter referred to as polyurethane (3)) was obtained.
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.
Moreover, the solid content concentration in the solution containing this polyurethane (3) was 45.0% by mass.
攪拌装置、温度計およびコンデンサーを備えた反応容器に、C−1015N(株式会社クラレ製(ポリ)カーボネートジオールと原料ジオール(即ち、1,9−ノナンジオール及び2−メチル−1,8−オクタンジオール)の混合物、原料ジオールの仕込みモル比;1,9−ノナンジオール:2−メチル−1,8−オクタンジオール=15:85、水酸基価112.3mgKOH/g、1,9−ノナンジオールの残存濃度2.1質量%、2−メチル−1,8−オクタンジオールの残存濃度9.3質量%)38.6gおよびSovermol(登録商標)908(ダイマージオール、コグニス社製)30.7g、2,2−ジメチロールブタン酸(日本化成株式会社製)12.2g及びγ−ブチロラクトン120.2gを仕込み、100℃に加熱してすべての原料を溶解した。滴下ロートにより、メチレンビス(4−シクロヘキシルイソシアネート)43.5gを5分かけて滴下した。滴下終了後、110℃で7時間反応を行い、ほぼイソシアネートが消失したことを確認した後、イソブタノール(和光純薬工業株式会社製)2.0gを滴下し、さらに120℃にて2時間反応を行い、ポリウレタン(以下、ポリウレタン(4)と記す。)を含む溶液を得た。
また、ポリウレタン(4)を含む溶液中に含まれるポリウレタン(4)の数平均分子量は12,000であり、ポリウレタン(4)の酸価は39.8mg−KOH/gであった。
また、このポリウレタン(4)を含む溶液中の固形分濃度は50.3質量%であった。 (Reference Synthesis Example 3)
In a reaction vessel equipped with a stirrer, a thermometer and a condenser, C-1015N (Kuraray Co., Ltd. (poly) carbonate diol and raw diol (ie 1,9-nonanediol and 2-methyl-1,8-octanediol) ), Molar ratio of raw material diol; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15: 85, hydroxyl value 112.3 mgKOH / g, residual concentration of 1,9-nonanediol 2.1% by mass, 38.6 g of 2-methyl-1,8-octanediol residual concentration of 9.3% by mass) and Sovermol (registered trademark) 908 (dimer diol, manufactured by Cognis) 30.7 g, 2,2 -Charge 12.2 g of dimethylol butanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 120.2 g of γ-butyrolactone and heat to 100 ° C To dissolve all of the raw materials Te. With a dropping funnel, 43.5 g of methylenebis (4-cyclohexylisocyanate) was added dropwise over 5 minutes. After completion of dropping, the reaction was carried out at 110 ° C. for 7 hours. After confirming that the isocyanate had almost disappeared, 2.0 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the reaction was further carried out at 120 ° C. for 2 hours. And a solution containing polyurethane (hereinafter referred to as polyurethane (4)) was obtained.
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.
攪拌装置、温度計およびコンデンサーを備えた反応容器に、C−1015N(株式会社クラレ製(ポリ)カーボネートジオールと原料ジオール(即ち、1,9−ノナンジオール及び2−メチル−1,8−オクタンジオール)の混合物、原料ジオールの仕込みモル比;1,9−ノナンジオール:2−メチル−1,8−オクタンジオール=15:85、水酸基価112.3mgKOH/g、1,9−ノナンジオールの残存濃度2.1質量%、2−メチル−1,8−オクタンジオールの残存濃度9.3質量%)178.1g、ジオクチル錫ジラウレート(日東化成株式会社製 商品名ネオスタンU−810)0.23g、γ−ブチロラクトン191.3g、及びジエチレングリコールジエチルエーテル33.8gを仕込み、80℃に加熱してすべての原料を溶解した。滴下ロートにより、メチレンビス(4−シクロヘキシルイソシアネート)47.0gを5分かけて滴下した。滴下終了後、80℃で4時間反応を行い、ほぼイソシアネートが消失したことを確認した後、イソブタノール(和光純薬工業株式会社製)2.0gを滴下し、さらに80℃にて1時間反応を行い、ポリウレタン(以下、ポリウレタン(5)と記す。)を含む溶液を得た。
また、ポリウレタン(5)を含む溶液中に含まれるポリウレタン(5)の数平均分子量は19,000であり、ポリウレタン(5)の酸価は0mg−KOH/gであった。
また、このポリウレタン(5)を含む溶液中の固形分濃度は50.1質量%であった。 (Reference Synthesis Example 4)
In a reaction vessel equipped with a stirrer, a thermometer and a condenser, C-1015N (Kuraray Co., Ltd. (poly) carbonate diol and raw diol (ie 1,9-nonanediol and 2-methyl-1,8-octanediol) ), Molar ratio of raw material diol; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15: 85, hydroxyl value 112.3 mgKOH / g, residual concentration of 1,9-nonanediol 2.1% by mass, residual concentration of 2-methyl-1,8-octanediol (9.3% by mass) 178.1 g, dioctyltin dilaurate (trade name Neostan U-810 manufactured by Nitto Kasei Co., Ltd.) 0.23 g, γ -191.3 g of butyrolactone and 33.8 g of diethylene glycol diethyl ether were charged and heated to 80 ° C. It was dissolved fee. With a dropping funnel, 47.0 g of methylenebis (4-cyclohexylisocyanate) was added dropwise over 5 minutes. After completion of the dropping, the reaction was carried out at 80 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, 2.0 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the reaction was further carried out at 80 ° C. for 1 hour. And a solution containing polyurethane (hereinafter referred to as polyurethane (5)) was obtained.
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.
ポリウレタンポリイミド(1)を含む溶液に、ポリウレタンポリイミド(1)100質量部に対して、硬化促進剤として1,8−ジアザビシクロ(4.5.0)ウンデセン−7(以下、DBUと記す。)(サンアプロ株式会社製)1質量部を加え、均一に撹拌・混合した。更にシリカ粉(日本アエロジル株式会社製 商品名;アエロジルR972)7質量部、タルク(日本タルク株式会社製 商品名:SG2000)を5質量部加え、まず粗混練し、次いで三本ロールミル(株式会社井上製作所製 型式:S−43/4×11)を用いて、3回混練を繰り返して本混練を行い、均一に混合されたポリウレタンポリイミド(1)を含む組成物(以下、主剤組成物A1と記す。)を得た。
また、撹拌機、温度計およびコンデンサーを備えた容器に、下記式(2)の構造を有するエポキシ樹脂(DIC株式会社製 グレード名;HP−7200H エポキシ当量278g/eq)300g、γ−ブチロラクトン180g及びジエチレングリコールジエチルエーテル120gを添加し、撹拌を開始した。撹拌を継続しながら、オイルバスを用いて、容器内の温度を70℃に昇温した。内温を70℃に昇温後、30分間撹拌を継続した。その後、HP−7200Hが完全に溶解したのを確認して、室温まで冷却し、濃度50質量%のHP−7200H含有溶液(以下、硬化剤溶液B1と記す。)を取得した。
(式中、lは、0または1以上の整数を表す。)
100質量部の主剤組成物A1及び9,65質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名:TSA750S)0.5質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=85:15(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物G1と記す。)を得た。 (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. 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 γ-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. After the internal temperature was raised to 70 ° C., stirring was continued for 30 minutes. Then, it confirmed that HP-7200H melt | dissolved completely, it cooled to room temperature, and the HP-7200H containing solution (henceforth hardening agent solution B1) with a density | concentration of 50 mass% was acquired.
(In the formula, 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. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 85: 15 (mass ratio) necessary for adjusting the thixotropy index to 1.3. , Written as thermosetting composition G1).
ポリウレタンポリイミド(2)を含む溶液に、ポリウレタンポリイミド(2)100質量部に対して、アエロジル380(日本アエロジル株式会社製)7.9質量部及び硬化触媒であるDBU(サンアプロ株式会社製)1質量部を加え、まず粗混練し、次いで三本ロールミル(株式会社井上製作所製 型式:S−43/4×11)を用いて、3回混練を繰り返して本混練を行い、ポリウレタンポリイミド(2)を含む組成物(以下、主剤組成物A2と記す。)を得た。
100質量部の主剤組成物A2に対して、20質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名:TSA750S)0.5質量部を加え、γ−ブチロラクトン:ジエチレングリコールジエチルエーテル=85:15(質量比)で希釈して、粘度35Pa・s、チクソトロピー指数2.2、不揮発分40質量%のポリウレタンポリイミド(2)を含む熱硬化性組成物(以下、熱硬化性組成物G2と記す。)を得た。 (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. A composition containing the composition (hereinafter referred to as main agent composition A2) was obtained.
To 100 parts by mass of the main agent composition A2, 20 parts by mass of 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 γ-butyrolactone: A thermosetting composition diluted with diethylene glycol diethyl ether = 85: 15 (mass ratio) and containing polyurethane polyimide (2) having a viscosity of 35 Pa · s, a thixotropy index of 2.2, and a nonvolatile content of 40% by mass (hereinafter, thermosetting) To be referred to as sex composition G2.).
前記のポリウレタン(1)を含む溶液111.1質量部、シリカ粉(日本アエロジル株式会社製 商品名;アエロジルR974)5.0質量部、硬化促進剤としてメラミン(日産化学工業株式会社製)0.36質量部を混合し、三本ロールミル(株式会社井上製作所製 型式:S−43/4×11)を用いて、3回混練を繰り返して本混練を行い、ポリウレタン(1)を含む組成物(以下、主剤組成物A3と記す。)を得た。
100質量部の主剤組成物A3に対して、22.7質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名;TSA750S)0.60質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=85:15(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物G3と記す。)を得た。 (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).
22.7 parts by mass of the curing agent solution B1 and 0.60 parts by mass of the antifoaming agent (trade name; TSA750S manufactured by Momentive Performance Materials) are mixed with 100 parts by mass of the main agent composition A3, and the spatula is mixed. Was thoroughly stirred and mixed. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 85: 15 (mass ratio) necessary for adjusting the thixotropy index to 1.3. , Written as thermosetting composition G3).
前記のポリウレタン(2)を含む溶液111.1質量部、シリカ粉(日本アエロジル株式会社製 商品名;アエロジルR974)5.0質量部、硬化促進剤としてメラミン(日産化学工業株式会社製)0.36質量部を混合し、三本ロールミル(株式会社井上製作所製 型式:S−43/4×11)を用いて、3回混練を繰り返して本混練を行い、ポリウレタン(2)を含む組成物(以下、主剤組成物A4と記す。)を得た。
100質量部の主剤組成物A4に対して、25.5質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名;TSA750S)0.60質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=60:40(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物G4と記す。)を得た。 (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).
100 parts by mass of main agent composition A4 is mixed with 25.5 parts by mass of curing agent solution B1 and 0.60 parts by mass of antifoaming agent (trade name; TSA750S, manufactured by Momentive Performance Materials), and spatula Was thoroughly stirred and mixed. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 60: 40 (mass ratio) necessary for adjusting the thixotropy index to 1.3. , Written as thermosetting composition G4).
前記のポリウレタン(3)を含む溶液111.1質量部、シリカ粉(日本アエロジル株式会社製 商品名;アエロジルR974)5.0質量部、硬化促進剤としてメラミン(日産化学工業株式会社製)0.36質量部を混合し、三本ロールミル(株式会社井上製作所製 型式:S−43/4×11)を用いて、3回混練を繰り返して本混練を行い、ポリウレタン(3)を含む組成物(以下、主剤組成物A5と記す。)を得た。
100質量部の主剤組成物A5に対して、19.1質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名;TSA750S)0.60質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=60:40(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物G5と記す。)を得た。 (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).
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. Was thoroughly stirred and mixed. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 60: 40 (mass ratio) necessary for adjusting the thixotropy index to 1.3, and a thermosetting composition (hereinafter referred to as a thermosetting composition). , Written as thermosetting composition G5).
100質量部の主剤組成物A3に対して、30.3質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名;TSA750S)0.60質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=85:15(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物G6と記す。)を得た。 (Example of formulation 6)
A spatula is mixed with 30.3 parts by mass of a curing agent solution B1 and an antifoaming agent (trade name; TSA750S, manufactured by Momentive Performance Materials) of 100 parts by mass of the main agent composition A3. Was thoroughly stirred and mixed. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 85: 15 (mass ratio) necessary for adjusting the thixotropy index to 1.3. , Written as thermosetting composition G6).
100質量部の主剤組成物A4に対して、34.0質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名;TSA750S)0.60質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=60:40(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物G7と記す。)を得た。 (Example formulation 7)
A spatula is mixed with 34.0 parts by mass of the curing agent solution B1 and an antifoaming agent (trade name; TSA750S, manufactured by Momentive Performance Materials) with respect to 100 parts by mass of the main agent composition A4. Was thoroughly stirred and mixed. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 60: 40 (mass ratio) necessary for adjusting the thixotropy index to 1.3. , Written as thermosetting composition G7).
100質量部の主剤組成物A5に対して、25.5質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名;TSA750S)0.60質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=60:40(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物G8と記す。)を得た。 (Example of formulation 8)
A spatula is mixed with 25.5 parts by mass of the curing agent solution B1 and an antifoaming agent (trade name; TSA750S, manufactured by Momentive Performance Materials) with respect to 100 parts by mass of the main agent composition A5. Was thoroughly stirred and mixed. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 60: 40 (mass ratio) necessary for adjusting the thixotropy index to 1.3. , Written as thermosetting composition G8).
100質量部の主剤組成物A1に対して、セロキサイド2021P(ダイセル化学工業株式会社製、(3′,4′−エポキシシクロヘキサン)メチル−3,4−エポキシシクロヘキサンカルボキシレート、エポキシ当量126g/eq)4.2質量部及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名:TSA750S)0.5質量部を前記のポリウレタンポリイミド(1)を含む組成物に均一に混合し、ポリウレタンポリイミド(1)を含む熱硬化性組成物(以下、熱硬化性組成物H1と記す。)を得た。 (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.
100質量部の主剤組成物A2に対して、YH−434(東都化成株式会社製 アミン型エポキシ樹脂の商品名、エポキシ当量120g/eq)10質量部及びTSA750S(モメンティブ・パフォーマンス・マテリアルズ社製の消泡剤の商品名)0.5質量部を加え、γ−ブチロラクトンで希釈して、粘度35Pa・s、チクソトロピー指数2.4、不揮発分40質量%のポリウレタンポリイミド(2)を含む熱硬化性組成物(以下、熱硬化性組成物H2と記す。)を得た。 (Comparative Formulation Example 2)
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 γ-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.
撹拌機およびコンデンサーを備えた容器に、jER828EL(ジャパンエポキシレジン株式会社製 ビスフェノールA型エポキシ樹脂 エポキシ当量190g/eq)300質量部、ジエチレングリコールモノエチルエーテルアセテート300質量部を添加し、撹拌を開始した。撹拌を1時間を継続した。その後、jER828ELが完全に溶解したのを確認して、濃度50質量%のjER828EL含有溶液を取得した。この溶液を硬化剤溶液B2とする。
前記のポリウレタン(4)を含む溶液111.1質量部、シリカ粉(日本アエロジル株式会社製 商品名;アエロジルR974)5.0質量部、硬化促進剤としてメラミン(日産化学工業株式会社製)0.36質量部を混合し、三本ロールミル(株式会社井上製作所製 型式:S−43/4×11)を用いて、3回混練を繰り返して本混練を行い、ポリウレタン(4)を含む組成物(以下、主剤組成物A6と記す。)を得た。
100質量部の主剤組成物A6に対して、14.2質量部の硬化剤溶液B2及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名;TSA750S)0.60質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールモノエチルエーテルアセテート=1:1(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物H3と記す。)を得た。 (Comparative Formulation Example 3)
To a container equipped with a stirrer and a condenser, 300 parts by mass of jER828EL (Bisphenol A type epoxy resin, epoxy equivalent 190 g / eq, manufactured by Japan Epoxy Resin Co., Ltd.) and 300 parts by mass of diethylene glycol monoethyl ether acetate were added, and stirring was started. Stirring was continued for 1 hour. Thereafter, it was confirmed that jER828EL was completely dissolved, and a jER828EL-containing solution having a concentration of 50% by mass was obtained. This solution is designated as a curing agent solution B2.
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).
To 100 parts by mass of the main agent composition A6, 14.2 parts by mass of the curing agent solution B2 and 0.60 parts by mass of an antifoaming agent (product name: TSA750S manufactured by Momentive Performance Materials) are mixed, and a spatula Was thoroughly stirred and mixed. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol monoethyl ether acetate = 1: 1 (mass ratio) necessary for adjusting the thixotropy index to 1.3, and the thermosetting composition. (Hereinafter referred to as thermosetting composition H3).
前記のポリウレタン(5)を含む溶液88.9質量部、シリカ粉(日本アエロジル株式会社製 商品名;アエロジルR974)5.0質量部、硬化促進剤としてメラミン(日産化学工業株式会社製)0.36質量部を混合し、三本ロールミル(株式会社井上製作所製 型式:S−43/4×11)を用いて、3回混練を繰り返して本混練を行い、ポリウレタン(5)を含む組成物(以下、主剤組成物A7と記す。)を得た。
80.9質量部の主剤組成物A7に対して、22.7質量部の硬化剤溶液B1及び消泡剤(モメンティブ・パフォーマンス・マテリアルズ社製 商品名;TSA750S)0.60質量部を混合し、スパチュラを用いて、十分に撹拌混合した。その後、チクソトロピー指数を1.3に合わせるのに必要量のγ−ブチロラクトン:ジエチレングリコールジエチルエーテル=85:15(質量比)の混合溶媒を添加して、粘度調整を行い、熱硬化性組成物(以下、熱硬化性組成物H4と記す。)を得た。 (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).
82.7 parts by mass of the main agent composition A7 is mixed with 22.7 parts by mass of the curing agent solution B1 and 0.60 parts by mass of the defoaming agent (trade name; TSA750S manufactured by Momentive Performance Materials). The mixture was thoroughly stirred using a spatula. Thereafter, a viscosity adjustment is performed by adding a mixed solvent of γ-butyrolactone: diethylene glycol diethyl ether = 85: 15 (mass ratio) necessary for adjusting the thixotropy index to 1.3. , Referred to as thermosetting composition H4).
表1に記したように、それぞれ熱硬化性組成物G1~熱硬化性組成物G8、熱硬化性組成物H1~熱硬化性組成物H4を用いて、後述の方法により、ポリイミド及び錫メッキ処理を施した銅への密着性の評価、反り性の評価及び長期電気絶縁信頼性の評価を行った。その結果を表1に記す。 (Examples 1-8, Comparative Examples 1-3)
As described in Table 1, polyimide and tin plating treatments were performed by the methods described later using thermosetting composition G1 to thermosetting composition G8 and thermosetting composition H1 to 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.
フレキシブル銅張り積層板(住友金属鉱山株式会社製 グレード名;エスパーフレックス 銅厚;8μm、ポリイミド厚;38μm)に錫メッキを施した基板及びポリイミドフィルム〔カプトン(登録商標)300H、東レ・デュポン株式会社製〕に、熱硬化性組成物G1を、スクリーン印刷法により、熱硬化性組成物の厚みが15μmの厚さ(乾燥後の厚さ)になるように塗布し、80℃の熱風循環式乾燥機に30分間入れ、その後、120℃の熱風循環式乾燥機に120分間入れることにより硬化させた。この硬化塗膜に、1mm間隔で100個の格子状パターンを切込み、約75mmの長さに切ったテープを格子の部分に接着し、剥離用テープ(JIS Z 1522に規定する物)を60°に近い角度で0.5~1.0秒の時間で引きはがした。
なお、剥離用テープは日東電工株式会社製を用いて、下記の基準で評価した。
○:碁盤目の数が80個以上残る場合、
△:碁盤目の数が50個以上80個未満残る場合、
×:碁盤目の数が50個未満しか残らない場合。
結果を表1に記す。
また、熱硬化性組成物G2~熱硬化性組成物G8、熱硬化性組成物H1~熱硬化性組成物H4を用いて、同様の評価を行った。
それらの結果もあわせて表1に記す。 Evaluation of adhesion to polyimide and tin-plated copper Flexible copper-clad laminate (grade name; Esperflex copper thickness: 8 μm, polyimide thickness; 38 μm, manufactured by Sumitomo Metal Mining Co., Ltd.) 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 μm (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. In this cured coating film, 100 grid patterns were cut at 1 mm intervals, a tape cut to a length of about 75 mm was bonded to the grid portion, and a peeling tape (thing specified in JIS Z 1522) was 60 °. It was peeled off at an angle near 0.5 to 0.5 to 1.0 seconds.
In addition, the peeling tape evaluated by the following reference | standard using the product made from Nitto Denko Corporation.
○: When 80 or more grids remain,
△: When the number of grids is 50 or more and less than 80,
×: When the number of grids remains less than 50.
The results are shown in Table 1.
In addition, 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.
熱硬化性組成物G1を、基板にスクリーン印刷により塗布し、80℃の熱風循環式乾燥機に30分間入れ、その後、120℃の熱風循環式乾燥機に60分間入れることにより硬化させた。基板は38μm厚ポリイミドフィルム〔カプトン(登録商標)150EN、東レ・デュポン株式会社製〕を用いた。
熱硬化性組成物を塗布し、乾燥機を用いて硬化した塗膜について、50mmφにサークルカッターでカットした。円形にカットされたものは中心付近が凸状または凹状に反る形の変形を呈する。試験片を、温度23±0.5℃、湿度60±5%RHの条件で12時間以上放置した後に、下に凸の状態で静置し、平面上から最も大きく反っている箇所と、円の中心を挟んで対称となる箇所の2箇所に関して、平面上からの反りの高さを、長さ計を用いて測定し、平均した。符号は反りの方向を表し、下に凸の状態で静置した際、ポリイミドフィルムに対し硬化膜が上側になる場合を「+」、硬化膜が下側になる場合を「−」とした。
結果を表1に記す。
また、熱硬化性組成物G2~熱硬化性組成物G8、熱硬化性組成物H1~熱硬化性組成物H4を用いて、同様の評価を行った。
それらの結果もあわせて表1に記す。 Evaluation of warpage The 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 μm-thick polyimide film [Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.] was used as the substrate.
About the coating film which apply | coated the thermosetting composition and hardened | cured using the dryer, it cut with a circle cutter to 50 mmphi. What is cut into a circle exhibits a deformation in which the vicinity of the center warps in a convex or concave shape. 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 “−”.
The results are shown in Table 1.
In addition, 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.
フレキシブル銅張り積層板(住友金属鉱山株式会社製 グレード名;エスパーフレックス 銅厚;8μm、ポリイミド厚;38μm)の銅上に、幅75mm、長さ110mmの大きさ、硬化後の塗膜の厚み15μmになるように熱硬化性組成物G1を、クリーン印刷により塗布し、10分間室温で保持し、120℃の熱風循環式乾燥機に60分間入れることにより硬化させた。作製した試験片の裏打ちのPETフィルムを剥離し、幅10mmの短冊状にカッターナイフで切り出した後、塗膜面が外側になる様に約180度折り曲げ、圧縮機を用いて0.5±0.2MPaで3秒間圧縮した。屈曲部を曲げた状態で30倍の顕微鏡で観察し、クラックの発生の有無を確認した。
結果を表1に記す。
また、熱硬化性組成物G2~熱硬化性組成物G8、熱硬化性組成物H1~熱硬化性組成物H4を用いて、同様の評価を行った。
それらの結果もあわせて表1に記す。 Evaluation of flexibility Flexible copper-clad laminate (manufactured by Sumitomo Metal Mining Co., Ltd. grade name: Esperflex copper thickness: 8 μm, polyimide thickness: 38 μm) on copper of 75 mm width and 110 mm length, after curing The thermosetting composition G1 was applied by clean printing so that the thickness of the coating film was 15 μm, 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. 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.
In addition, 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.
フレキシブル銅張り積層板(住友金属鉱山株式会社製 グレード名;エスパーフレックス 銅厚;8μm、ポリイミド厚:38μm)をエッチングして製造した、JPCA−ET01に記載の微細くし形パターン形状の基板(銅配線幅/銅配線間幅=15μm/15μm)に錫メッキ処理を施したフレキシブル配線板に、熱硬化性組成物G1を、スクリーン印刷法により、ポリイミド面からの厚みが15μmの厚さ(乾燥後)になるように塗布し、80℃の熱風循環式乾燥機に30分間入れ、その後、120℃の熱風循環式乾燥機に120分間いれることにより硬化させた。
この試験片を用いて、バイアス電圧60Vを印加し、温度120℃、湿度85%RHの条件での温湿度定常試験を、MIGRATION TESTER MODEL MIG−8600(IMV社製)を用いて行った。上記温湿度定常試験をスタートしてから1時間、100時間後、200時間後、300時間後、400時間後の抵抗値を表1に記す。
また、熱硬化性組成物G2~熱硬化性組成物G8、熱硬化性組成物H1~熱硬化性組成物H4を用いて、同様の評価を行った。
それらの結果についてもあわせて表1に記す。 Long-term electrical insulation reliability evaluation (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 μm, polyimide thickness: 38 μm) Width / width between copper wirings = 15 μm / 15 μm) A thickness of 15 μm from the polyimide surface after drying the thermosetting composition G1 by screen printing on a flexible wiring board subjected to tin plating (after drying) Then, it was placed in a hot air circulating dryer at 80 ° C. for 30 minutes, and then cured by placing it in a 120 ° C. hot air circulating dryer for 120 minutes.
Using this test piece, a bias voltage of 60 V was applied, and a constant temperature and humidity test under the conditions of a temperature of 120 ° C. and a humidity of 85% RH was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV). Table 1 shows resistance values at 1 hour, 100 hours, 200 hours, 300 hours, and 400 hours after starting the temperature and humidity steady state test.
In addition, 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.
フレキシブル銅張り積層板(住友金属鉱山株式会社製 グレード名;エスパーフレックス 銅厚;8μm、ポリイミド厚:38μm)をエッチングして製造した、JPCA−ET01に記載の微細くし形パターン形状の基板(銅配線幅/銅配線間幅=15μm/15μm)に錫メッキ処理を施したフレキシブル配線板に、熱硬化性組成物G1を、スクリーン印刷法により、ポリイミド面からの厚みが15μmの厚さ(乾燥後)になるように塗布し、80℃の熱風循環式乾燥機に30分間入れ、その後、120℃の熱風循環式乾燥機に120分間いれることにより硬化させた。
この試験片を用いて、バイアス電圧60Vを印加し、温度85℃、湿度85%RHの条件での温湿度定常試験を、MIGRATION TESTER MODEL MIG−8600(IMV社製)を用いて行った。上記温湿度定常試験をスタート初期及びスタートしてから10時間後、500時間後、1000時間後、2000時間後の抵抗値を表1に記す。
また、熱硬化性組成物G2~熱硬化性組成物G8、熱硬化性組成物H1~熱硬化性組成物H4を用いて、同様の評価を行った。
それらの結果についてもあわせて表1に記す。 Long-term electrical insulation reliability evaluation (2)
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 μm, polyimide thickness: 38 μm) Width / width between copper wirings = 15 μm / 15 μm) A thickness of 15 μm from the polyimide surface after drying the thermosetting composition G1 by screen printing on a flexible wiring board subjected to tin plating (after drying) Then, it was placed in a hot air circulating dryer at 80 ° C. for 30 minutes, and then cured by placing it in a 120 ° C. hot air circulating dryer for 120 minutes.
Using this test piece, a bias voltage of 60 V was applied, and a temperature and humidity steady test under conditions of a temperature of 85 ° C. and a humidity of 85% RH was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV). Table 1 shows the resistance values after 10 hours, 500 hours, 1000 hours, and 2000 hours after the start of the temperature and humidity steady test.
In addition, 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.
Claims (15)
- トリシクロデカン構造を有するエポキシ基含有化合物、エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有するポリウレタン及び溶剤を必須成分とする配線板の保護膜用熱硬化性組成物。
(式中、R1は、炭素数3~18のアルキレン基を表し、nは1以上の整数を表す。) Thermosetting for protective film of wiring board having epoxy group-containing compound having tricyclodecane structure, polyurethane having functional group capable of reacting with epoxy group and having structural unit represented by formula (1) and solvent as essential components Sex composition.
(In the formula, R 1 represents an alkylene group having 3 to 18 carbon atoms, and n represents an integer of 1 or more.) - トリシクロデカン構造を有するエポキシ基含有化合物が、トリシクロ[5.2.1.02,6]デカン構造またはトリシクロ[3.3.1.13,7]デカン構造を有し、かつ芳香環構造を有するエポキシ基含有化合物であることを特徴とする請求項1に記載の配線板の保護膜用熱硬化性組成物。 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, and an aromatic ring The thermosetting composition for a protective film for a wiring board according to claim 1, which is an epoxy group-containing compound having a structure.
- トリシクロデカン構造を有するエポキシ基含有化合物が、式(2)で示される化合物であることを特徴とする請求項2に記載の配線板の保護膜用熱硬化性組成物。
(式中、lは、0または1以上の整数を表す。) The thermosetting composition for a protective film of a wiring board according to claim 2, wherein the epoxy group-containing compound having a tricyclodecane structure is a compound represented by the formula (2).
(In the formula, l represents 0 or an integer of 1 or more.) - エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有するポリウレタンが、エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有し、さらにイミド結合を有するポリウレタンポリイミドであることを特徴とする請求項1~3のいずれか1項に記載の配線板の保護膜用熱硬化性組成物。 The polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by formula (1) has a functional group capable of reacting with an epoxy group and having a structural unit represented by formula (1). The thermosetting composition for a protective film for a wiring board according to any one of claims 1 to 3, which is a polyurethane polyimide further having an imide bond.
- エポキシ基と反応可能な官能基が、カルボキシル基であることを特徴とする請求項1~4のいずれか1項に記載の配線板の保護膜用熱硬化性組成物。 The thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 4, wherein the functional group capable of reacting with an epoxy group is a carboxyl group.
- エポキシ基と反応可能な官能基が、酸無水物基であることを特徴とする請求項1~4のいずれか1項に記載の配線板の保護膜用熱硬化性組成物。 The thermosetting composition for a protective film for a wiring board according to any one of claims 1 to 4, wherein the functional group capable of reacting with an epoxy group is an acid anhydride group.
- エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有し、さらにイミド結合を有するポリウレタンポリイミドが、下記成分(a)~成分(d)を反応して得られるポリウレタンポリイミドであることを特徴とする請求項4または5に記載の配線板の保護膜用熱硬化性組成物。
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c) カルボキシル基を有するジオール、および
成分(d) 式(3)で示される2官能性水酸基末端イミド。
(式中、R2、R3は、それぞれ独立に、2価の脂肪族または芳香族炭化水素基を示し、Y1はテトラカルボン酸またはその酸無水物基から誘導される4価の有機基を示し、X1はジアミン或いはジイソシアネートから誘導される2価の有機基を示し、mは、0~20の整数である。) 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 is obtained by reacting the following components (a) to (d): The thermosetting composition for a protective film of a wiring board according to claim 4, which is a polyurethane polyimide.
Component (a) diisocyanate,
Component (b) (poly) carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms,
Component (c) Diol having a carboxyl group, and Component (d) A bifunctional hydroxyl-terminated imide represented by the formula (3).
Wherein R 2 and R 3 each independently represents a divalent aliphatic or aromatic hydrocarbon group, and 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.) - エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有し、さらにイミド結合を有するポリウレタンポリイミドが、式(4)~式(6)からなる群より選ばれる少なくとも1種の構造単位を有するポリウレタンポリイミドであることを特徴とする請求項4または6に記載の配線板の保護膜用熱硬化性組成物。
式中、複数個のR4は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR5は、それぞれ独立に炭素数3~18のアルキレン基であり、a及びbは、それぞれ独立に1~20の整数であり、複数個のX2は、それぞれ独立に2価の有機基である。
式中、複数個のR6は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR7は、それぞれ独立に炭素数3~18アルキレン基であり、c及びdは、それぞれ独立に1~20の整数であり、複数個のX3は、それぞれ独立に2価の有機基であり、Y2は、CH2、SO2またはOである。
式中、複数個のR8は、それぞれ独立に炭素数3~18のアルキレン基であり、複数個のR9は、それぞれ独立に炭素数3~18のアルキレン基であり、e及びfは、それぞれ独立に1~20の整数であり、複数個のX4は、それぞれ独立に2価の有機基であり、Y3は、下記式(7)~式(33)のいずれかの基である。
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 is selected from the group consisting of the formulas (4) to (6): The thermosetting composition for a protective film of a wiring board according to claim 4, wherein the thermosetting composition is a polyurethane polyimide having one type of structural unit.
In the formula, 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, and a and b are Each independently represents an integer of 1 to 20, and the plurality of X 2 are each independently a divalent organic group.
In the formula, 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, and c and d are each 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;
In the formula, 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, and e and f are: Each independently represents an integer of 1 to 20, a plurality of X 4 are each independently a divalent organic group, and Y 3 is any one of the following formulas (7) to (33): .
- エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有するポリウレタンが、下記成分(a)、成分(b)、成分(c)及び成分(e)を反応して得られるポリウレタンであることを特徴とする請求項1~3のいずれか1項に記載の配線板の保護膜用熱硬化性組成物。
成分(a) ジイソシアネート、
成分(b) 炭素数3~18のジオールから誘導される有機残基を有する(ポリ)カーボネートポリオール、
成分(c) カルボキシル基を有するジオール、
成分(e) 1分子中に水酸基を3個以上有する化合物。 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 the following components (a), (b), (c) and (e): The thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 3, which is a polyurethane obtained.
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. - エポキシ基と反応可能な官能基を有しかつ式(1)で示される構造単位を有するポリウレタンが、さらに、ダイマージオールから誘導された有機残基を含有するポリウレタンであることを特徴とする請求項1~3、5、6及び9のいずれか1項に記載の配線板の保護膜用熱硬化性組成物。 The polyurethane having a functional group capable of reacting with an epoxy group and having a structural unit represented by the formula (1) is a polyurethane further containing an organic residue derived from a dimer diol. The thermosetting composition for a protective film for a wiring board according to any one of 1 to 3, 5, 6, and 9.
- 溶剤が、大気圧下で170℃以上200℃未満の沸点を有する少なくとも1種の溶剤と大気圧下で200℃~220℃の沸点を有する少なくとも1種の溶剤を含む混合溶剤であることを特徴とする請求項1~10のいずれか1項に記載の配線板の保護膜用熱硬化性組成物。 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 thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 10.
- 大気圧下で170℃以上200℃未満の沸点を有する溶剤が下記A群の中から選ばれる少なくとも1種であり、かつ大気圧下で200℃~220℃の沸点を有する溶剤が下記B群の中から選ばれる少なくとも1種であることを特徴とする請求項11に記載の配線板の保護膜用熱硬化性組成物。
A群:ジエチレングリコールジメチルエーテル(沸点162℃)、ジエチレングリコールジエチルエーテル(沸点189℃)、ジエチレングリコールエチルメチルエーテル(沸点176℃)、ジプロピレングリコ−ルジメチルエーテル(沸点171℃)、3−メトキシブチルアセテート(沸点171℃)、エチレングリコールモノブチルエーテルアセテート(沸点192℃)
B群:ジエチレングリコールブチルメチルエーテル(沸点212℃)、トリプロピレングリコールジメチルエーテル(沸点215℃)、トリエチレングリコールジメチルエーテル(沸点216℃)、エチレングリコールジブチルエーテル(沸点203℃)、ジエチレングリコールモノエチルエーテルアセテート(沸点217℃)、γ−ブチロラクトン(沸点204℃)。 The solvent having a boiling point of 170 ° C. or more and less than 200 ° C. under atmospheric pressure is at least one selected from the following group A, and the solvent having a boiling point of 200 ° C. to 220 ° C. under atmospheric pressure is the following group B: It is at least 1 sort (s) chosen from the inside, The thermosetting composition for protective films of the wiring board of Claim 11 characterized by the above-mentioned.
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 (boiling point) 217 ° C.), γ-butyrolactone (boiling point 204 ° C.). - 請求項1~12のいずれか1項に記載の配線板の保護膜用熱硬化性組成物を硬化して得られる配線板の保護膜。 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 claims 1 to 12.
- フレキシブル基板上に配線が形成されてなるフレキシブル配線板の、配線が形成されている表面の一部または全部が請求項13に記載の配線板の保護膜によって被覆されたことを特徴とする、保護膜によって被覆されたフレキシブル配線板。 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 claim 13. A flexible wiring board covered with a film.
- 請求項1~12のいずれか1項に記載の配線板の保護膜用熱硬化性組成物をフレキシブル配線板の錫メッキ処理された配線パターン部に印刷することで該パターン上に印刷膜を形成し、該印刷膜を80~130℃で加熱硬化させることで保護膜を形成することを特徴とする、保護膜によって被覆されたフレキシブル配線板の製造方法。 A printed film is formed on the pattern by printing the thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 12 on a wiring pattern portion subjected to a tin plating treatment of a flexible wiring board. A method for producing a flexible wiring board covered with a protective film, wherein the printed film is heated and cured at 80 to 130 ° C. to form a protective film.
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