WO2011040560A1 - Composition durcissable de résine d'uréthane modifiée et son produit durci - Google Patents

Composition durcissable de résine d'uréthane modifiée et son produit durci Download PDF

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Publication number
WO2011040560A1
WO2011040560A1 PCT/JP2010/067133 JP2010067133W WO2011040560A1 WO 2011040560 A1 WO2011040560 A1 WO 2011040560A1 JP 2010067133 W JP2010067133 W JP 2010067133W WO 2011040560 A1 WO2011040560 A1 WO 2011040560A1
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urethane resin
modified urethane
curable composition
modified
resin curable
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PCT/JP2010/067133
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English (en)
Japanese (ja)
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亮一 高澤
幸徳 小濱
美晴 中川
修 池上
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宇部興産株式会社
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Priority to JP2011534326A priority Critical patent/JP5741441B2/ja
Publication of WO2011040560A1 publication Critical patent/WO2011040560A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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 modified urethane resin curable composition
  • a modified urethane resin curable composition comprising a modified urethane resin modified by introducing a polycarbonate component or a polybutadiene component.
  • This modified urethane resin curable composition is excellent in solder heat resistance, low warpage and tack-free properties, and also has excellent antifoaming properties, and at the same time, defects such as fine phase separation and voids occur in the cured film. Therefore, the appearance is good and the insulation reliability is excellent.
  • the modified urethane resin curable composition of the present invention is suitably used for forming an insulating film (protective film, solder resist, interlayer insulating layer, etc.) of a flexible wiring board in a chip-on-film (COF) format, for example. be able to.
  • COF chip-on-film
  • insulating films such as flexible wiring boards are formed using a resin curable composition made of polyimide resin, polyamideimide resin, polyurethane resin, epoxy resin, or the like.
  • resin curable compositions in order to impart flexibility, bendability, low warpage, etc. to the cured product, polysiloxane, polycarbonate, polybutadiene, etc. are introduced into the resin components as flexible oligomer components. It has been denatured. (For example, see Patent Documents 1 to 5)
  • the resin curable composition for forming an insulating film for a flexible wiring board has excellent antifoaming properties, and at the same time, it is easy to suppress the occurrence of defects such as phase separation structures of several micron scale and voids. Instead, an improved resin curable composition that can achieve both of these performances has been demanded.
  • the present invention is a modified urethane resin curable composition modified by introducing a polycarbonate component or a polybutadiene component, which has excellent solder heat resistance, low warpage, tack-free properties, and excellent antifoaming properties while being cured.
  • An object of the present invention is to provide a composition capable of easily obtaining a cured film that is uniform and excellent in insulation reliability because it can suitably suppress the occurrence of defects such as fine phase separation and voids in the film.
  • the present invention relates to the following items.
  • a modified urethane resin (A) obtained by reacting a diisocyanate compound (a) with a diol compound (b) containing at least a polycarbonate diol (b1) or a polybutadiene diol (b2), and a defoaming agent fluorine-modified polysiloxane ( B) Modified urethane resin curable composition characterized by containing.
  • C epoxy resin
  • D amino resin
  • E blocked polyfunctional isocyanate
  • modified urethane resin (A) according to any one of 1 to 5 above, wherein the fluorine-modified siloxane (B) is contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the solid content. Modified urethane resin curable composition.
  • modified urethane resin curable composition according to any one of the above 1 to 6, further comprising an antifoaming agent other than the fluorine-modified polysiloxane (B) in addition to the fluorine-modified polysiloxane (B).
  • a flexible wiring board having a wiring pattern formed of a conductive metal on an insulating film; Applying the modified urethane resin curable composition according to any one of 1 to 8 above to a wiring pattern surface excluding at least a lead portion of a flexible wiring board, and then curing to form an insulating film;
  • a method for producing a flexible wiring board for a tape carrier package comprising: a step of inspecting the obtained flexible wiring board for a tape carrier package with an optical automatic visual inspection apparatus.
  • a method for reducing an inspection failure rate by an optical automatic visual inspection apparatus for a flexible wiring board for a tape carrier package comprises: An insulating film; A wiring pattern formed on the insulating film; Covering part of the wiring pattern excluding the lead part, modified urethane resin (A) obtained by reacting diisocyanate compound (a) with diol compound (b) containing at least polycarbonate diol (b1) or polybutadiene diol (b2) And an insulating film obtained by curing a modified urethane resin curable composition containing an antifoaming agent, 9.
  • a method for reducing the inspection defect rate wherein the composition according to any one of 1 to 8 is used as the modified urethane resin curable composition.
  • a modified urethane resin curable composition modified by introducing a polycarbonate component or a polybutadiene component, which has excellent solder heat resistance, low warpage, and tack-free properties, and further has excellent antifoaming properties.
  • a polycarbonate component or a polybutadiene component which has excellent solder heat resistance, low warpage, and tack-free properties, and further has excellent antifoaming properties.
  • it is possible to suitably suppress the occurrence of defects such as fine phase separation and voids in the cured film it is possible to suitably obtain a composition that can easily obtain a cured film that is uniform and excellent in insulation reliability.
  • This modified urethane resin curable composition can be suitably used particularly as a solder resist for a flexible wiring board in a chip-on-film (COF) format. Moreover, since it can suppress suitably that generation
  • the modified urethane resin curable composition of the present invention comprises at least a modified urethane resin (A) and a fluorine-modified polysiloxane (B).
  • the modified urethane resin (A) includes, for example, a diisocyanate compound (a) and a diol compound (b) containing at least a polycarbonate diol (b1) or a polybutadiene diol (b2) as described in Patent Documents 1 and 2.
  • diisocyanate compound (a) those used for producing a normal polyurethane can be suitably used. That is, any one having two isocyanate groups in one molecule may be used, and it may be an aliphatic, alicyclic or aromatic polyisocyanate.
  • the diol compound (b) includes at least a polycarbonate diol (b1) or a polybutadiene diol (b2).
  • the polycarbonate diol (b1) is not particularly limited as long as it is a diol compound having a carbonate bond in the main chain, but a bifunctional hydroxyl-terminated polycarbonate diol represented by the following chemical formula (1) can be preferably used.
  • R 1 represents a divalent aliphatic or aromatic hydrocarbon group, preferably a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, and n is an integer of 1 to 40. is there.
  • the polycarbonate diol (b1) preferably has a number average molecular weight of 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 polycarbonate diol (b1) used in the present invention is specifically ETERNACOLL UH series, UN series, UD series, UC series, UB series manufactured by Ube Industries, Ltd., PLACEL series manufactured by Daicel Chemical Industries, Ltd., and Kuraray Co., Ltd.
  • the Kuraray polyol series manufactured by the company, the PCDL series manufactured by Asahi Kasei Chemicals Corporation, and the like can be preferably exemplified. These polycarbonate diols are used alone or in combination of two or more.
  • the polybutadiene diol (b2) is not limited, but is preferably a polybutadiene diol having a bifunctional hydroxyl group, preferably having a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. .
  • the polybutadiene diol (b2) may have a double bond in the molecule or may be a hydrogenated double bond in the molecule, but the double bond remains in the molecule.
  • the polybutadiene diol (b2) used in the present invention includes G series and GI series manufactured by Nippon Soda Co., Ltd., Poly bd series, Poly ip series, Epaul series, KRASOL series manufactured by Idemitsu Petrochemical Co., Ltd., A preferred example is the Polytail H series manufactured by Mitsubishi Chemical Corporation.
  • the diol compound (b) preferably comprises a diol compound other than the polycarbonate diol (b1) or the polybutadiene diol (b2).
  • a diol compound (b3) having a carboxyl group as a substituent can be used as the diol compound other than the polycarbonate diol (b1) or the polybutadiene diol (b2).
  • a diol compound (b3) having a carboxyl group as a substituent By using the diol compound (b3) having a carboxyl group as a substituent, a carboxyl group can be introduced into the modified urethane resin molecule.
  • the modified urethane resin can easily react with a compound having an epoxy group or an isocyanate group. That is, when the modified urethane resin is crosslinked, it can be effectively crosslinked, and the heat resistance and solvent resistance of the resulting cured product can be increased.
  • the diol compound (b3) having a carboxyl group as a substituent is not particularly limited, but a diol compound having a carboxyl group as a substituent and having 1 to 30 carbon atoms and further 2 to 20 carbon atoms is preferable. It is. Specific examples include 2,2-bis (hydroxymethyl) propionic acid and 2,2-bis (hydroxymethyl) butyric acid.
  • a diol compound (b4) having an imide ring in the main chain can be used as the diol compound (b).
  • the diol compound (b4) having an imide ring in the main chain is not limited as long as it is a diol compound having an imide ring in the main chain, but, for example, an alcoholic hydroxyl group terminal represented by the following chemical formula (2) Imide oligomers can be suitably used.
  • R 2 represents a divalent aliphatic or aromatic hydrocarbon group, preferably a divalent aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and X represents a carboxyl group of a tetracarboxylic acid. And Y represents a divalent group excluding the amino group of diamine, and m represents an integer of 0 to 20.
  • the diol compound (b4) having an imide ring in the main chain By using the diol compound (b4) having an imide ring in the main chain, it becomes possible to introduce an imide structure into the modified urethane resin molecule. Thereby, the mechanical strength, heat resistance, and insulation reliability of the cured product can be increased.
  • the alcoholic hydroxyl-terminated imide oligomer represented by the chemical formula (2) is obtained from a tetracarboxylic acid component and an amine component containing a diamine compound and a monoamine compound having one hydroxyl group.
  • m represents an integer of 0 to 20, particularly 0 to 10, and more preferably 0 to 5.
  • the imide oligomer terminated with an alcoholic hydroxyl group is not limited, but can be easily obtained by a known method described in, for example, JP-A-2007-238818.
  • the modified urethane resin (A) of the present invention is obtained by reacting a diisocyanate compound (a) and a diol compound (b).
  • the molar ratio of the diisocyanate compound (a) to the diol compound (b) to be used [number of moles of diol compound (b) / number of moles of diisocyanate compound (a)] is preferably 0.5 to 3. The range is 0, more preferably 0.8 to 2.5, and still more preferably 0.9 to 2.0. If the molar ratio is too small, the reaction solution may thicken, which is not preferable. If the molar ratio is too large, the molecular weight of the modified urethane resin is lowered, and heat resistance and the like are lowered.
  • the molar ratio of using the diol compound (b3) having a carboxyl group as a substituent is preferably 0.01 to 10, more preferably 0.1 to 5. It is a range. If the molar ratio is too small, the crosslinking density is low because the number of crosslinking groups is low, and the heat resistance of the cured product may be reduced. If the molar ratio is too large, the crosslinking density may be too high and the crosslinking density may be high. Deformation (particularly warpage) at the time of curing of the cured product is increased.
  • a molar ratio using the diol compound (b4 having a imide ring in the main chain (b4) is used.
  • ) / (Number of moles of total diol compound (b) ⁇ number of moles of diol compound (b4) having an imide ring in the main chain)] is preferably 0.01 to 10, more preferably 0.1. It is in the range of ⁇ 5. If the molar ratio is too small, the heat resistance of the cured product may decrease, and if the molar ratio is too large, flexibility may decrease.
  • the method for producing the modified urethane resin (A) of the present invention will be specifically described.
  • the reaction of the diisocyanate compound (a) and the diol compound (b) can be carried out without solvent or dissolved in an organic solvent.
  • the reaction temperature is 30 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., and the reaction time is usually 1 to 48 hours.
  • a well-known urethanization catalyst can be used as a catalyst. This reaction is preferably performed in a nitrogen atmosphere in order to prevent the isocyanate from being deactivated by moisture.
  • the solvent used for the reaction in the solvent is not particularly limited, but nitrogen-containing solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, etc., sulfur-containing atomic solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfuramide
  • Oxygenated solvents such as phenolic solvents cresol, phenol, xylenol, diglyme solvents diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate, propylene glycol methyl ether acetate , Propylene glycol ethyl ether acetate, dipropylene glycol
  • Examples include ketone solvents such as acetone, acetophenone, propiophenone, cyclohexanone, and isophorone, ether solvents such as ethylene glycol, dioxane, and tetrahydrofuran, and lactone solvents such as ⁇ -butyrolactone.
  • ketone solvents such as acetone, acetophenone, propiophenone, cyclohexanone, and isophorone
  • ether solvents such as ethylene glycol, dioxane, and tetrahydrofuran
  • lactone solvents such as ⁇ -butyrolactone.
  • ⁇ -butyrolactone, diethylene glycol ethyl ether acetate, triethylene glycol dimethyl ether, and the like can be preferably used.
  • the number average molecular weight of the modified urethane resin (A) used in the present invention is not limited, but is preferably 3000 to 100,000, more preferably 5000 to 50000.
  • the number average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC). If the number average molecular weight is lower than the above range, mechanical properties such as elongation, flexibility and strength of the resulting cured film may be impaired. On the other hand, if the number average molecular weight exceeds the above range, the viscosity increases more than necessary. There is a risk that the application will be limited.
  • Fluorine-modified polysiloxane (B) which is an essential component of the modified urethane resin curable composition of the present invention, means a compound having a polysiloxane skeleton and containing fluorine atoms.
  • the fluorine-modified polysiloxane (B) preferably has a fluorine content of about 5 to 45% by mass.
  • a fluorine content rate is the ratio (mass%) of the mass of the fluorine atom in the total mass of fluorine-modified polysiloxane.
  • the viscosity of the fluorine-modified polysiloxane (type B) rotational viscometer at 25 ° C. is preferably 10 to 100,000 mPa ⁇ sec.
  • the viscosity is high, it becomes easy to form a microscale phase separation structure or void in the cured product, and when it is low, the outgas amount of the fluorine-modified siloxane component may increase.
  • fluorine-modified polysiloxane examples include FA-600, FA-630 manufactured by Shin-Etsu Chemical Co., Ltd., FS1265 manufactured by Toray Dow Corning Co., Ltd., BYK-065, BYK-066N, BYK-067A manufactured by BYK Japan Japan Co., Ltd. It can be used suitably.
  • the fluorine-modified polysiloxane (B) may be used alone or in combination of two or more.
  • the blending amount is preferably in the range of 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the modified urethane resin (A). If the blending amount is lower than the above range, sufficient defoaming property may not be obtained. On the other hand, if it exceeds the above range, outgas increases, which is not suitable.
  • the solid content of the modified urethane resin (A) is the mass after heat-treating the modified urethane resin solution at 200 ° C. for 2 hours in a hot air dryer.
  • an antifoaming agent other than the fluorine-modified polysiloxane (B) is further added together with the fluorine-modified polysiloxane (B) as the antifoaming agent. It is preferable to contain.
  • the antifoaming agent other than the fluorine-modified polysiloxane (B) is not particularly limited, and examples thereof include other antifoaming agents such as polyacryls, polyvinyls, and polysiloxanes containing no fluorine.
  • a fluorine-modified polysiloxane (B) and a polyacrylic antifoaming agent mainly composed of an acrylic polymer and / or a polyvinyls mainly composed of a vinyl polymer are used.
  • a fluorine-modified polysiloxane (B) and a polyacrylic antifoaming agent mainly composed of an acrylic polymer and / or a polyvinyls mainly composed of a vinyl polymer are used.
  • Use in combination with an antifoaming agent is preferred because the antifoaming effect is increased.
  • polyacrylic antifoaming agents include Disparon OX-70, OX-77, OX-710, OX-715, OX720, OX-77EF, OX-881, OX manufactured by Enomoto Kasei Co., Ltd. -883 and the like.
  • defoaming agent for polyvinyls include Disparon P-410EF, P420, and P-425 manufactured by Enomoto Kasei Co., Ltd.
  • the polyacrylic antifoaming agent and / or the defoaming of polyvinyls when the fluorine-modified polysiloxane (B) is used in combination with a polyacrylic antifoaming agent and / or a polyvinyl antifoaming agent.
  • the compounding amount of the agent is in the range of 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the modified urethane resin (A).
  • the modified urethane resin curable composition of the present invention is not particularly limited, but is further selected from the group consisting of epoxy resin (C), amino resin (D) and blocked polyfunctional isocyanate (E) as a crosslinking component. Any one or more compounds (components) can be suitably contained.
  • Examples of the epoxy resin (C) include a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolak.
  • Type epoxy resin alicyclic epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic Type epoxy resin, silicone-modified epoxy resin, ⁇ -caprolactone-modified epoxy resin, epoxidized polybutadiene, and other epoxy compounds having two or more epoxy groups in one molecule. It can be used suitably. In particular, alicyclic epoxy resins and epoxidized polybutadiene can be suitably used because they have few chlorine impurities and good insulation reliability. In order to impart flame retardancy, an epoxy compound in which atoms such as halogen such as chlorine and bromine and phosphorus are introduced into the structure may be used.
  • amino resin (D) for example, fully alkylated type, methylol group type, imino group type, imino / methylol type melamine resin, urea resin, benzoguanamine resin, glycoluril resin and the like can be suitably used.
  • a benzoguanamine resin is preferable because it has good insulation reliability.
  • blocked polyfunctional isocyanate (E) those in which the isocyanate group of a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule is blocked can be suitably used.
  • an isocyanate group of an aliphatic, alicyclic or aromatic polyfunctional isocyanate is blocked, preferably an aliphatic, alicyclic or aromatic polyfunctional group having 2 to 30 carbon atoms excluding the isocyanate group
  • Isocyanate group of isocyanate is blocked, but is not limited to, for example, 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)
  • a polyfunctional isocyanate blocked with an oxime derivative, a pyrazole derivative or an active methylene compound can be suitably used.
  • a polyfunctional isocyanate blocked with a pyrazole derivative or an active methylene compound is preferable because of its high reactivity.
  • the modified urethane resin curable composition of the present invention may further contain a filler (F).
  • a well-known thing can be used conveniently as a filler (F).
  • inorganic fine particles such as silica, alumina, titanium oxide, barium sulfate, talc, calcium carbonate, glass powder, quartz powder, epoxy resin powder, melamine resin powder, urea resin powder, guanamine resin powder, polyester resin powder, polyamide resin
  • Organic fine particles such as powder, polyimide resin powder, rubber particles, and silicone powder
  • the particle diameter (average particle diameter) may be 0.001 to 10 ⁇ m, but is preferably 0.01 to 5 ⁇ m. When the particle diameter exceeds 5 ⁇ m, erroneous detection with an automatic visual inspection apparatus tends to occur.
  • the blending amount is 1 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the solid content of the modified urethane resin (A).
  • the organic solvent (G) used in the modified urethane resin curable composition of the present invention is not particularly limited, but is a nitrogen-containing solvent such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethyl.
  • sulfur-containing atomic solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone
  • isophorone, dioxane, tetrahydrofuran, lactone-based solvents, e.g. ⁇ - butyrolactone, etc. can be mentioned.
  • N-methyl-2-pyrrolidone, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, ⁇ -butyrolactone, tri Ethylene glycol dimethyl ether or the like can be preferably used.
  • denatured urethane resin can be used as it is.
  • curing catalysts such as imidazoles and tertiary amines, pigments such as organic coloring pigments and inorganic coloring pigments, hindered phenolic compounds, phosphorus compounds, hindered amines. You may mix
  • the viscosity with a rotational viscometer at 25 ° C. is usually 5 Pa ⁇ sec to 500 Pa ⁇ sec, preferably 25 Pa ⁇ sec to 200 Pa ⁇ sec. It is a range of sec.
  • the cured urethane resin curable composition of the present invention can obtain a cured film, preferably by heat treatment.
  • a solution composition for example, a coating film is formed by screen printing or the like, the solvent is removed at a low temperature, and then subjected to heat treatment, for example, modified polyurethane (A) and epoxy resin (C), amino resin (D) and A cured film can be suitably obtained by performing a crosslinking reaction with any one compound selected from the group consisting of blocked isocyanate (E).
  • the heat treatment conditions are, for example, 60 to 200 ° C., preferably 80 to 150 ° C., more preferably 100 to 130 ° C., 5 minutes to 5 hours, preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours. Heating with infrared rays is preferred.
  • the modified urethane resin curable composition of the present invention is excellent in antifoaming properties by using fluorine-modified polysiloxane, and therefore a cured film obtained by heat-treating it can suppress defects such as voids and is large. Does not form a phase separation structure. It is preferable to suppress or reduce the voids and the phase separation structure by optimizing the addition amount of the fluorine-modified polysiloxane and combining an antifoaming agent and other additives.
  • the maximum length of the void or phase separation structure is preferably 5 ⁇ m or less, and more preferably 2 ⁇ m or less. When the size of the void or the phase separation structure is larger than 5 ⁇ m, it cannot be distinguished from a true foreign substance by the optical automatic inspection device, and is likely to be erroneously detected.
  • the modified urethane resin curable composition of the present invention is excellent in solder heat resistance, low warpage and tack-free properties, and further has excellent antifoaming properties, and at the same time, defects such as fine phase separation and voids occur in the cured film. It can suppress suitably. For this reason, in a printed wiring board, a flexible printed wiring board, a chip-on film (COF), etc., in which an insulating film (cured film) is formed using the curable resin composition of the present invention, the cured film has a solder heat resistance and low warpage.
  • the optical automatic appearance inspection device has good characteristics such as the property and the tack-free property, and the occurrence of defects such as fine phase separation and voids in the cured film is suitably suppressed and the uniformity is high. There is no misrecognition in and excellent insulation reliability.
  • the modified urethane resin curable composition of the present invention is particularly useful as a solder resist ink or overcoat ink used for a wiring board.
  • the curable resin composition of the present invention can be suitably used for electronic parts such as an electrical insulating material such as an interlayer insulating film, a sealing material for IC and VLSI, and a material for laminated board.
  • Curing by heat treatment when used as a solder resist is applied to the pattern surface of an insulating film having a wiring pattern made of a conductive metal, for example, by screen printing so that the dry film thickness is about 3 to 60 ⁇ m. Thereafter, it can be achieved by heat treatment at about 80 to 210 ° C., preferably at 110 to 200 ° C. for 5 to 120 minutes, preferably about 10 to 60 minutes.
  • the insulating film has excellent solder heat resistance, low warpage, and tack-free property, and has high uniformity in which generation of defects such as fine phase separation and voids in the cured film is suppressed ( Cured film) can be obtained.
  • a method for producing a flexible wiring board for a tape carrier package when used as a solder resist for a chip-on-film (COF) type flexible wiring board is, for example, a wiring pattern formed of a conductive metal on an insulating film such as a polyimide film.
  • the flexible wiring board for a tape carrier package obtained in the process is configured to include a step of inspecting defects of wiring and a cured film by an optical automatic visual inspection apparatus, particularly a roll toe roll optical automatic inspection apparatus.
  • the tape carrier package is suitably manufactured through a process of injecting and then heat-treating at a temperature of about 60 to 200 ° C. to cure the underfill material.
  • the present invention also relates to a method for reducing an inspection defect rate by an optical automatic visual inspection apparatus for a flexible wiring board for a tape carrier package.
  • the flexible wiring board for a tape carrier package includes an insulating film, a wiring pattern formed on the insulating film, a partial cover excluding a lead portion of the wiring pattern, a diisocyanate compound (a), and at least a polycarbonate.
  • Insulating film obtained by curing a modified urethane resin curable composition containing a modified urethane resin (A) obtained by reacting a diol (b1) or a diol compound (b) containing a polybutadiene diol (b2) and an antifoaming agent The inspection defect rate is effectively reduced.
  • This method is characterized in that the modified urethane resin curable composition of the present invention described above and below is used as the modified urethane resin curable composition.
  • the defect rate due to voids and phase separation structures based on the material of the cured insulating film is reduced. Therefore, foreign substances, pattern defects, and the like can be properly recognized by the optical automatic visual inspection apparatus.
  • the evaluation was performed by the following method.
  • [Defoaming] Using a screen printer (screen plate SUS 150 mesh), the resin composition was printed on a polyimide film (UPILEX 35 SGA manufactured by Ube Industries), and the time until the bubbles generated during printing disappeared was measured. The case of less than 2 minutes was marked with ⁇ , the case of 2 to 3 minutes was marked with ⁇ , and the case of 3 minutes or more was marked with ⁇ .
  • the protective layer composition was applied, dried at 80 ° C. for 30 minutes, and then thermally cured at 120 ° C. for 1 hour to obtain a substrate on which an insulating layer was applied to a thickness of 10 ⁇ m.
  • a bias voltage of 60 V was applied in an 85% atmosphere, and the insulation reliability was evaluated according to the following criteria.
  • ⁇ ⁇ No migration for 200 hours or more, no decrease in resistance value.
  • X Migration or decrease in resistance value ( ⁇ 10 6 ⁇ ) within 200 hours.
  • the resin composition was applied to a glossy surface of an electrolytic copper foil having a thickness of 35 ⁇ m and cured to form an insulating film having a thickness of 10 ⁇ m.
  • a rosin flux (SUNFLUX SF-270, manufactured by Sanwa Chemical Industry Co., Ltd.) on the insulating film, the insulating film was brought into contact with a solder bath at 260 ° C. for 10 seconds. The state of the subsequent sample was observed and evaluated. A case where no abnormality occurred was indicated by ⁇ , and a case where abnormality such as blistering occurred was indicated by ⁇ .
  • the resin composition was applied to a polyimide film (Ube Industries Upilex 35SGA) and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to form a cured film having a thickness of about 10 ⁇ m.
  • This polyimide cured film was cut into 5 cm ⁇ 5 cm, and the average of the heights of the four corners from the horizontal surface of the horizontal platform was determined with the cured film facing up.
  • the resin composition was applied to a polyimide film (Ube Industries Upilex 35SGA) and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to form a cured film having a thickness of about 10 ⁇ m.
  • This polyimide cured film was cut into a width of 2.5 cm and a length of 5 cm to prepare a sample. This sample is placed on a hot plate heated to 160 ° C. with the coating surface facing upward, and a SUS weight (bottom area 2 cm ⁇ 5 cm, weight 500 g) is placed on it for 30 seconds, and there is no sticking when lifted. When sticking, it was set as x.
  • Death Module W Methylene bis (cyclohexyl isocyanate), manufactured by Sumika Bayer Urethane Co., Ltd. Millionate MT: manufactured by Nippon Polyurethane Industry Co., Ltd., diphenylmethane-4,4′-diisocyanate [polycarbonate diol] Kuraray polyol C-1065N: Kuraray Co., Ltd. hydroxyl value 112 mg KOH / g, 1,9-nonanediol, 2-methyl-1,8-octanediol-based polycarbonate diol EETNACOLL UH-200: Ube Industries, Ltd.
  • polysiloxane (no fluorine) KF603 Shin-Etsu Chemical Co., Ltd., polysiloxane (containing no fluorine) F-444: Mega Japan made by Dainippon Ink Co., Ltd., fluorine compound (no polysiloxane) P410EF: Enomoto Kasei Kogyo Co., Ltd. Disparon, Polyvinyls (Non-contained fluorine or polysiloxane) OX881: Disparon, polyacrylics manufactured by Enomoto Kasei Kogyo Co., Ltd. (Neither fluorine nor polysiloxane is contained) [Epoxy resin, amino resin] Celoxide 2021P: Daicel Chemical Industries, Ltd.
  • BET method 50 m 2 / g [Barium sulfate]
  • BARIFINE B-30 manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 0.3 ⁇ m
  • BARIFINE B-54 Sakai Chemical Industry Co., Ltd., average particle size 0.8 ⁇ m [Organic solvent]
  • ⁇ -Butyrolactone Diethylene glycol ethyl ether acetate manufactured by Mitsubishi Chemical Corporation: Curing catalyst manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 1 [Preparation of modified urethane resin curable composition and creation of cured film]
  • PU1 modified urethane resin
  • PU1 solution obtained in Reference Example 1 5 parts by mass of fluorine-modified polysiloxane FA600, 4 parts by mass of epoxy resin 2021P, and amino resin M136 5 with respect to 100 parts by mass of resin solid content.
  • 3 parts by mass of vinyl defoamer P-410EF as an antifoaming agent, 0.5 parts by mass of DBU as a curing catalyst, 0.5 parts by mass of Curesol 2E4MZ, and a pigment are added and stirred and mixed uniformly. did.
  • silica R972 and 30 parts by mass of barium sulfate B30 were added and mixed as fillers, and then kneaded using three rolls.
  • the composition was diluted with ⁇ -butyrolactone so that the viscosity was 20 to 60 Pa ⁇ sec to obtain a modified urethane resin curable composition.
  • This composition was evaluated for antifoaming properties, and for its cured film, appearance observation, support for automatic appearance inspection equipment, insulation reliability, solder heat resistance, low warpage, bendability, and tack-free properties. These evaluation results are shown in Table 1.
  • the modified urethane resin curable composition of the present invention has good antifoaming properties, and the cured product has good solder heat resistance, low warpage, and tack-free properties.
  • the appearance corresponding to an optical automatic appearance inspection apparatus
  • insulation reliability are greatly improved.
  • the cured product has excellent properties such as good solder heat resistance, low warpage, and tack-free property, and has improved appearance (corresponding to optical automatic visual inspection equipment) and insulation reliability.
  • a modified urethane resin curable composition comprising a modified urethane resin modified by introducing a component or a polybutadiene component can be obtained.
  • This modified urethane resin curable composition can be suitably used as a solder resist, particularly a solder resist for a chip-on-film (COF) type flexible wiring board.
  • COF chip-on-film
  • an external appearance is favorable and can test
  • electronic parts such as an electrical insulating material such as an interlayer insulating film, a sealing material for IC and VLSI, and a laminated board material.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

L'invention concerne une composition durcissable de résine d'uréthane modifiée qui comprend une résine d'uréthane modifiée (A) obtenue par mise en réaction d'un composé de diisocyanate (a) avec un composé de diol (b) contenant au moins un polycarbonate diol (b1) ou un polybutadiène diol (b2), et un polysiloxane modifié par du fluor (B) qui sert d'agent antimousse. La composition durcissable de résine d'uréthane modifiée présente une excellente résistance à la chaleur de soudure, des propriétés de faible gauchissement et des propriétés de non-adhérence, et présente également d'excellentes propriétés antimousse, et peut de préférence supprimer l'occurrence d'une séparation de microphases ou de défauts tels que des vides dans un film durci. En conséquence, un film durci qui est uniforme et présente une grande fiabilité d'isolation peut facilement être obtenu.
PCT/JP2010/067133 2009-09-30 2010-09-30 Composition durcissable de résine d'uréthane modifiée et son produit durci WO2011040560A1 (fr)

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WO2016129565A1 (fr) * 2015-02-09 2016-08-18 株式会社有沢製作所 Composition de résine à faible constante diélectrique
CN112604325A (zh) * 2020-12-14 2021-04-06 浙江传化华洋化工有限公司 一种有机硅改性不饱和高级脂肪醇酯消泡剂及其制备方法
CN112662325A (zh) * 2020-12-21 2021-04-16 四川东材科技集团股份有限公司 一种抗翘曲高模量有机硅绝缘胶带及其制备方法

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WO2016129565A1 (fr) * 2015-02-09 2016-08-18 株式会社有沢製作所 Composition de résine à faible constante diélectrique
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CN112604325A (zh) * 2020-12-14 2021-04-06 浙江传化华洋化工有限公司 一种有机硅改性不饱和高级脂肪醇酯消泡剂及其制备方法
CN112662325A (zh) * 2020-12-21 2021-04-16 四川东材科技集团股份有限公司 一种抗翘曲高模量有机硅绝缘胶带及其制备方法

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