WO2011096295A1 - 熱硬化性組成物 - Google Patents
熱硬化性組成物 Download PDFInfo
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- WO2011096295A1 WO2011096295A1 PCT/JP2011/051267 JP2011051267W WO2011096295A1 WO 2011096295 A1 WO2011096295 A1 WO 2011096295A1 JP 2011051267 W JP2011051267 W JP 2011051267W WO 2011096295 A1 WO2011096295 A1 WO 2011096295A1
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- thermosetting composition
- polyurethane
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- wiring board
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
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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
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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
- 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
- C08G59/40—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 curing agents used
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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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0212—Resin particles
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0227—Insulating particles having an insulating coating
Definitions
- the present invention relates to the following.
- Thermosetting composition capable of forming an insulating film (cured product) that suppresses disconnection of the flexible wiring board
- Cured product obtained by thermosetting the composition (3)
- Wiring with the cured product Flexible wiring board (4) in which at least a part of the pattern forming surface is coated.
- a method for manufacturing such a flexible wiring board is described.
- Patent Document 1 Japanese Patent Laid-Open No. 2003-198105
- Wiring breakage occurs due to repeated bending and vibration of the flexible wiring board.
- the strength of the wiring itself has no significant effect on whether or not disconnection occurs.
- the wiring width is narrowed to 20 ⁇ m or less, and there is a problem that the wiring itself is not strong and disconnection occurs. Therefore, there is a demand for a resist ink that can form a protective film that can effectively suppress the disconnection of the wiring.
- the protective film is required to have electrical insulation to prevent malfunction of the flexible wiring board.
- Patent Document 2 Japanese Patent Laid-Open No. 2002-185110
- the low warpage of the flexible wiring board (this is determined by the balance between the hardness of the wiring board and the flexibility of the protective film, the thickness of each other, etc.
- a technique for improving the balance of folding resistance a technique disclosed in Japanese Patent Application Laid-Open No. 2007-279489 (Patent Document 3) can be given.
- the technique is a method of using a curable composition capable of forming a cured product having a tensile modulus of 0.5 to 1.5 GPa.
- the curable composition is a photosensitive resin composition that requires a photoinitiator. In the case of a photosensitive composition, an exposure process is essential to form a protective film, and therefore the process for producing a flexible wiring board having a protective film becomes complicated.
- the flexible wiring board may impair electrical insulation.
- the distance between wirings of the flexible wiring board is expected to become even narrower (for example, 20 ⁇ m pitch or less). Therefore, development of a resist ink (curable composition) that can suppress the disconnection of the wiring board as described above and can form a flexible cured film has been demanded.
- a curable composition containing a compound having an epoxy group that causes a curing reaction for example, an epoxy resin
- a compound having a functional group that reacts with the epoxy group is used for the resist.
- a polyurethane having such a functional group and a carbonate bond a polyurethane having an acid anhydride group and / or an isocyanate group and a carbonate bond is disclosed in JP-A-2003-198105 (Patent Document 1). And the compounds disclosed in.
- An object of the present invention is to provide a thermosetting composition capable of forming an insulating film (cured product) having an effect of suppressing disconnection of wiring of a flexible wiring board.
- an object of the present invention is to provide a thermosetting composition that is excellent in low warpage and long-term electrical insulation reliability and that can form an insulating film that suppresses disconnection of wiring of a flexible wiring board.
- thermosetting composition capable of forming a cured product having a tensile elastic modulus in a specific range
- the present invention has been completed.
- (2) The warp of the flexible wiring board when the thermosetting composition is cured is small.
- the obtained insulating film (cured product) is excellent in long-term electrical insulation characteristics.
- the present invention (I) is a thermosetting composition for forming an insulating film on a flexible wiring board in which a wiring pattern is formed on a flexible substrate by curing the composition.
- the thermosetting composition is characterized in that the cured product obtained by curing is a tensile elastic modulus of 0.5 to 2.0 GPa.
- the present invention (II) is a cured product obtained by thermosetting the thermosetting composition of the present invention (I).
- the present invention (III) is a method of applying the thermosetting composition of the present invention (I) onto a wiring pattern of a flexible wiring board having a wiring pattern formed on a flexible substrate by a printing method.
- a method for producing a flexible wiring board having an insulating film comprising: forming a printed film on a pattern and heat-curing the printed film to form an insulating film from the printed film.
- the present invention relates to the following matters.
- thermosetting composition for forming an insulating film on a flexible wiring board in which a wiring pattern is formed on a flexible substrate by curing, and is obtained by curing the composition
- a thermosetting composition wherein the cured product has a tensile modulus of 0.5 to 2.0 GPa.
- thermosetting composition according to [1] wherein a wiring width of the flexible wiring board is 20 ⁇ m or less.
- thermosetting composition comprises two or more polyurethanes (a) having a functional group reactive with an epoxy group and a carbonate bond, inorganic fine particles and / or organic fine particles (b) in one molecule.
- the functional group having reactivity with the epoxy group in the polyurethane (a) is at least one functional group selected from the group consisting of a carboxyl group, an isocyanate group, a hydroxyl group, and a cyclic acid anhydride group.
- thermosetting composition according to [3] or [4], wherein the compound (c) has an aromatic ring structure and / or an alicyclic structure.
- thermosetting composition obtained by thermosetting the thermosetting composition according to any one of [1] to [6].
- thermosetting composition according to any one of [1] to [6] onto a wiring pattern of a flexible wiring board having a wiring pattern formed on a flexible substrate by a printing method. Then, a printed film is formed on the pattern,
- a method for producing a flexible wiring board having an insulating film comprising: a step of forming the insulating film from the printed film by heating and curing the printed film at 80 to 130 ° C.
- thermosetting composition when the thermosetting composition is cured, the warp of the flexible wiring board on which the composition is printed is small, and an insulating film (cured product) obtained by curing the thermosetting composition Has excellent long-term electrical insulation properties.
- the present invention (I) is a thermosetting composition characterized in that the cured product has a tensile elastic modulus of 0.5 to 2.0 GPa, and the composition is cured to form a flexible wiring. Used to form an insulating film on the plate. In particular, when the insulating film is formed on a flexible wiring board having a wiring width of 20 ⁇ m or less, which is likely to cause disconnection of the wiring, the effect is remarkably achieved by using the thermosetting composition of the present invention (I).
- thermosetting component examples include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, and thermosetting polyimide. Two or more of these may be used in combination, and from such a single resin or a resin mixture obtained by combining a plurality of resins, those whose tensile modulus of cured product is 0.5 to 2.0 GPa Appropriate selection can be applied to the present invention.
- thermosetting composition of this invention may contain the other component mentioned later other than the said thermosetting component. Even in that case, a combination in which the tensile elastic modulus of the cured product obtained by curing the thermosetting composition falls within the above range is appropriately selected.
- the tensile modulus of the cured product is obtained by cutting the cured product into strips having a width of 10 mm and a length of 60 mm, a tensile tester (for example, a distance between chucks of 30 mm and a pulling speed of 5 mm / min at 25 ° C.
- Equipment A numerical value obtained by evaluation using a small desktop testing machine (EZGraph) manufactured by Shimadzu Corporation.
- the present inventor examined the tensile modulus of cured products obtained from various thermosetting compositions.
- the tensile modulus was 0.5 to 2.0 GPa
- the cured product was used as the wiring of a flexible wiring board. It has been found that by using it as an insulating film, the disconnection of the wiring is suppressed and the warp when the thermosetting composition is cured is sufficiently small.
- the flexible wiring board is made of a substrate material, metal wiring, and a cured product such as a solder resist. When there is no cured product, the metal wiring is exposed on the wiring board, and when a bending load is applied to the wiring board, the wiring may crack and lead to disconnection.
- the tensile modulus of the cured product is less than 0.5 GPa, even when the cured product is used as an insulating film (protective film) for metal wiring, when a bending load is applied to the flexible wiring board, Cracks in the wiring lead to disconnection. This is because the cured product is soft and the cured product does not have the ability to protect metal wiring.
- the metal wiring protecting ability of the cured product is increased, and even when a bending load is applied, cracks are hardly generated in the wiring.
- the tensile modulus of the cured product exceeds 2.0 GPa, although there is a metal wiring protection ability, the hardness of the cured product exceeds the hardness of the flexible wiring board, and the flexibility and low warpage of the flexible wiring board. Will adversely affect sex.
- the cured product has a tensile elastic modulus of 0.5 to 2.0 GPa. Furthermore, the tensile elastic modulus of the cured product is preferably 0.7 to 1.5 GPa, from the viewpoint of the ability to protect the wiring, the flexibility of the flexible wiring board, and the low warpage.
- thermosetting composition of the present invention that can form a cured product that has excellent wiring protection ability and does not adversely affect the flexibility and low warpage of the flexible wiring board is used for wiring protection. It is useful as an excellent solder resist ink.
- thermosetting composition of the present invention (I) has a functional group having a reactivity with an epoxy group and a carbonate bond from the viewpoint of achieving excellent low warpage and long-term insulation in addition to suppressing disconnection of wiring.
- polyurethane (a) hereinafter also simply referred to as “polyurethane (a)”
- inorganic fine particles and / or organic fine particles (b) inorganic fine particles and / or organic fine particles (b)
- compound (c) having two or more epoxy groups in one molecule hereinafter simply referred to as “polyurethane (a)”.
- Compound (c) each of these components will be described.
- the polyurethane (a) is not particularly limited as long as it is a polyurethane having a functional group reactive with an epoxy group and a carbonate bond.
- the polyurethane may be used alone or in combination of two or more.
- the “functional group having reactivity with an epoxy group” is not particularly limited as long as it is a functional group capable of reacting with a compound (c) having two or more epoxy groups in one molecule, which will be described later.
- the reaction of the polyurethane (a) and the compound (c) is a curing reaction, and the cured product formed by the reaction is suitable as an insulating film for protecting wiring such as a flexible wiring board.
- Examples of the functional group having reactivity with the epoxy group include a carboxyl group, an isocyanate group, a hydroxyl group, and a cyclic acid anhydride group.
- preferred functional groups among these are a carboxyl group, an isocyanate group, and a cyclic acid anhydride group.
- more preferred functional groups are carboxyl groups and cyclic acid anhydride groups, and particularly preferred functional groups are carboxyl groups. is there.
- the cyclic acid anhydride group refers to the ring structure when the acid anhydride group forms part of the ring structure.
- Examples of the polyurethane having a cyclic acid anhydride group and a carbonate bond include an imide bond described in JP-A-2003-198105, [0023] to [0067] and Example 1, and Mention may be made of polyurethanes having acid anhydride groups and carbonate bonds.
- polyurethane A having a carboxyl group, an isocyanate group or a hydroxyl group
- polyurethane A a polyurethane having a carboxyl group, an isocyanate group or a hydroxyl group
- polyurethane A (Poly) carbonate polyol, diisocyanate compound using a solvent such as diethylene glycol diethyl ether or ⁇ -butyrolactone, or a mixed solvent containing these in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate
- a solvent such as diethylene glycol diethyl ether or ⁇ -butyrolactone
- a mixed solvent containing these in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate
- the polyurethane A can be synthesized by reacting the carboxyl group-containing diol.
- the solvent that can be used when synthesizing the polyurethane A is not particularly limited as long as the raw material for the synthesis of the polyurethane A can be dissolved and the polyurethane A can also be dissolved.
- the solvent besides diethylene glycol diethyl ether and ⁇ -butyrolactone, diethylene glycol monoethyl ether acetate, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, butyl phenyl ether, amyl phenyl ether, diethylene glycol Examples include monoisopropyl ether, diethylene glycol monoisobutyl ether and dipropylene glycol monopropyl ether.
- polyols other than (poly) carbonate polyols and carboxyl group-containing diols, monohydroxyl compounds and monoisocyanate compounds may be further used as necessary.
- thermosetting the thermosetting composition of the present invention (I) are improved. This is preferable. Even without a catalyst, the above reaction proceeds sufficiently because alcohol and isocyanate, or alcohols are highly reactive.
- the (poly) carbonate polyol which is one of the synthetic raw materials for polyurethane A, is not particularly limited as long as it is a compound having one or more carbonate bonds and two or more alcoholic hydroxyl groups in the molecule. Specific examples thereof include (poly) carbonate diol having two hydroxyl groups in one molecule, (poly) carbonate triol and (poly) carbonate tetraol having three or more hydroxyl groups in one molecule. Can be mentioned.
- the number of carbonate bonds in the (poly) carbonate polyol is usually 50 or less, and the number of alcoholic hydroxyl groups is usually 2, but 3 or 4 can also be used.
- the (poly) carbonate polyol can be obtained by using a diol or a polyol mixture whose main component is a diol as a raw material and reacting it with a carbonate or phosgene.
- a diol is used as the raw material of the (poly) carbonate polyol to be reacted with the carbonate ester or phosgene, a (poly) carbonate diol is produced, and the structure thereof is represented by the following formula (1). ).
- R 1 s are each independently a residue (alkylene group) obtained by removing a hydroxyl group from the corresponding diol, n is a natural number, and usually n is an integer of 3 to 50 It is.
- the (poly) carbonate polyol represented by the formula (1) include 1,4-butanediol, 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, 2-ethyl-4- It can be produced by using a diol compound such as butyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,10-decandiol or 1,2-tetradecanediol as a raw material.
- a diol compound such as butyl-1,3-propanediol, 2,4-diethyl-1,5-pentan
- the (poly) carbonate polyol may be a (poly) carbonate polyol having a plurality of types of alkylene groups in its skeleton (copolymerized (poly) carbonate polyol).
- polyurethane A is advantageous from the viewpoint of preventing crystallization of the polyurethane A in the synthesis reaction solvent.
- a synthesis reaction solvent such as diethylene glycol diethyl ether and ⁇ -butyrolactone
- the (poly) carbonate polyols described above may be used singly or in combination of two or more.
- the diisocyanate compound which is one of the raw materials for the synthesis of polyurethane A, is not particularly limited as long as it is a compound having two isocyanate groups.
- diisocyanate compound examples include 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, isophorone diisocyanate biuret, hexamethylene diisocyanate Biuret form, isophorone diisocyanate isocyanurate form, hexamethylene diisocyanate isocyanurate form, lysine triisocyanate, ricin di Mention may be made of isocyanate, hexamethylene diisocyan
- 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanate) are used from the viewpoint of maintaining high electrical insulation performance of the cured product of the present invention (II) described later.
- the diisocyanate compounds described above may be used singly or in combination of two or more.
- the carboxyl group-containing diol which is one of the raw materials for the synthesis of polyurethane A, is not particularly limited as long as it is a compound having two alcoholic hydroxyl groups in the molecule and one or more carboxyl groups.
- the number of the carboxyl groups is usually one.
- carboxyl group-containing diol examples include dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and N, N-bis (hydroxyethyl) glycine.
- dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferable from the viewpoint of solubility of polyurethane A in the synthesis reaction solvent.
- These carboxyl group-containing diols may be used alone or in combination of two or more.
- Polyols other than (poly) carbonate polyol and carboxy group-containing diol As described above, as a synthesis raw material for polyurethane A, a polyol other than (poly) carbonate polyol and carboxyl group-containing diol (hereinafter also simply referred to as “polyol”) can be used as necessary. By using a polyol as a synthetic raw material for polyurethane A, the molecular weight and viscosity of polyurethane A can be adjusted.
- the polyol is not particularly limited as long as it is a compound having two or more alcoholic hydroxyl groups other than the (poly) carbonate polyol and other than the carboxyl group-containing diol.
- the number of alcoholic hydroxyl groups is usually 6 or less.
- polystyrene resin examples include 1,4-butanediol, 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, 2-ethyl-4-butyl-1,3-propanediol, 2,4- Diols such as diethyl-1,5-pentanediol, 1,10-decanedyl or 1,2-tetradecanediol, Examples thereof include compounds having three or more alcoholic hydroxyl groups in one molecule such as trimethylolpropane, trimethylolethane, glycerin and pentaerythritol.
- the polyols described above may be used singly or in combination of two or more.
- a monohydroxyl compound can be used as a raw material for the synthesis of polyurethane A, if necessary. By adding a monohydroxyl compound during the synthesis reaction of polyurethane A, the synthesis reaction can be stopped.
- the monohydroxyl compound has one alcoholic hydroxyl group in the molecule and does not have a substituent (for example, an amino group) that is more reactive with an isocyanate group than the alcoholic hydroxyl group.
- a substituent for example, an amino group
- the monohydroxyl compound examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether. , Diethylene glycol monoisobutyl ether and dipropylene glycol monopropyl ether.
- These monohydroxyl compounds may be used alone or in combination of two or more.
- a monoisocyanate compound can be used as a raw material for synthesizing polyurethane A, if necessary.
- a monoisocyanate compound as a synthetic raw material for polyurethane A, the molecular weight of polyurethane A can be adjusted.
- the monoisocyanate compound is not particularly limited as long as it is a compound having one isocyanate group. Specific examples thereof include cyclohexyl isocyanate, octadecyl isocyanate, phenyl isocyanate and toluyl isocyanate.
- thermosetting composition of the present invention (I)
- cyclohexyl isocyanate and octadecyl isocyanate are preferable.
- polyurethane A having carboxyl group, isocyanate group or hydroxyl group
- polyurethane A is prepared by using (poly) carbonate polyol, diisocyanate compound, carboxyl group-containing diol using a solvent such as diethylene glycol diethyl ether or ⁇ -butyrolactone in the presence or absence of a known urethanization catalyst. If necessary, it can be synthesized by reacting a polyol other than (poly) carbonate polyol and carboxyl group-containing diol, a monohydroxyl compound and a monoisocyanate compound.
- the order in which these raw materials are charged into the reactor is not particularly limited. Usually, (poly) carbonate polyol, carboxyl group-containing diol, and if necessary, polyol are charged first and dissolved in a solvent. . Then, the temperature of the solution is set to 20 to 140 ° C., more preferably 60 to 120 ° C., and the diisocyanate compound is added dropwise, and then the polyurethane A raw material is added at 50 to 160 ° C., more preferably 60 to 150 ° C. React.
- the charge molar ratio of the raw materials is adjusted according to the molecular weight and acid value of the target polyurethane A.
- the molecular weight can be adjusted by the raw material charge molar ratio, the reaction temperature, and the reaction time, but can also be adjusted by using a monohydroxyl compound. That is, at the timing when it is assumed that the polyurethane A has reached the target number average molecular weight (or close to the target number average molecular weight), the terminal isocyanate group of the polyurethane growing by the reaction of the synthetic raw material.
- a monohydroxyl compound is added for the purpose of blocking and further increasing the number average molecular weight.
- the timing can be derived, for example, by measuring the number average molecular weight of polyurethane A obtained by keeping the raw material and reaction temperature conditions constant and changing the reaction time, and collecting data.
- the number of isocyanate groups in the diisocyanate compound may be less than, equal to, or greater than the total number of hydroxyl groups in the (poly) carbonate polyol, carboxyl group-containing diol and polyol. No problem. This is because no further reaction occurs if the end is blocked by the monohydroxyl compound.
- the excess monohydroxyl compound is used as it is as a part of the polyurethane A solvent. Alternatively, it may be removed by distillation or the like.
- the introduction of the monohydroxyl compound into the polyurethane A is to suppress an increase in the molecular weight of the polyurethane A (that is, the reaction is stopped).
- the monohydroxyl compound is usually added to the reaction solution.
- the hydroxyl compound is added dropwise at 20 to 150 ° C, more preferably at 70 to 140 ° C. Thereafter, the reaction is completed by maintaining at the same temperature.
- a monoisocyanate compound can be introduced into the polyurethane A.
- the number of (poly) carbonate polyol, carboxyl group-containing diol and total number of hydroxyl groups in the polyol is determined in the synthesis of polyurethane A so that the terminal of the polyurethane molecule becomes a hydroxyl group.
- the hydroxyl groups remaining at the ends of the polyurethane react with the monoisocyanate compound.
- the monoisocyanate compound is usually dropped into the polyurethane reaction solution at 20 to 150 ° C., more preferably at 70 to 140 ° C. Thereby, the monoisocyanate compound is introduced into the polyurethane A, and then the reaction is completed by maintaining the same at the same temperature.
- the number average molecular weight of the polyurethane (a) used in the present invention including the polyurethane A obtained as described above is preferably 1,000 to 100,000, more preferably 3, 000 to 50,000, particularly preferably 5,000 to 30,000.
- the “number average molecular weight” 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 within the above range, the cured film obtained by thermosetting the thermosetting composition of the present invention (I) has sufficient elongation, flexibility and strength, and polyurethane ( The solubility of the a) in the reaction solvent is sufficient, and the viscosity of the thermosetting composition is in a range where there is no particular limitation in terms of use.
- the GPC measurement conditions are as follows.
- the acid value of the polyurethane (a) is 5 to 5 from the viewpoint of the balance of physical properties such as long-term insulation, low warpage and tensile elastic modulus of the cured product obtained by curing the thermosetting composition of the present invention (I). It is preferably 120 mgKOH / g, more preferably 10 to 50 mgKOH / g.
- the acid value is within the above range, the reactivity between the polyurethane (a) and other components contained in the curable composition such as the compound (c) described later does not decrease, and the present invention (I A sufficient heat resistance is achieved for the cured product of the thermosetting composition.
- the polyurethane (a) preferably has a number average molecular weight of 1,000 to 100,000, an acid value of 5 to 120 mgKOH / g, a number average molecular weight of 3,000 to 50,000, and The acid value is more preferably 10 to 50 mgKOH / g.
- the acid value of polyurethane (a) is the value of the acid value measured by the potentiometric titration method of JIS K0070.
- solvent Since the polyurethane (a) is solid by itself, it can be easily mixed with inorganic fine particles and / or organic fine particles (b) and the compound (c), which will be described later, by being dissolved in a solvent. Become. Therefore, it is preferable to dissolve the polyurethane (a) in a solvent.
- the polyurethane (a) is usually synthesized in a reaction solvent as described above, it is usually present in a state dissolved in the reaction solvent when synthesized.
- This reaction solvent can be used as it is as the solvent.
- an additional solvent can be added.
- solvent used here examples include ⁇ -butyrolactone, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, butyl phenyl ether, and amyl phenyl. Mention may be made of ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether and dipropylene glycol monopropyl ether.
- the solvents may be used alone or in combination of two or more.
- thermosetting composition By adding these inorganic fine particles and / or organic fine particles (b) to the thermosetting composition, heat resistance can be imparted to a cured product obtained by curing the composition.
- inorganic fine particles and / or organic fine particles includes not only inorganic fine particles and organic fine particles but also a powdery inorganic compound that is physically coated with an organic compound or chemically surface-treated. Organic-inorganic composite fine particles are also included.
- the inorganic fine particles used in the present invention (I) are not particularly limited as long as they are dispersed in the thermosetting composition of the present invention (I) to form a paste.
- 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 ), silicon nitride (Si 3 ).
- silica is preferable from the viewpoint of the balance between electrical insulation and heat resistance of the cured product obtained from the thermosetting composition.
- the organic fine particles used in the present invention (I) are not particularly limited as long as they are dispersed in the thermosetting composition of the present invention (I) to form a paste.
- Such organic fine particles are preferably heat-resistant resin fine particles having an amide bond, an imide bond, an ester bond or an ether bond.
- These resins are preferably a polyimide resin or a precursor thereof, a polyamideimide resin or a precursor thereof and 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 (b) is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
- the inorganic fine particles and / or organic fine particles (b) described above may be used alone or in combination of two or more, and the thermosetting composition of the present invention (I).
- the blending amount is usually 1 to 150 parts by weight, preferably 1 to 120 parts by weight, and more preferably 1 to 60 parts by weight with respect to 100 parts by weight of the component (a) contained in the thermosetting composition. It is.
- Compound (c) is not particularly limited as long as it is a compound other than polyurethane (a) and has two or more epoxy groups in one molecule.
- the number of epoxy groups in the compound (c) is usually 25 or less, but preferably 2 to 4.
- the compound (c) functions as a curing agent in the thermosetting composition of the present invention (I).
- Examples of the compound (c) include phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, phenol, cresol, xylenol, resorcin, catechol, phenols and / or ⁇ -naphthol, ⁇ -naphthol, dihydroxy
- a novolak epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of a naphthol such as naphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, or the like under an acidic catalyst Diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, and stilbene phenols (bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound,
- the compound (c) is preferably an aromatic ring structure and / or Or it is a compound which has an alicyclic structure.
- glycidyl ether of dicyclopentadiene-modified phenol resin that is, tricyclo [5,2,1,0 2,6] compound having a decane structure and aromatic ring structure
- 1,3-bis (1-adamantyl) -4,6-bis (glycidylyl) benzene 1- [2 ′, 4′-bis (glycidylyl) phenyl] adamantane
- l represents an integer of 0 or more and 20 or less.
- polyurethane (a) among compounds having an aromatic ring structure and / or an alicyclic structure, the activity bonded to the nitrogen atom of aniline or bis (4-aminophenyl) methane Active hydrogen bonded to the nitrogen atom of aminophenols such as glycidyl-type or methylglycidyl-type epoxy resins such as those in which hydrogen is substituted with glycidyl groups, and p-aminophenol, and active hydrogen of phenolic hydroxyl groups are substituted with glycidyl groups
- one type may be used alone, or two or more types may be used in combination.
- the compounding amount of the compound (c) with respect to 100 parts by mass of the polyurethane (a) cannot be generally described because it varies depending on the acid value of the polyurethane (a).
- the ratio of the number of functional groups reactive with the epoxy groups contained in the polyurethane (a) to the number of epoxy groups in the compound (c) having two or more epoxy groups in one molecule is preferably in the range of 1/3 to 2/1, more preferably in the range of 1 / 2.5 to 1.5 / 1. If the ratio is within the above range, it is unlikely that a large amount of unreacted polyurethane (a) or compound (c) will remain, and therefore the reactivity with unreacted epoxy groups in the polyurethane (a) is reduced. Since the functional group possessed does not remain so much, sufficient electrical insulation performance is achieved for the cured product of the thermosetting composition of the present invention (I).
- thermosetting composition containing components (a) to (c) The tensile modulus of the cured product obtained by curing the thermosetting composition containing the components (a) to (c) described above is also 0.5 to 2.0 GPa.
- the composition of the components (a) to (c) may be adjusted. For example, if the blending amount of the component (b) is adjusted to be within the range of the tensile elastic modulus. Good. Increasing the amount of component (b) increases the tensile modulus. In order to increase the tensile modulus, Tg or a component having a high softening point may be used as the component (c).
- the tensile elastic modulus can be increased. Further, when the blending amount of the component (c) having a high Tg or softening point is increased, the tensile elastic modulus can be increased.
- the component (c) one molecule Those containing 3 to 5 epoxy groups are preferably used, and those that are solid at room temperature are preferably used.
- the curing accelerator is preferably used in combination when the thermosetting composition of the present invention (I) contains polyurethane (a) and compound (c).
- the curing accelerator is not particularly limited as long as it is a compound that promotes the reaction between the epoxy group in the compound (c) and the functional group having reactivity with the epoxy group in the polyurethane (a).
- curing accelerator examples include melamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2,4-methacryloyloxyethyl-s-triazine, 2,4-diamino- Triazine compounds such as 6-vinyl-s-triazine and 2,4-diamino-6-vinyl-s-triazine / isocyanuric acid adduct, 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-methylimid
- These curing accelerators may be used alone or in combination of two or more.
- preferred curing accelerators are melamine, imidazole compounds, cycloamidine compounds and derivatives thereof.
- Phosphine compounds and amine compounds more preferably melamine, 1,5-diazabicyclo (4.3.0) nonene-5 and salts thereof, 1,8-diazabicyclo (5.4.0) undecene- 7 and its salts.
- the blending amount of these curing accelerators is not particularly limited as long as the curing acceleration effect can be achieved.
- the curing accelerator is preferably blended in the range of 0.05 to 5 parts by weight, and blended in the range of 0.1 to 3.0 parts by weight. Is more preferable. If a curing accelerator is blended in the above range, the thermosetting composition of the present invention (I) can be cured in a short time, and the resulting cured product has sufficient electrical insulation properties and water resistance. .
- thermosetting composition of the present invention (I) provides a cured product having good electrical insulation properties
- the composition can be used as a composition for an insulating protective film such as a resist. .
- thermosetting composition of the present invention (I) is used as a resist composition (that is, a resist ink composition)
- an antifoaming agent is used for the purpose of eliminating or suppressing the generation of bubbles during printing.
- the antifoaming agent is not particularly limited as long as it literally has an action of eliminating or suppressing bubbles generated when the resist ink composition is printed.
- thermosetting composition of the present invention (I) examples include, for example, BYK-077 (manufactured by Big Chemie Japan), SN deformer 470 (manufactured by San Nopco), TSA750S (momentive Silicone antifoaming agents such as Performance Materials) and silicone oil SH-203 (Toray Dow Corning) Acrylic polymer antifoaming agents such as Dappo SN-348 (manufactured by San Nopco), Dappo SN-354 (manufactured by San Nopco), Dappo SN-368 (manufactured by San Nopco) and Disparon 230HF (manufactured by Enomoto Kasei) Acetylene diol type antifoaming agents such as Surfynol DF-110D (manufactured by Nissin Chemical Industry) and Surfynol DF-37 (manufactured by Nissin Chemical Industry), Mention
- thermosetting composition of the present invention (I) includes surfactants such as a leveling agent, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, carbon black as necessary.
- surfactants such as a leveling agent, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, carbon black as necessary.
- known colorants such as naphthalene black can be added.
- an antioxidant such as a phenol-based antioxidant, a phosphite-based antioxidant, and a thioether-based antioxidant is added It can be added to the thermosetting composition of the invention (I) and is preferably added.
- phenol-based antioxidant examples include compounds represented by the following formulas (4) to (14).
- n is an integer of 1 to 5.
- examples of the phosphite antioxidant include compounds represented by the following formulas (15) to (25).
- thioether-based antioxidant examples include compounds represented by the following formulas (26) to (31).
- thermosetting composition of this invention (I) can also be added to the thermosetting composition of this invention (I) as needed.
- thermosetting composition of the present invention (I) can be obtained, for example, by uniformly kneading and mixing all of the blending components with a roll mill, a bead mill or the like.
- thermosetting composition contains the components (a) to (c), the polyurethane (a) and the compound (c) are prevented from being thermoset by shearing heat generation during kneading and mixing.
- thermosetting composition of the present invention (I) can also be obtained by the following method.
- a base compound formulation is obtained by mixing components other than the compound (c).
- the polyurethane (a) is usually synthesized using a solvent and used in a state dissolved in the solvent, each component other than the compound (c) is contained in the solvent. It is dissolved or dispersed in.
- thermosetting composition of this invention (I) is obtained by mixing this hardening
- the solvent that can be used to dissolve the compound (c) is the same as the solvent that can be used to dissolve the polyurethane (a).
- the thixotropy index of the thermosetting composition of the present invention (I) is not particularly limited, but is preferably 1.1 or more from the viewpoints of printability and prevention of sedimentation of the component (b).
- the thixotropy index is usually 2.0 or less.
- the cured product of the present invention (II) removes part or all of the solvent in the thermosetting composition of the present invention (I) (when the thermosetting composition of the present invention (I) does not contain a solvent). In general, this operation is not necessary), and it is generally obtained by causing the curing reaction to proceed by heating.
- the cured product of the present invention (II) is obtained as a cured film, the cured film can be obtained through the following first to third steps.
- thermosetting composition of the present invention (I) (especially when the composition contains the components (a) to (c)), the reaction solvent usually used for the synthesis of the polyurethane (a) is included. Is printed on a substrate or the like to obtain a coating film.
- the first step is a step of obtaining a coating film by printing the thermosetting composition of the present invention (I) on a substrate or the like, but there is no particular limitation on the printing method.
- the thermosetting composition can be applied to a substrate by a screen printing method, a roll coater method, a spray method, a curtain coater method, or the like to obtain a coating film.
- the coating film obtained in the first step is placed in an atmosphere of 50 ° C. to 100 ° C. to evaporate the solvent in the coating film, thereby obtaining a coating film from which part or all of the solvent has been removed. It is a process.
- the time for removing the solvent is preferably 4 hours or less, more preferably 2 hours or less. As described above, this step is not necessary when the thermosetting composition of the present invention (I) does not contain a solvent.
- the third step is a step of obtaining a cured film by performing heat curing on the coating film obtained in the second step in an atmosphere of 100 ° C. to 250 ° C.
- the heat curing time is preferably in the range of 20 minutes to 4 hours, more preferably in the range of 30 minutes to 2 hours.
- the cured product of the present invention (II) produced through such a process and having a tensile modulus of elasticity within the above specific range is excellent in wiring protection ability, and further has flexibility and low warpage of a flexible wiring board. Therefore, it is useful as a wiring protective film such as a solder resist. Moreover, as will be apparent from the examples to be described later, the cured product is excellent in electrical insulation, and therefore can be suitably used for general applications of insulating films.
- the present invention (III) is a method of applying the curable composition according to the present invention (I) on a flexible wiring board having a wiring pattern formed on a flexible substrate by a printing method.
- a flexible film having an insulating film comprising: forming a printed film on the pattern; and heating and curing the printed film at 80 to 130 ° C. to form an insulating film from the printed film. It is a manufacturing method of a wiring board.
- the wiring width of the flexible wiring board is 20 ⁇ m or less (normal wiring width is 3 ⁇ m or more), the effects of the present invention are remarkably achieved as described above.
- the wiring pattern of the board is tin-plated.
- thermosetting composition of the present invention (I) can be used as, for example, a solder resist ink as described above, and the cured product of the present invention (II) can be used as an insulating protective film for wiring.
- the cured product can be suitably used as a solder resist used to cover at least a part of the wiring of a flexible wiring board such as a chip-on film.
- a flexible wiring board having an insulating film can be manufactured through the following steps A to C.
- thermosetting composition of this invention (I) on the wiring pattern of a flexible wiring board by methods, such as screen printing, and obtaining a printed film.
- Process B A step of obtaining a printed film from which part or all of the solvent has been removed by evaporating the solvent in the printed film by placing the printed film obtained in step A in an atmosphere of 40 to 100 ° C.
- Process C A step of thermally curing the printed film obtained in the step B in an atmosphere of 80 to 130 ° C. to form a protective film for a flexible wiring board from the printed film.
- the temperature at the time of evaporating the solvent in Step B is 40 to 100 ° C., preferably 60 to 100 ° C., taking into consideration the evaporation rate of the solvent and a quick transition to the next step (Step C). Preferably, it is 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. In addition, when the thermosetting composition of this invention (I) does not contain a solvent, this process is unnecessary.
- thermosetting performed in the step C From the viewpoint of obtaining low warpage and flexibility suitable as an insulating protective film, and the condition of thermosetting performed in the step C, and from the viewpoint of preventing diffusion of the tin plating layer when the wiring pattern is tin-plated, It is carried out in the range of 80 to 130 ° C.
- the heating temperature is preferably 90 to 130 ° C, more preferably 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 acid value of the polyurethane (a) obtained by the above method was measured according to the potentiometric titration method of JIS K0070.
- Electrode Composite glass electrode C-173 manufactured by Kyoto Electronics Industry Co., Ltd.
- the number average molecular weight is a polystyrene-reduced number average molecular weight measured by GPC, and the GPC measurement conditions employed in this example are as follows.
- the temperature of the reaction solution was lowered to 90 ° C., and 150.4 g of methylenebis (4-cyclohexylisocyanate) (trade name; Desmodur-W, manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise over 30 minutes as a diisocyanate compound with a dropping funnel.
- methylenebis (4-cyclohexylisocyanate) (trade name; Desmodur-W, manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise over 30 minutes as a diisocyanate compound with a dropping funnel.
- polyurethane AU1 The number average molecular weight of the polyurethane having a carboxyl group and a carbonate bond (hereinafter referred to as “polyurethane AU1”) contained in the obtained polyurethane solution A1 is 14,000, and the acid value of the polyurethane AU1 is 40.0 mg ⁇ KOH / g. Moreover, solid content concentration in the polyurethane solution A1 was 45.0 mass%.
- the temperature of the reaction solution was lowered to 90 ° C., and 145.6 g of methylene bis (4-cyclohexylisocyanate) (trade name; Desmodur-W, manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise over 30 minutes as a diisocyanate compound with a dropping funnel.
- methylene bis (4-cyclohexylisocyanate) (trade name; Desmodur-W, manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise over 30 minutes as a diisocyanate compound with a dropping funnel.
- polyurethane solution A2 a polyurethane solution having a carboxyl group and a carbonate bond
- polyurethane AU2 The number average molecular weight of the polyurethane having a carboxyl group and a carbonate bond (hereinafter referred to as “polyurethane AU2”) contained in the obtained polyurethane solution A2 is 13,000, and the acid value of the polyurethane AU2 is 40.0 mg ⁇ KOH / g. Moreover, solid content concentration in the polyurethane solution A2 was 45.0 mass%.
- Example formulation 1 111.1 g of polyurethane solution A1, silica powder (trade name; Aerosil R-974, manufactured by Nippon Aerosil Co., Ltd.) 5.0 g, melamine (manufactured by Nissan Chemical Industries, Ltd.) 0.36 g and a defoaming agent (momentive performance) -Material company brand name; TSA750S) 0.70g was mixed.
- silica powder trade name; Aerosil R-974, manufactured by Nippon Aerosil Co., Ltd.
- melamine manufactured by Nissan Chemical Industries, Ltd.
- TSA750S defoaming agent
- Example of formulation 2 A polyurethane solution, silica powder, melamine and an antifoaming agent were mixed in the same manner as in Example Formulation Example 1 except that the polyurethane solution A1 was changed to the polyurethane solution A2 in Example Formulation Example 1.
- the obtained blend was named main ingredient blend C2.
- JER YL6121H was confirmed to be uniformly dispersed, the solution was cooled to room temperature, and a 50% by mass JER YL6121H-containing solution was obtained.
- This solution is designated as a curing agent solution E6.
- thermosetting composition F1 ⁇ Mixing of base compound and curing agent solution> (Formulation example 1 of thermosetting composition) 117.16 g of the main compound formulation C1 and 19.8 g of the curing agent solution E1 were placed in a plastic container. Mixing was performed by stirring for 5 minutes at room temperature using a spatula to obtain a thermosetting composition (hereinafter referred to as “thermosetting composition F1”).
- thermosetting composition (hereinafter referred to as “thermosetting”) is the same as the thermosetting composition Formulation Example 1 except that the base composition C1 in the thermosetting composition Formulation Example 1 is replaced with the base composition C2. (Referred to as composition F2).
- thermosetting composition F3 thermosetting composition (Composition example 3 of thermosetting composition) 117.16 g of the main compound formulation C1 and 11.7 g of the curing agent solution E2 were placed in a plastic container. Mixing was performed by stirring for 5 minutes at room temperature using a spatula to obtain a thermosetting composition (hereinafter referred to as “thermosetting composition F3”).
- thermosetting composition G1 (Comparative formulation example 1 of thermosetting composition) 117.16 g of the main compound formulation C1 and 16.3 g of the curing agent solution E3 were placed in a plastic container. Mixing was performed by stirring for 5 minutes at room temperature using a spatula to obtain a thermosetting composition (hereinafter referred to as “thermosetting composition G1”).
- thermosetting composition G2 (Comparative formulation example 2 of thermosetting composition) 117.16 g of the main compound formulation C1 and 65.8 g of the curing agent solution E4 were placed in a plastic container. Mixing was performed by stirring for 5 minutes at room temperature using a spatula to obtain a thermosetting composition (hereinafter referred to as “thermosetting composition G2”).
- thermosetting composition G3 (Comparative blending example 3 of thermosetting composition) 117.16 g of the main compound formulation C1 and 9.60 g of the curing agent solution E5 were placed in a plastic container. Mixing was performed by stirring for 5 minutes at room temperature using a spatula to obtain a thermosetting composition (hereinafter referred to as “thermosetting composition G3”).
- thermosetting composition (hereinafter referred to as “heat”) was the same as the comparative formulation example 3 of the thermosetting composition, except that the main compound formulation C1 of the comparative formulation example 3 of the thermosetting composition was replaced with the main compound formulation C2. Curable composition G4 ”) was obtained.
- thermosetting composition G5 (Comparative formulation example 5 of thermosetting composition) 117.16 g of the main compound formulation C1 and 12.44 g of the curing agent solution E6 were placed in a plastic container. Mixing was performed by stirring for 5 minutes at room temperature using a spatula to obtain a thermosetting composition (hereinafter referred to as “thermosetting composition G5”).
- thermosetting compositions F1 to F3 and thermosetting compositions G1 to G5 By using the thermosetting compositions F1 to F3 and the thermosetting compositions G1 to G5, the wiring breakage suppression effect evaluation (MIT test), the warpage evaluation and the long-term electricity The insulation reliability was evaluated. The results are shown in Table 1 below.
- a folding resistance test was performed in accordance with JIS C-5016.
- the number of bends was increased by 10 times, the presence or absence of cracks in the wiring was visually observed, and the number of bends when a crack occurred was recorded. The results are shown in Table 1.
- thermosetting compositions F2 and F3 were also shown in Table 1.
- thermosetting composition F1 was applied to the substrate by screen printing with a # 100 mesh polyester plate.
- the obtained coating film-formed substrate was placed in an 80 ° C. hot air circulation dryer for 30 minutes, and then placed in a 120 ° C. hot air circulation dryer for 60 minutes to cure the coating film.
- a 25 ⁇ m-thick polyimide film [Kapton (registered trademark) 100EN, manufactured by Toray DuPont Co., Ltd.] was used as the substrate.
- the cured coating film (hereinafter referred to as “cured film”) was cut with a circle cutter to 50 mm ⁇ together with the substrate.
- a cured film and a substrate (hereinafter also referred to as a test piece) cut into a circular shape exhibit deformation in a shape in which the vicinity of the center warps in a convex shape or a concave shape.
- the test piece cut by the circle cutter is left in a state of convex downward after 1 hour, that is, with the vicinity of the center of the test piece being in contact with the horizontal plane (the cured film or substrate is in contact with the horizontal plane), and from the horizontal plane.
- the maximum and minimum warpage heights were measured with a ruler and averaged.
- thermosetting compositions F2 and F3 were also shown in Table 1.
- thermosetting compositions F2 and F3 were also shown in Table 1.
- thermosetting composition F1 On the fluororesin sheet having a thickness of 1 mm, the thermosetting composition F1 was applied so that the thickness of the coating film after drying was 40 to 60 ⁇ m.
- the obtained coating film forming sheet was 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 to cure the coating film.
- the fluororesin sheet was peeled off to obtain a cured product.
- the cured product was cut into a strip with a width of 10 mm and a length of 60 mm, and the obtained cured film was used at 25 ° C. with a distance between chucks of 30 mm and a pulling speed of 5 mm / min.
- a tensile test was performed using this.
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Abstract
Description
(1)フレキシブル配線板の断線を抑制する絶縁膜(硬化物)を形成しうる熱硬化性組成物
(2)該組成物を熱硬化して得られる硬化物
(3)該硬化物で、配線パターン形成表面の少なくとも一部が被覆されたフレキシブル配線板
(4)そのようなフレキシブル配線板の製造方法。
(1)フレキシブル配線板の配線の断線を抑制することができる
(2)熱硬化性組成物が硬化する際のフレキシブル配線板の反りが小さい
(3)この熱硬化性組成物を硬化することによって得られる絶縁膜(硬化物)が、長期電気絶縁特性にも優れている。
該印刷膜を80~130℃で加熱して硬化させることで、前記印刷膜から絶縁膜を形成する工程を有することを特徴とする、絶縁膜を有するフレキシブル配線板の製造方法。
本発明(I)は、その硬化物の引張弾性率が0.5~2.0GPaであることを特徴とする熱硬化性組成物であって、当該組成物は、硬化させることにより、フレキシブル配線板の上に絶縁膜を形成するために用いられる。特に、配線の断線が起こりやすい、配線幅が20μm以下のフレキシブル配線板上に絶縁膜を形成する際に本発明(I)の熱硬化性組成物を用いることによって、その効果が顕著に奏される。
前記熱硬化性組成物の熱硬化成分としては、フェノール樹脂、エポキシ樹脂、メラミン樹脂、尿素樹脂、不飽和ポリエステル樹脂、アルキド樹脂、ポリウレタンまたは熱硬化性ポリイミドなどを挙げることができる。これらを2種以上組み合わせて用いてもよく、そのような単独の樹脂、又は複数の樹脂を組み合わせて得られる樹脂混合物の中から、その硬化物の引張弾性率が0.5~2.0GPaとなるものを適切に選んで、本発明に適用することができる。
本発明において、前記硬化物の引張弾性率は、硬化物を幅10mm、長さ60mmの短冊状に切り出し、25℃でチャック間距離30mm、引張り速度5mm/分の条件で引張り試験機(たとえば、装置:島津製作所製 小型卓上試験機 EZGraph)を用いて評価して得られる数値である。
そして特に本発明(I)の熱硬化性組成物は、配線の断線抑制の他、優れた低そり性及び長期絶縁性も達成する観点から、エポキシ基と反応性を有する官能基及びカーボネート結合を有するポリウレタン(a)(以下単に「ポリウレタン(a)とも言う」)と、無機微粒子及び/又は有機微粒子(b)と、1分子中に2個以上のエポキシ基を有する化合物(c)(以下単に「化合物(c)」とも言う)とを含むことが好ましい。以下、これら各成分について説明する。
前記ポリウレタン(a)は、エポキシ基と反応性を有する官能基及びカーボネート結合を有するポリウレタンであれば、特に制限されない。前記ポリウレタンは、1種単独で用いても2種以上を組み合わせて用いてもよい。
ポリウレタンAの合成原料の一つである(ポリ)カーボネートポリオールは、分子中にカーボネート結合を1個以上有し、アルコール性水酸基を2個以上有する化合物であれば、特に制限はない。その具体例としては、水酸基を1分子中に2個有している(ポリ)カーボネートジオール、水酸基を1分子中に3個以上有している(ポリ)カーボネートトリオールや(ポリ)カーボネートテトラオールが挙げられる。なお、(ポリ)カーボネートポリオールにおけるカーボネート結合の数は、通常50個以下であり、アルコール性水酸基の数は、通常2個であるが、3または4個のものも使用できる。
ポリウレタンAの合成原料の一つであるジイソシアネート化合物は、イソシアネート基を2つ有する化合物であれば、特に制限はない。
ポリウレタンAの合成原料の一つであるカルボキシル基含有ジオールは、分子中にアルコール性水酸基を2個有し、かつカルボキシル基を1個以上有する化合物であれば、特に制限はない。前記カルボキシル基の数は、通常1個である。
前述のように、ポリウレタンAの合成原料として、必要に応じて、(ポリ)カーボネートポリオール及びカルボキシル基含有ジオール以外のポリオ-ル(以下単に「ポリオール」ともいう)を使用することができる。ポリウレタンAの合成原料としてポリオールを使用することで、ポリウレタンAの分子量及び粘度を調節することが出来る。
トリメチロールプロパン、トリメチロールエタン、グリセリン及びペンタエリスリトール等の1分子中に3個以上のアルコール性水酸基を有する化合物が挙げられる。
前述のように、ポリウレタンAの合成原料として、必要に応じて、モノヒドロキシル化合物を使用することが出来る。ポリウレタンAの合成反応中にモノヒドロキシル化合物を添加することで、合成反応を停止させることができる。
前述のように、ポリウレタンAの合成原料として、必要に応じて、モノイソシアネート化合物を使用することが出来る。ポリウレタンAの合成原料としてモノイソシアネート化合物を使用することで、ポリウレタンAの分子量を調節することが出来る。
前述のように、ポリウレタンAは、公知のウレタン化触媒の存在下または非存在下で、ジエチレングリコールジエチルエーテルやγ-ブチロラクトンなどの溶媒を用いて、(ポリ)カーボネートポリオール、ジイソシアネート化合物、カルボキシル基含有ジオール、必要に応じて(ポリ)カーボネートポリオール及びカルボキシル基含有ジオール以外のポリオ-ル、モノヒドロキシル化合物およびモノイソシアネート化合物を反応させることにより合成することが出来る。
モノヒドロキシル化合物によって末端が封鎖されれば、それ以上反応が起こることはないからである。
たとえば上記のようにして得られるポリウレタンAをはじめとする、本発明に使用されるポリウレタン(a)の数平均分子量は、1,000~100,000であることが好ましく、さらに好ましくは、3,000~50,000であり、特に好ましくは、5,000~30,000である。
カラム:ShodexカラムLF-804(3本連結)
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)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%前後に調整。
ポリウレタン(a)は、それ単独では固体であるため、溶媒に溶解することで、後述する無機微粒子及び/又は有機微粒子(b)および化合物(c)とも均一に混合しやすく、また取り扱いも容易となる。したがって、ポリウレタン(a)を溶媒に溶解することが好ましい。
次に、上記無機微粒子及び/又は有機微粒子(b)について説明する。
酸化ガリウム(Ga2O3)、スピネル(MgO・Al2O3)、ムライト(3Al2O3・2SiO2)、コーディエライト(2MgO・2Al2O3・5SiO2)、タルク(3MgO・4SiO2・H2O)、チタン酸アルミニウム(TiO2-Al2O3)、イットリア含有ジルコニア(Y2O3-ZrO2)、珪酸バリウム(BaO・8SiO2)、窒化ホウ素(BN)、炭酸カルシウム(CaCO3)、硫酸カルシウム(CaSO4)、酸化亜鉛(ZnO)、チタン酸マグネシウム(MgO・TiO2)、硫酸バリウム(BaSO4)、有機ベントナイトおよびカーボン(C)が挙げられる。
次に、上記化合物(c)について説明する。
ビスフェノールA、ビスフェノールF、ビスフェノールS、アルキル置換又は非置換のビフェノール、スチルベン系フェノール類等のジグリシジルエーテル(ビスフェノールA型エポキシ化合物、ビスフェノールF型エポキシ化合物、ビスフェノールS型エポキシ化合物、ビフェニル型エポキシ化合物、スチルベン型エポキシ化合物)、
ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテル、
フタル酸、イソフタル酸、テトラヒドロフタル酸等のカルボン酸類のグリシジルエステル型エポキシ樹脂、
アニリン、ビス(4-アミノフェニル)メタン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したもの等のグリシジル型またはメチルグリシジル型のエポキシ樹脂、
p-アミノフェノール等のアミノフェノール類の窒素原子に結合した活性水素およびフェノール性水酸基の活性水素をグリシジル基で置換したもの等のグリシジル型またはメチルグリシジル型のエポキシ樹脂、
分子内のオレフィン結合をエポキシ化して得られるビニルシクロヘキセンジエポキシド、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、2-(3,4-エポキシ)シクロヘキシル-5,5-スピロ(3,4-エポキシ)シクロヘキサン-m-ジオキサン等の脂環型エポキシ樹脂、
パラキシリレン及び/又はメタキシリレン変性フェノール樹脂のグリシジルエーテル、テルペン変性フェノール樹脂のグリシジルエーテル、ジシクロペンタジエン変性フェノール樹脂のグリシジルエーテル、シクロペンタジエン変性フェノール樹脂のグリシジルエーテル、多環芳香環変性フェノール樹脂のグリシジルエーテル、ナフタレン環含有フェノール樹脂のグリシジルエーテル、
ハロゲン化フェノールノボラック型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、トリメチロールプロパン型エポキシ樹脂、オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂、ジフェニルメタン型エポキシ樹脂、
フェノールアラルキル樹脂、ナフトールアラルキル樹脂等のアラルキル型フェノール樹脂のエポキシ化物、
硫黄原子含有エポキシ樹脂、
トリシクロ[5,2,1,02,6]デカンジメタノールのジグリシジルエーテル、1,3-ビス(1-アダマンチル)-4,6-ビス(グリシジロイル)ベンゼン、1-[2',4'-ビス(グリシジロイル)フェニル]アダマンタン、1,3-ビス(4'-グリシジロイルフェニル)アダマンタン及び1,3-ビス[2',4'-ビス(グリシジロイル)フェニル]アダマンタン等のアダマンタン構造を有するエポキシ樹脂を挙げることができる。
1,3-ビス(1-アダマンチル)-4,6-ビス(グリシジロイル)ベンゼン、1-[2',4'-ビス(グリシジロイル)フェニル]アダマンタン、1,3-ビス(4'-グリシジロイルフェニル)アダマンタン及び1,3-ビス[2',4'-ビス(グリシジロイル)フェニル]アダマンタン等のアダマンタン構造を有するエポキシ樹脂(即ち、トリシクロ[3,3,1,13,7]デカン構造及び芳香環構造を有する化合物)等の、トリシクロデカン構造及び芳香環構造を有する化合物が、吸水率の低い硬化物を提供できるので好ましく、特に好ましくは、下記式(2)の化合物である。
一方、ポリウレタン(a)との反応性を重視する場合には、芳香環構造および/または脂環構造を有する化合物の中で、アニリン、ビス(4-アミノフェニル)メタンの窒素原子に結合した活性水素をグリシジル基で置換したもの等のグリシジル型またはメチルグリシジル型のエポキシ樹脂、p-アミノフェノール等のアミノフェノール類の窒素原子に結合した活性水素およびフェノール性水酸基の活性水素をグリシジル基で置換したもの等のグリシジル型またはメチルグリシジル型のエポキシ樹脂などの、アミノ基及び芳香環構造を有する化合物が好ましく、特に好ましくは、下記式(3)の化合物である。
以上説明した(a)~(c)成分を含む熱硬化性組成物を硬化させて得られる硬化物の引張弾性率も0.5~2.0GPaである。この引張弾性率の範囲を実現するには、(a)~(c)成分の組成を調整すればよく、たとえば(b)成分の配合量を当該引張弾性率の範囲になるように調整すればよい。(b)成分の配合量を増やすと、引張弾性率は高くなる。また引張弾性率を高めるには、(c)成分としてTgあるいは軟化点の高い成分を使用してもよい。たとえば(c)成分として、芳香環構造および/または脂環構造を有するもの(このような化合物はTgが高い)を使用すれば、引張弾性率を高めることができる。また、そのようなTgあるいは軟化点の高い(c)成分の配合量を多くすると、引張弾性率を高めることができる。本願発明の熱硬化性組成物を硬化させて得られる硬化物の引張弾性率が0.5~2.0GPaの範囲に入ることを達成しやすくするには、特に(c)成分として、1分子中に3~5個のエポキシ基を含有するものを使用することが好ましく、さらには常温で固体であるものを使用することが好ましい。
(硬化促進剤)
硬化促進剤は、本発明(I)の熱硬化性組成物が、ポリウレタン(a)および化合物(c)を含む場合に併用することが好ましい。硬化促進剤は、化合物(c)中のエポキシ基と、ポリウレタン(a)中のエポキシ基と反応性を有する官能基との反応を促進する化合物であれば特に制限はない。
イミダゾール、2-メチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、2-ウンデシルイミダゾール、2-ヘプタデシルイミダゾール、1-ベンジルー2-メチルイミダゾール、2-フェニルー4-メチルイミダゾール、1-シアノエチル-2-メチルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール、1-アミノエチルー2-エチルー4-メチルイミダゾール、1-アミノエチル-2-メチルイミダゾール、1-(シアノエチルアミノエチル)-2-メチルイミダゾール、N-[2-(2-メチルー1-イミダゾリル)エチル]尿素、1-シアノエチル-2-ウンデシルイミダゾール、1-シアノエチル-2-メチルイミダゾリウムトリメリテート、1-シアノエチル-2-フェニルイミダゾリウムトリメリテート、1-シアノエチル-2-エチル-4-メチルイミダゾリウムトリメリテート、1-シアノエチル-2-ウンデシルイミダゾリウムトリメリテート、2,4-ジアミノ-6-[2'-メチルイミダゾリル-(1')]-エチル-s-トリアジン、2,4-ジアミノ-6-[2'-ウンデシルイミダゾリル-(1')]-エチル-s-トリアジン、2,4-ジアミノ-6-[2'-エチル-4'-メチルイミダゾリル-(1')]-エチル-s-トリアジン、1-ドデシル-2-メチル-3-ベンジルイミダゾリウムクロライド、N,N'-ビス(2-メチル-1-イミダゾリルエチル)尿素、N,N'-ビス(2-メチル-1-イミダゾリルエチル)アジポアミド、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール、2-フェニル-4.5-ジヒドロキシメチルイミダゾール、2-メチルイミダゾール・イソシアヌル酸付加物、2-フェニルイミダゾール・イソシアヌル酸付加物、2,4-ジアミノ-6-[2'-メチルイミダゾリル-(1')]-エチル-s-トリアジン・イソシアヌル酸付加物、2―メチルー4-フォルミルイミダゾール、2-エチルー4-メチルー5-フォルミルイミダゾール、2-フェニル-4-メチルフォルミルイミダゾール、1-ベンジル-2-フェニルイミダゾール、1,2-ジメチルイミダゾール、1-(2-ヒドロキシエチル)イミダゾール、ビニルイミダゾール、1-メチルイミダゾール、1-アリルイミダゾール、2-エチルイミダゾール、2-ブチルイミダゾール、2-ブチル-5-ヒドロキシメチルイミダゾール、2,3-ジヒドロ-1H-ピロロ[1,2-a]ベンズイミダゾール、1-ベンジル-2-フェニルイミダゾール臭化水素塩および1-ドデシル-2-メチル-3-ベンジルイミダゾリウムクロライド等のイミダゾール系化合物、
1,5-ジアザビシクロ(4.3.0)ノネン-5及びその塩、1,8-ジアザビシクロ(5.4.0)ウンデセン-7及びその塩等のジアザビシクロアルケンなどのシクロアミジン化合物及びその誘導体、
トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノールおよびトリス(ジメチルアミノメチル)フェノール等の3級アミノ基含有化合物、
トリフェニルホスフィン、ジフェニル(p-トリル)ホスフィン、トリス(アルキルフェニル)ホスフィン、トリス(アルコキシフェニル)ホスフィン、トリス(アルキル・アルコキシフェニル)ホスフィン、トリス(ジアルキルフェニル)ホスフィン、トリス(トリアルキルフェニル)ホスフィン、トリス(テトラアルキルフェニル)ホスフィン、トリス(ジアルコキシフェニル)ホスフィン、トリス(トリアルコキシフェニル)ホスフィン、トリス(テトラアルコキシフェニル)ホスフィン、トリアルキルホスフィン、ジアルキルアリールホスフィンおよびアルキルジアリールホスフィン等の有機ホスフィン化合物、
ジシアンジアジド等を挙げることができる。
本発明(I)の熱硬化性組成物からは、電気絶縁特性の良好な硬化物が得られるので、前記組成物は、例えば、レジストなどの絶縁性保護膜用の組成物として使用可能である。
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)およびディスパロン230HF(楠本化成社製)等のアクリル重合体系消泡剤、
サーフィノールDF-110D(日信化学工業社製)およびサーフィノールDF-37(日信化学工業社製)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を挙げることができる。
さらに、本発明(I)の熱硬化性組成物には、必要に応じて、レベリング剤等の界面活性剤類、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、カーボンブラックおよびナフタレンブラック等の公知の着色剤を添加することができる。
本発明(I)の熱硬化性組成物は、例えば、配合成分の全部をロールミル、ビーズミル等で均一に混練、混合することによって得ることができる。
本発明(I)の熱硬化性組成物のチクソトロピー指数は、特に制限されないが、印刷性、成分(b)の沈降防止の観点から、1.1以上であることが好ましい。なお、チクソトロピー指数は通常2.0以下である。
次に、本発明(II)の硬化物について説明する。
本発明(I)の熱硬化性組成物(特に該組成物が上記(a)~(c)成分を含む場合には、通常ポリウレタン(a)の合成に使用した反応溶媒を含んでいる)を基板などに印刷して塗膜を得る工程。
第一工程で得られた塗膜を50℃~100℃の雰囲気下におくことで、塗膜中の溶媒を蒸発させ、一部或いは全量の溶媒が除去された塗膜を得る工程。
第二工程で得られた塗膜を、100℃~250℃の雰囲気下で熱硬化させ、硬化膜を得る工程。
次に、本発明(III)について説明する。
本発明(I)の熱硬化性組成物を、フレキシブル配線板の配線パターン上に、スクリーン印刷等の方法により印刷し、印刷膜を得る工程。
工程Aで得られた印刷膜を40~100℃の雰囲気下におくことで、印刷膜中の溶媒を蒸発させ、一部或いは全量の溶媒が除去された印刷膜を得る工程。
工程Bで得られた印刷膜を、80~130℃の雰囲気下で熱硬化させ、前記印刷膜からフレキシブル配線板の保護膜を形成する工程。
以下の実施合成例で得られたポリウレタン溶液中の溶媒を、加熱下で減圧留去してポリウレタン(a)を得た。
電極:京都電子工業社製 複合ガラス電極C-173。
数平均分子量は、GPCで測定したポリスチレン換算の数平均分子量であり、本実施例で採用したGPCの測定条件は以下のとおりである。
カラム:ShodexカラムLF-804(3本連結)
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)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%前後に調整。
(実施合成例1)
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、
(ポリ)カーボネートポリオールとして、C-1015N(クラレ社製 ポリカーボネートジオール:原料ジオールは1,9-ノナンジオール及び2-メチル-1,8-オクタンジオールであって、その仕込みモル比は、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である。水酸基価は112.3mgKOH/g、1,9-ノナンジオールの残存濃度は2.1質量%、2-メチル-1,8-オクタンジオールの残存濃度は9.3質量%である。)248.0g、
カルボキシル基含有ジオールとして、2,2-ジメチロールブタン酸(日本化成社製)47.5g、
(ポリ)カーボネートポリオール及びカルボキシル基含有ジオール以外のポリオ-ルとして、トリメチロールエタン(三菱ガス化学社製)2.7g、
溶媒としてγ―ブチロラクトン(三菱化学社製)467.5gおよびジエチレングリコールジエチルエーテル(日本乳化剤社製)82.5gを仕込み、100℃に加熱してすべての原料を溶解した。
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、
(ポリ)カーボネートポリオールとして、C-1015N(クラレ社製 ポリカーボネートジオール:原料ジオールは1,9-ノナンジオール及び2-メチル-1,8-オクタンジオールであって、その仕込みモル比は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である。水酸基価は112.3mgKOH/g、1,9-ノナンジオールの残存濃度は7.5質量%、2-メチル-1,8-オクタンジオールの残存濃度は4.4質量%である。)252.8g、
カルボキシル基含有ジオールとして、2,2-ジメチロールブタン酸(日本化成社製)47.5g、
溶媒としてγ―ブチロラクトン(三菱化学社製)467.5gとジエチレングリコールジエチルエーテル(日本乳化剤社製)82.5gを仕込み、100℃に加熱してすべての原料を溶解した。
(実施配合例1)
ポリウレタン溶液A1を111.1g、シリカ粉(日本アエロジル社製 商品名;アエロジルR-974)5.0g、硬化促進剤としてメラミン(日産化学工業社製)0.36g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)0.70gを混合した。
実施配合例1において、ポリウレタン溶液A1をポリウレタン溶液A2に変更した以外は、実施配合例1と同様の方法によって、ポリウレタン溶液、シリカ粉、メラミンおよび消泡剤を混合した。得られた配合物を、主剤配合物C2とした。
(製造例1)
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)で表わされるエポキシ樹脂(DIC社製 グレード名;HP-7200H エポキシ当量278g/eq 1分子当たりのエポキシ基の数が3のものが主成分、常温で固体)300gおよびγ-ブチロラクトン(三菱化学社製)300g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。容器内温を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、溶液を室温まで冷却し、濃度50質量%のHP-7200H含有溶液を取得した。この溶液を硬化剤溶液E1とする。
(製造例2)
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(32)で表わされるエポキシ樹脂(DIC社製 グレード名; HP-4700 エポキシ当量165g/eq 1分子中にエポキシ基を4個有する、常温で固体)300g、γ-ブチロラクトン(三菱化学社製)300g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。容器内温を70℃に昇温後、30分間撹拌を継続した。その後、HP-4700が完全に溶解したのを確認して、溶液を室温まで冷却し、濃度50質量%のHP-4700含有溶液を取得した。この溶液を硬化剤溶液E2とする。
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(33)で表される繰り返し構造単位を有するエポキシ樹脂(日本化薬社製 グレード名;NC-7000 エポキシ当量230g/eq 1分子当たりのエポキシ基の数が8のものが主成分、常温で固体)300g、γ-ブチロラクトン(三菱化学社製)300g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、NC-7000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NC-7000含有溶液を取得した。この溶液を硬化剤溶液E3とする。
撹拌機、温度計およびコンデンサーを備えた容器に、ビスフェノールA型の構造を有するエポキシ樹脂(ジャパンエポキシレジン社製 グレード名;JER1004 エポキシ当量925g/eq、1分子中にエポキシ基を2個有する、常温で固体)300g、γ-ブチロラクトン(三菱化学社製)300g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。容器内温を70℃に昇温後、30分間撹拌を継続した。その後、JER1004が完全に溶解したのを確認して、溶液を室温まで冷却し、濃度50質量%のJER1004含有溶液を取得した。この溶液を硬化剤溶液E4とする。
撹拌機、温度計およびコンデンサーを備えた容器に、ビスフェノールA型の構造を有するエポキシ樹脂(ジャパンエポキシレジン社製 グレード名;JER828 エポキシ当量135g/eq、1分子中にエポキシ基を2個有する、常温で液状)300g、γ-ブチロラクトン(三菱化学社製)300g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。容器内温を70℃に昇温後、30分間撹拌を継続した。その後、JER828が完全に溶解したのを確認して、溶液を室温まで冷却し、濃度50質量%のJER828含有溶液を取得した。この溶液を硬化剤溶液E5とする。
撹拌機、温度計およびコンデンサーを備えた容器に、ビフェニル構造を有するエポキシ樹脂(ジャパンエポキシレジン社製 グレード名;JER YL6121H エポキシ当量175g/eq、1分子中にエポキシ基を2個有する、常温で固体)300g、γ-ブチロラクトン(三菱化学社製)300g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。容器内温を70℃に昇温後、30分間撹拌を継続した。その後、JER YL6121Hが均一に分散したのを確認して、溶液を室温まで冷却し、濃度50質量%のJER YL6121H含有溶液を取得した。この溶液を硬化剤溶液E6とする。
(熱硬化性組成物の配合例1)
主剤配合物C1を117.16gと硬化剤溶液E1を19.8gとをプラスチック容器に入れた。混合は、スパーテルを用い、室温で5分間攪拌することで行い、熱硬化性組成物(以下、「熱硬化性組成物F1」と記す。)を得た。
熱硬化性組成物の配合例1の主剤配合物C1を主剤配合物C2に置き換えた以外は、熱硬化性組成物の配合例1と同様にし、熱硬化性組成物(以下、「熱硬化性組成物F2」と記す。)を得た。
主剤配合物C1を117.16gと硬化剤溶液E2を11.7gとをプラスチック容器に入れた。混合は、スパーテルを用い、室温で5分間攪拌することで行い、熱硬化性組成物(以下、「熱硬化性組成物F3」と記す。)を得た。
主剤配合物C1を117.16gと硬化剤溶液E3を16.3gとをプラスチック容器に入れた。混合は、スパーテルを用い、室温で5分間攪拌することで行い、熱硬化性組成物(以下、「熱硬化性組成物G1」と記す。)を得た。
主剤配合物C1を117.16gと硬化剤溶液E4を65.8gとをプラスチック容器に入れた。混合は、スパーテルを用い、室温で5分間攪拌することで行い、熱硬化性組成物(以下、「熱硬化性組成物G2」と記す。)を得た。
主剤配合物C1を117.16gと硬化剤溶液E5を9.60gとをプラスチック容器に入れた。混合は、スパーテルを用い、室温で5分間攪拌することで行い、熱硬化性組成物(以下、「熱硬化性組成物G3」と記す。)を得た。
熱硬化性組成物の比較配合例3の主剤配合物C1を主剤配合物C2に置き換えた以外は、熱硬化性組成物の比較配合例3と同様にし、熱硬化性組成物(以下、「熱硬化性組成物G4」と記す。)を得た。
主剤配合物C1を117.16gと硬化剤溶液E6を12.44gとをプラスチック容器に入れた。混合は、スパーテルを用い、室温で5分間攪拌することで行い、熱硬化性組成物(以下、「熱硬化性組成物G5」と記す。)を得た。
熱硬化性組成物F1~F3及び熱硬化性組成物G1~G5を用いて、以下に説明する方法により、フレキシブル配線板の配線の断線抑制効果評価(MIT試験)、反り性の評価及び長期電気絶縁信頼性の評価を行った。結果は後記の表1に記されている。
フレキシブル銅張り積層板(住友金属鉱山社製 グレード名;エスパーフレックスUS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/銅配線幅=15μm/15μm)に錫メッキ処理を施したフレキシブル配線板に、硬化性組成物F1を、スクリーン印刷法により、塗膜の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た。得られた塗膜形成配線板を、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前記塗膜を硬化させた。
熱硬化性組成物F1を、#100メッシュポリエステル版で、基板にスクリーン印刷により塗布した。得られた塗膜形成基板を、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前記塗膜を硬化させた。前記基板としては25μm厚ポリイミドフィルム〔カプトン(登録商標)100EN、東レ・デュポン社製〕を用いた。
フレキシブル銅張り積層板(住友金属鉱山社製 グレード名;エスパーフレックスUS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F1を、スクリーン印刷法により、塗膜の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た。得られた塗膜形成配線板を、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前記塗膜を硬化させた。
厚さ1mmのフッ素樹脂シート上に、熱硬化性組成物F1を、乾燥後の塗膜の膜厚が40~60μmとなるように塗布した。得られた塗膜形成シートを、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前記塗膜を硬化させた。
Claims (10)
- 硬化させることにより、フレキシブル基板上に配線パターンが形成されてなるフレキシブル配線板の上に絶縁膜を形成するための熱硬化性組成物であって、該組成物を硬化させて得られる硬化物の引張弾性率が0.5~2.0GPaであることを特徴とする熱硬化性組成物。
- 前記フレキシブル配線板の配線幅が20μm以下であることを特徴とする請求項1に記載の熱硬化性組成物。
- 前記熱硬化性組成物が、エポキシ基と反応性を有する官能基及びカーボネート結合を有するポリウレタン(a)と、無機微粒子及び/又は有機微粒子(b)と、1分子中に2個以上のエポキシ基を有する化合物(c)とを含むことを特徴とする請求項1または2に記載の熱硬化性組成物。
- 前記ポリウレタン(a)におけるエポキシ基と反応性を有する官能基が、カルボキシル基、イソシアネート基、水酸基及び環状酸無水物基からなる群より選ばれる少なくとも1種の官能基であることを特徴とする請求項3に記載の熱硬化性組成物。
- 前記化合物(c)が、芳香環構造および/または脂環構造を有することを特徴とする請求項3または4に記載の熱硬化性組成物。
- 前記化合物(c)が、トリシクロデカン構造及び芳香環構造を有することを特徴とする請求項5に記載の熱硬化性組成物。
- 請求項1~6のいずれか1項に記載の熱硬化性組成物を熱硬化して得られる硬化物。
- フレキシブル基板上に配線パターンが形成されてなるフレキシブル配線板の、該配線パターンが形成されている表面の少なくとも一部が、請求項7に記載の硬化物からなる絶縁膜によって被覆されていることを特徴とする、絶縁膜を有するフレキシブル配線板。
- 請求項1~6のいずれか1項に記載の熱硬化性組成物を、フレキシブル基板上に配線パターンが形成されてなるフレキシブル配線板の、該配線パターン上に印刷法により塗布することで、該パターン上に印刷膜を形成し、
該印刷膜を80~130℃で加熱して硬化させることで、前記印刷膜から絶縁膜を形成する工程を有することを特徴とする、絶縁膜を有するフレキシブル配線板の製造方法。 - 前記配線パターンが錫メッキ処理されていることを特徴とする請求項9に記載の絶縁膜を有するフレキシブル配線板の製造方法。
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JP2020079359A (ja) * | 2018-11-13 | 2020-05-28 | 株式会社Adeka | 硬化性樹脂組成物 |
WO2021005913A1 (ja) * | 2019-07-08 | 2021-01-14 | 日本ポリテック株式会社 | 硬化性組成物、硬化物、オーバーコート膜、並びにフレキシブル配線板及びその製造方法 |
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JP7521814B2 (ja) | 2019-07-08 | 2024-07-24 | 日本ポリテック株式会社 | 硬化性組成物、硬化物、オーバーコート膜、並びにフレキシブル配線板及びその製造方法 |
JP2021075586A (ja) * | 2019-11-05 | 2021-05-20 | 大日精化工業株式会社 | 熱硬化性樹脂組成物、塗料、及び積層シート |
JP7222871B2 (ja) | 2019-11-05 | 2023-02-15 | 大日精化工業株式会社 | 熱硬化性樹脂組成物、塗料、及び積層シート |
Also Published As
Publication number | Publication date |
---|---|
KR20120120395A (ko) | 2012-11-01 |
TWI500695B (zh) | 2015-09-21 |
KR101503987B1 (ko) | 2015-03-18 |
US20120305295A1 (en) | 2012-12-06 |
TW201141946A (en) | 2011-12-01 |
JP5726094B2 (ja) | 2015-05-27 |
JPWO2011096295A1 (ja) | 2013-06-10 |
CN102741351A (zh) | 2012-10-17 |
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