JP4872335B2 - Wiring board mounting method - Google Patents

Description

  The present invention relates to a method for mounting a wiring board having a cured insulating film formed using a polyimidesiloxane solution composition, and also relates to an improved polyimidesiloxane solution composition that can be suitably used for the mounting method.

  When mounting electronic components on a wiring board that has an electric circuit line part on the surface, first form the electric circuit wiring on the surface of the wiring board, and harden it to cover most of the electric circuit wiring part except for the lead part. The coating resin film composition is applied to form a coating film, and the coating film is heated to form a cured insulating film. Next, an electrical joint is formed on the lead portion of the electric circuit wiring not covered with the cured insulating film to mount the electronic component.

  By the way, although the polyimidesiloxane solution composition is suitably used as a cured insulating film of a wiring board, bubbles generated when a coating film is formed are broken in a short time to obtain an efficient uniform cured insulating film. Therefore, it is known to add a silicone antifoaming agent. If the bubble removal property of the solution composition is improved, the process of forming a coating film and then obtaining a cured insulating film by heat treatment is facilitated, the working efficiency is improved, and the quality of the obtained cured insulating film is improved. Can do. As described above, the bubble removal property of the polyimidesiloxane solution composition used for forming the cured insulating film is an important characteristic, and it has been demanded to further improve the bubble removal property.

  In addition to the method of using solder or the method of using a conductive material such as gold as a bump, the electrical connection of electronic components to the wiring board is different when mounting electric parts such as liquid crystal display elements on the wiring board. An anisotropic conductive material such as an anisotropic conductive film (ACF) or an anisotropic conductive paste (ACP) is used. In such a mounting method, when the cured insulating film is formed of the polyimide siloxane solution composition, repelling occurs in the peripheral portion of the cured insulating film, and as a result, sufficient adhesive force for electrical bonding cannot be obtained, causing adhesion failure. The problem that it is easy to become.

  Patent Document 1 discloses that a polyimide siloxane solution composition containing a silicone antifoaming agent composed of a polysiloxane compound having a hydrophilic group at a side chain or at a terminal portion has a good defoaming property and formed as a solution composition. It is disclosed that the repellency of the peripheral portion of the cured insulating film is suppressed and the bonding reliability of the electric bonding portion by the anisotropic conductive material is improved. However, in the polyimidesiloxane solution composition containing a silicone antifoaming agent, there is no description that a predetermined mixed solvent is suitable in order to further improve the foam removal properties.

WO2005 / 080505 gazette

  An object of the present invention is an improved mounting method when mounting an electronic component with an anisotropic conductive material on a wiring board on which a cured insulating film is formed with a polyimidesiloxane solution composition, and suitable for such a mounting method. It is to provide a polyimide siloxane solution composition having improved defoaming properties.

  The present invention relates to a wiring board mounting method comprising a step of forming a cured insulating film partially covering the electric circuit wiring portion on a surface of the wiring substrate on which the electric circuit wiring portion is formed. Comprising at least one curable component selected from the group consisting of an organic solvent-soluble polyimidesiloxane, an epoxy compound and a polyvalent isocyanate compound, and a silicone antifoaming agent, wherein the organic solvent is (A) glyme And (B) a solvent selected from the group consisting of amides, pyrrolidones, anones, and any mixture thereof, the weight ratio ((A) / (B)) is 85/15 to 99 It is related with the mounting method of the wiring board characterized by forming using the polyimidesiloxane solution composition which consists of a mixed organic solvent mixed in the ratio of / 1.

  In particular, the present invention provides an electric circuit wiring in which a cured insulating film partially covering the electric circuit wiring portion is formed on the surface of the wiring substrate on which the electric circuit wiring portion is formed, and then not covered with the cured insulating film. In a method for mounting a wiring board comprising a step of forming an electrical junction with an anisotropic conductive material on the part, the cured insulating film is made of an organic solvent-soluble polyimide siloxane, an epoxy compound and a polyvalent isocyanate compound in an organic solvent. At least one curable component selected from the group consisting of: and a silicone antifoaming agent, wherein the organic solvent is a solvent comprising (A) glymes, (B) amides, pyrrolidones, anones and their A mixed organic solvent obtained by mixing a solvent selected from the group consisting of any mixture at a weight ratio ((A) / (B)) of 85/15 to 99/1 Made on how to implement the wiring board and forming with the polyimide siloxane solution composition.

  In the method for mounting a wiring board of the present invention, the organic solvent-soluble polyimide siloxane of the polyimide siloxane solution composition is (a) a tetracarboxylic acid compound and 30 to 95 mol% of a diaminopolysiloxane represented by the general formula (1), It is preferably an organic solvent-soluble polyimide siloxane obtained from 0.5 to 40 mol% of an aromatic diamine having a polar group and a diamine compound consisting of 0 to 69.5 mol% of a diamine compound other than the diamine.

（式中、Ｒ_１は２価の炭化水素基又は芳香族基を示し、Ｒ_２は独立に１価の炭素水素基又は芳香族基を示し、ｎ１は１〜５０の整数を示す。）

(In the formula, R ₁ represents a divalent hydrocarbon group or an aromatic group, R ₂ independently represents a monovalent carbon hydrogen group or an aromatic group, and n 1 represents an integer of 1 to 50.)

  Moreover, the polyimidesiloxane solution composition contains 1 to 50 parts by mass of at least one curable component selected from the group consisting of an epoxy compound and a polyvalent isocyanate compound with respect to 100 parts by mass of the organic solvent-soluble polyimidesiloxane. It is preferable that a polyimide siloxane solution composition contains 0.1-10 mass parts of silicone defoamers with respect to 100 mass parts of organic solvent-soluble polyimide siloxane.

  Furthermore, in the method for mounting a wiring board of the present invention, the solvent consisting of (A) glymes of the mixed solvent of the polyimidesiloxane solution composition is triglyme, diglyme or a mixture thereof, and the mixed solvent of the polyimidesiloxane solution composition (B) the solvent selected from the group consisting of amides, pyrrolidones, anones and any mixture thereof is dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, cyclohexanone or any of them It is preferable that it is a mixture.

  Furthermore, the present invention comprises, in an organic solvent, an organic solvent-soluble polyimide siloxane, at least one curable component selected from the group consisting of an epoxy compound and a polyvalent isocyanate compound, and a silicone antifoaming agent. , (A) a solvent composed of glymes and (B) a solvent selected from the group consisting of amides, pyrrolidones, anones, and mixtures of any of them ((A) / (B)) The present invention relates to a polyimidesiloxane solution composition having improved defoaming characteristics, comprising a mixed organic solvent mixed at a ratio of 85/15 to 99/1.

  The present invention is an improved method for mounting a wiring board comprising a step of forming a cured insulating film partially covering the electric circuit wiring part on the surface of the wiring board on which the electric circuit wiring part is formed. Provided are an improved mounting method for mounting an electronic component with an anisotropic conductive material on a wiring board having a cured insulating film formed of a polyimidesiloxane solution composition, and a polyimidesiloxane solution composition suitable for such a mounting method. can do. According to this mounting method, since the bubble-removing property is improved, the process of forming a coating film by screen printing or the like and then obtaining a cured insulating film by heat treatment becomes very easy, and the work efficiency can be improved and homogeneous. A hardened insulating film can be easily formed.

  The mounting method of the present invention is characterized in that an improved wiring board comprising a step of forming a cured insulating film partially covering the electric circuit wiring part on the surface of the wiring board on which the electric circuit wiring part is formed. A mounting method, in particular, a hardened insulating film partially covering the electric circuit wiring part is formed on the surface of the wiring board on which the electric circuit wiring part is formed, and then different from the electric circuit wiring part not covered with the hardened insulating film. In the method for mounting a wiring board comprising a step of forming an electrical junction with an isotropic conductive material, the cured insulating film is formed of an organic solvent-soluble polyimide siloxane, an epoxy compound, and a polyvalent isocyanate compound in an organic solvent. At least one curable component selected from the group consisting of a silicone antifoaming agent, the organic solvent comprising (A) a glyme solvent, (B) an amide, From a mixed organic solvent in which a weight ratio ((A) / (B)) is mixed at a ratio of 85/15 to 99/1 with a solvent selected from the group consisting of dongs, anones and mixtures thereof The polyimide siloxane solution composition to be formed.

  The organic solvent-soluble polyimide siloxane is composed of a tetracarboxylic acid compound and a diamine compound containing diaminopolysiloxane in an approximately equimolar ratio, preferably a ratio of 1.0 to 1.2 mol of tetracarboxylic acid compound with respect to 1 mol of the diamine compound. And can be obtained by reacting in an organic solvent.

  Examples of tetracarboxylic acid compounds include 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyl Tetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetra Carboxylic acid, 2,2-bis (3,4-benzenedicarboxylic acid) hexafluoropropane, pyromellitic acid, 1,4-bis (3,4-benzenedicarboxylic acid) benzene, 2,2-bis [4- ( 3,4-phenoxydicarboxylic acid) phenyl] propane, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalene Aromatic tetracarboxylic acids such as tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,1-bis (2,3-dicarboxyphenyl) ethane, or their acid dianhydrides and lower alcohols -Ester esterified product can be preferably mentioned. Among these, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid Carboxylic acids or their acid dianhydrides or esterified products of lower alcohols are particularly suitable because they are excellent in solubility in organic solvents when polyimide siloxane is used, and 80 in aromatic tetracarboxylic acid compounds. It is preferable to use at a ratio of mol% or more, particularly 85% or more, and further 100%.

  The tetracarboxylic acid compound is preferably a tetracarboxylic dianhydride that can be easily reacted with a diamine compound. Further, when the amount of tetracarboxylic dianhydride used is 1.05 mol or more with respect to the diamine compound and an unreacted anhydrous ring remains, it may be left as it is. May be used.

  The diamine compound preferably contains diaminopolysiloxane and further contains an aromatic diamine, particularly an aromatic diamine compound having a polar group. Usually, the diaminopolysiloxane is 30 to 95 mol%, preferably 50 to 95 mol%, more preferably 60 to 95 mol%, the aromatic diamine compound having a polar group is 0.5 to 40 mol%, and the diaminopolysiloxane. And diamine compounds other than the aromatic diamine compound which has the said polar group are used in the ratio of 0-69.5 mol% (usually 0-30 mol%).

  The diaminopolysiloxane is preferably a compound represented by the following general formula (1).

式中、Ｒ_１は２価の炭化水素基又は芳香族基を示し、Ｒ_２は独立に１価の炭素水素基又は芳香族基を示し、ｎ１は１〜５０の整数を示す。ただし、Ｒ_１は独立に炭素数１〜６の２価の炭化水素基またはフェニレン基、特にプロピレン基であり、Ｒ_２は独立に炭素数１〜５のアルキル基またはフェニル基であり、ｎ１は３〜２０であることが好ましい。なお、ジアミノポリシロキサンが二種以上の混合物からなる場合は、ｎ１はアミノ当量から計算される。

In the formula, R ₁ represents a divalent hydrocarbon group or aromatic group, R ₂ independently represents a monovalent carbon hydrogen group or aromatic group, and n1 represents an integer of 1 to 50. However, R ₁ is independently a divalent hydrocarbon group or a phenylene group having 1 to 6 carbon atoms, in particular a propylene group, R ₂ is independently an alkyl group or a phenyl group having 1 to 5 carbon atoms, n1 is It is preferable that it is 3-20. In addition, when diaminopolysiloxane consists of 2 or more types of mixtures, n1 is calculated from an amino equivalent.

  Examples of diaminopolysiloxanes include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-aminophenyl) poly Dimethylsiloxane, α, ω-bis (4-amino-3-methylphenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis (4-aminobutyl) polydimethyl Examples thereof include siloxane.

  The aromatic diamine compound having a polar group constituting the diamine compound is an aromatic diamine having a polar group having reactivity with an isocyanate group or an epoxy group in the molecule, and preferably represented by the following general formula (2). Diamine.

式中、Ｘ及びＹは、それぞれ独立に直接結合、ＣＨ_２、Ｃ（ＣＨ_３）_２、Ｃ（ＣＦ_３）_２、Ｏ、ベンゼン環、ＳＯ_２を示し、ｒ１は水酸基又はカルボキシル基を示し、ｎ２は１又は２であり、ｎ３、ｎ４はそれぞれ独立に０、１又は２、好ましくは０又は１であり、ｎ３及びｎ４の少なくとも一方は１又は２である。

In the formula, X and Y each independently represent a direct bond, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , O, a benzene ring, SO ₂ , r1 represents a hydroxyl group or a carboxyl group, n2 is 1 or 2, n3 and n4 are each independently 0, 1 or 2, preferably 0 or 1, and at least one of n3 and n4 is 1 or 2.

  Examples of the diamine compound represented by the general formula (2) include diaminophenol compounds such as 2,4-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4 '-Diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2', 5,5'-tetrahydroxybiphenyl, etc. Hydroxybiphenyl compounds, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′- Dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydride Hydroxydiphenylalkane compounds such as xylphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′ Hydroxydiphenyl ether compounds such as dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenyl ether, 3,3′-diamino-4, 4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, 4,4 Hydroxydiphenyl sulfone compounds such as -diamino-2,2'-dihydroxydiphenyl sulfone, 4,4'-diamino-2,2 ', 5,5'-tetrahydroxydiphenyl sulfone, 2,2-bis [4- Bis (hydroxyphenoxyphenyl) alkane compounds such as (4-amino-3-hydroxyphenoxy) phenyl] propane, bis (hydroxyphenoxy) such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl Examples thereof include diamine compounds having a hydroxyl group such as biphenyl compounds and bis (hydroxyphenoxyphenyl) sulfone compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone.

  Furthermore, examples of the diamine compound represented by the general formula (2) include benzenecarboxylic acids such as 3,5-diaminobenzoic acid and 2,4-diaminobenzoic acid, 3,3′-diamino-4,4′- Dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, 4,4′-diamino-2,2 ′, 5 Carboxybiphenyl compounds such as 5′-tetracarboxybiphenyl, 3,3′-diamino-4,4′-dicarboxydiphenylmethane, 4,4′-diamino-3,3′-dicarboxydiphenylmethane, 4,4′- Diamino-2,2′-dicarboxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino- -Carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, carboxydiphenylalkanes such as 4,4'-diamino-2,2 ', 5,5'-tetracarboxybiphenyl Compounds, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4,4′-diamino-2, Carboxydiphenyl ether compounds such as 2′-dicarboxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenyl ether, 3,3′-diamino- 4,4′-dicarboxydiphenylsulfone, 4,4′-diamino-3,3′-dicarboxydiphenylsulfone, 4,4′-diamino- , 2 ′, 5,5′-tetracarboxydiphenylsulfone and other carboxydiphenylsulfone compounds, bis (carboxyphenoxyphenyl) such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane Alkane compounds, bis (carboxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-carboxyphenoxy) biphenyl, 2,2-bis [4- (4-amino-3-carboxyphenoxy) Examples thereof include diamine compounds having a carboxyl group such as bis (carboxyphenoxyphenyl) sulfone compounds such as phenyl] sulfone.

  The diamine compound other than the diaminopolysiloxane constituting the diamine compound and the aromatic diamine compound having the polar group is not particularly limited, but an aromatic diamine represented by the following general formula (3) is preferable. .

式中、Ｘ及びＹは、それぞれ独立に直接結合、ＣＨ_２、Ｃ（ＣＨ_３）_２、Ｃ（ＣＦ_３）_２、Ｏ、ベンゼン環、ＳＯ_２を示し、ｎ５は１又は２である。

In the formula, X and Y each independently represent a direct bond, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , O, a benzene ring, SO ₂ , and n5 is 1 or 2.

Examples of the aromatic diamine represented by the general formula (3) include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 1,4-diamino-2,5-dihalogeno Diamines containing one benzene such as benzene, bis (4-aminophenyl) ether, bis (3-aminophenyl) ether, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone Bis (4-aminophenyl) methane, bis (3-aminophenyl) methane, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, o-dianisidine, o Diamines containing two benzenes such as toridine and tolidine sulfonic acids, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-amino) Phenyl) benzene, 1,4-bis (3-aminophenyl) benzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, α, α′-bis (4-aminophenyl)- Diamines containing three benzenes such as 1,3-diisopropylbenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4 ′-(4-aminophenoxy) biphenyl, 9,9 Examples include diamine compounds such as diamines containing 4 or more benzenes such as -bis (4-aminophenyl) fluorene and 5,10-bis (4-aminophenyl) anthracene.
In addition, aliphatic diamine compounds such as hexamethylene diamine and diaminododecane can be used together with the diamine.

The polyimidesiloxane in the present invention can be obtained, for example, by the following method.
a) A method of obtaining polyimidesiloxane by polymerizing and imidizing continuously at 15 to 250 ° C. in an organic polar solvent using substantially equimolar amounts of a tetracarboxylic acid compound and a diamine compound.
b) A tetracarboxylic acid compound and a diamine compound are divided, and an excess amount of a tetracarboxylic acid compound and a diamine compound (for example, diaminopolysiloxane) are polymerized and imidized in an organic polar solvent at 15 to 250 ° C. to obtain an average. An imide siloxane oligomer having an acid anhydride group (or acid, esterified product thereof) at a terminal having a polymerization degree of about 1 to 10 is prepared, and a tetracarboxylic acid compound and an excess amount of a diamine compound are separately added in an organic polar solvent 15 to 15 Polymerize and imidize at 250 ° C. to prepare an imide oligomer having an amino group at the terminal with an average degree of polymerization of about 1 to 10, and then mix the two so that the acid component and the diamine compound are approximately equimolar. A method of reacting at 15 to 60 ° C. and further raising the temperature to 130 to 250 ° C. for reaction to obtain polyimide siloxane.
How the c) a tetracarboxylic acid compound and a diamine compound approximately equimolar used, after obtaining the polyamic acid is polymerized at first 20 to 80 ° C. in an organic polar solvent to give a polyimide siloxane imidized the polyamic acid .

The organic polar solvent used in these methods is preferably an organic polar solvent that dissolves each component of the reaction and the resulting polyimide siloxane. For example, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N A nitrogen-containing atomic solvent such as methylcaprolactam, for example, a sulfur-containing atomic solvent such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfuramide, for example, a phenolic solvent such as cresol, phenol, xylenol, for example, diethylene glycol dimethyl ether (Diglyme), diglyme solvents such as triethylene glycol dimethyl ether (triglyme), tetraglyme, such as acetone, methanol, ethanol, ethylene glycol, dioxane, Examples include oxygen-containing atomic solvents such as lahydrofuran, other pyridines, tetramethylureas, and other organic solvents such as benzene, toluene, xylene, and other organic solvents such as solvent naphtha and benzonitrile. You may use together.
In addition, when the mixed solvent which comprises the polyimidesiloxane solution composition of this invention is used from the preparation stage of a polyimidesiloxane, it is efficient when preparing the polyimidesiloxane solution composition of this invention.

The polyimide siloxane may be obtained by any method such as a) to b), but is at least 3% by mass, preferably 5 to 60% by mass, particularly 5 to 50% by mass in the organic solvent. It can be dissolved at a high concentration, and the solution viscosity at 25 ° C. (E-type rotational viscometer) is preferably 1 to 10,000 poise, particularly preferably 1 to 100 poise.
Polyimidesiloxane preferably has a high molecular weight and further preferably has a high imidization rate. Logarithmic viscosity (measurement concentration: 0.5 g / 100 ml, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30 ° C.) as a measure of molecular weight is 0.15 or more, particularly 0.16 to 2 This is preferable from the viewpoint of mechanical properties such as strength and elongation of the cured insulating film. Further, it is preferable that the imidation ratio obtained from the infrared absorption spectrum is 90% or more, particularly 95% or more, and substantially 100%.

The curable component which comprises the polyimidesiloxane solution composition of this invention is comprised including an epoxy compound and / or a polyvalent isocyanate compound.
The epoxy compound is preferably a liquid or solid epoxy resin having an epoxy equivalent of about 100 to 4000 and a molecular weight of about 300 to 10,000. For example, bisphenol A type or bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: Epicoat 806, Epicoat 825, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1055AF, Epicoat 1004AF, Epicoat 1007, Epicoat 1009, Epicoat 1010, etc.) Trifunctional or higher functional epoxy resin (Japan Epoxy Resins Co., Ltd .: Epicoat 152, Epicoat 154, Epicoat 180 Series, Epicoat 157 Series, Epicoat 1032 Series, Ciba-Geigy: MT0163, etc. ), Hiker ETBN 1300 × 40 manufactured by Ube Industries, Ltd., Denarex R-45EPT manufactured by Nagase ChemteX Corporation, epoxy-modified poly Rokisan (Shin-Etsu Chemical Co., Ltd., etc. KF105), and the like.

Any polyvalent isocyanate may be used as long as it has two or more isocyanate groups in one molecule. Examples of such polyisocyanate compounds include aliphatic, alicyclic or aromatic diisocyanates, such as 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 (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate -To, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate Cyanate - theft, etc. can be mentioned. In the present invention, a polyisocyanate having an adduct type structure added to trimethylolpropane by a urethane bond is suitable for improving the flame resistance of the cured insulating film.
Further, as the polyvalent isocyanate compound, those derived from aliphatic, alicyclic or aromatic polyvalent isocyanates such as isocyanurate-modified polyisocyanate, burette-modified polyisocyanate, It may be a urethane-modified polyvalent isocyanate.

As the polyvalent isocyanate compound, a blocked polyvalent isocyanate in which the isocyanate group is blocked with a blocking agent is preferably used.
Examples of the blocking agent include alcohol, phenol, active methylene, mercaptan, acid amide, acid imide, imidazole, urea, oxime, amine, and imide. There are compounds, pyridine compounds, etc., and these may be used alone or in combination. Specific blocking agents include alcohols such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methylcarpitol, benzyl alcohol, Cyclohexanol, etc., phenolic, phenol, cresol, ethyl phenol, butyl phenol, nonyl phenol, dinonyl phenol, styrenated phenol, hydroxybenzoate, etc., active methylene As systems, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc., as mercaptans, as butyl mercaptan, dodecyl mercaptan, etc., as acid amides, as acetanilide, acetate amide, ε-caprolactam, δ-valero Lactam, γ-Butirola Kutam, etc., acid imide series, succinimide, maleic imide, imidazole series, imidazole, 2-methylimidazole, urea series, urea, thiourea, ethylene urea etc., oxime series, Formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc., amine type, diphenylamine, aniline, carbazole, etc., imine type, ethyleneimine, polyethyleneimine, etc., bisulfite, bisulfite soda Examples of pyridine-based compounds include 2-hydroxypyridine and 2-hydroxyquinoline.

Examples of the block polyisocyanate include Vernock D-500 (tolylene diisocyanate blocked) and D-550 (1,6-hexamethylene diisocyanate block) manufactured by Dainippon Ink and Chemicals, Inc. ), Takenate Takenate B-830 (tolylene diisocyanate blocked) manufactured by Mitsui Takeda Chemical Co., Ltd., B-815N (4,4′-methylenebis (cyclohexyl isocyanate) blocked), B— 842N (1,3-bis (isocyanatemethyl) cyclohexane blocked), B-846N (1,3-bis (isocyanatemethyl) cyclohexane blocked), B-874N (isophorone diisocyanate blocked) , B-882N (1,6-hexamethylene diisocyanate blocked) Duranate MF-B60X (1,6-hexamethylene diisocyanate blocked product) manufactured by Asahi Kasei Co., Ltd., Duranate MF-K60X (1,6-hexamethylene diisocyanate blocked product), Daiichi Kogyo Seiyaku Co., Ltd. Elastolone BN-P17 (4,4′-diphenylmethane diisocyanate block), Elastolon BN-04, Elastolon BN-08, Elastolon BN-44, Elastolon BN-45 (above, urethane-modified polyisocyanate) Preferable examples include 3 to 5 functional groups per molecule of a blocked compound, all of which are water emulsion products that can be used after drying and isolation.

In the polyimidesiloxane solution composition of the present invention, at least one curable component selected from the group consisting of an epoxy compound and a polyvalent isocyanate compound is 1 to 50 parts by mass, preferably 1 to 40 parts per 100 parts by mass of polyimidesiloxane. More preferably, it is 5-40 mass parts rather than mass parts. If the amount used is more than the above range, phase separation is likely to occur, the adhesiveness of the cured insulating film to the base material or sealing material is reduced, or the bending resistance or heat resistance is too low. The above range is preferable because the heat resistance and chemical resistance of the cured insulating film are deteriorated.
More specifically, in the present invention, an epoxy compound alone or a combination of an epoxy compound and a blocked polyvalent isocyanate compound is preferably used. In the combination of the epoxy compound and the block polyvalent isocyanate compound, the epoxy compound is used in a combination of 0.5 to 30 parts by mass and the block polyvalent isocyanate compound in an amount of 2 to 40 parts by mass with respect to 100 parts by mass of the polyimidesiloxane. It is preferable because it can be easily cured at a low temperature of about 130 ° C. or lower and the adhesiveness of the cured insulating film to the sealing material is improved.

  The polyimidesiloxane composition of the present invention contains a silicone antifoaming agent. In the polyimidesiloxane solution composition, a silicone antifoaming agent is effective for improving the foam removal properties. With other types of antifoaming agents, it is not always possible to obtain effective defoaming properties. Polyimide siloxane has a low surface energy and weak cohesion due to its siloxane skeleton. In order to cause bubbles to break by acting on this, the defoaming effect cannot be sufficiently exhibited unless it has an affinity for polyimide siloxane and its surface energy and cohesive force are lower than those of polyimide siloxane. The content of the silicone antifoaming agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the organic solvent-soluble polyimidesiloxane.

  However, as described in Patent Document 1, when a silicone antifoaming agent made of ordinary dimethylpolysiloxane is used, the cured insulating film obtained from the composition for polyimidesiloxane insulating film is not only on its surface but also on its periphery. For example, when an electrical junction is formed with an anisotropic conductive film in the periphery of the cured insulating film, sufficient adhesion cannot be obtained and reliability cannot be ensured.

  On the other hand, in patent document 1, the above-mentioned repellency was suppressed by employ | adopting the silicone antifoamer containing the polysiloxane compound which has a hydrophilic group in a side chain or a terminal part. Also in the polyimidesiloxane solution composition of the present invention, a silicone antifoaming agent containing a polysiloxane compound having a hydrophilic group in the side chain or terminal portion described in Patent Document 1 can be preferably used. The silicone antifoaming agent containing a polysiloxane compound having a hydrophilic group in the side chain or terminal portion is as described in detail in Patent Document 1.

  Examples of the silicone antifoaming agent of the present invention include ordinary silicone antifoaming agents such as DB-100 manufactured by Dow Corning, KS-69 manufactured by Shin-Etsu Chemical Co., Ltd., and TSA-750 manufactured by Toshiba Silicone Co., Ltd. Can be mentioned. Furthermore, a silicone antifoaming agent containing a polysiloxane compound having a hydrophilic group other than a methyl group in the side chain or terminal portion, such as KS531, KS538 manufactured by Shin-Etsu Chemical Co., Ltd., or DC-75 manufactured by Dow Corning, is suitably used. Can be mentioned.

  The polyimidesiloxane solution composition of the present invention is characterized in that (A) a solvent composed of glymes and (B) a solvent selected from the group consisting of amides, pyrrolidones, anones and mixtures thereof are used as the organic solvent. A coating film was formed with this solution composition by using a mixed organic solvent mixed in a ratio ((A) / (B)) of 85/15 to 99/1, preferably 87/13 to 97/3. It is the point which improved so that the foam which arises in the case may be easily broken and it may become a uniform coating film in a very short time. In this mixed organic solvent, when the solvent (B) is less than 90/1, the bubble removal time becomes long and the effect of the present invention cannot be obtained. When the ratio of the solvent (B) exceeds 85/15, the solvent tends to remain in the cured insulating film. For example, when the cured insulating film is exposed to a high temperature in the soldering process, a swelling phenomenon that is caused by evaporation of the remaining solvent. This is not preferable because solder heat resistance is reduced. Furthermore, when the ratio of the solvent (B) is less than 90/1, the solution stability of the polyimidesiloxane solution composition is deteriorated, and the viscosity may be increased in a relatively short time, or solid-liquid separation may occur. In the polyimidesiloxane solution composition of the present invention in which the solvent (B) is mixed at a ratio exceeding 90/1, the solution stability is improved and the viscosity can be stabilized even after a long time.

  The solvent (A) is a solvent having a low affinity for polyimidesiloxane. For this reason, for example, 90% or more is vaporized and removed by heating at 80 ° C. for 30 minutes, so that scattering of the siloxane component that causes repelling is suppressed. On the other hand, the solvent (B) is a solvent having a high affinity for polyimide siloxane, and is present around the polyimide siloxane molecules to weaken the interaction between the polyimide siloxane molecules. It is thought to be promoted. However, when the solvent (B) is used in a proportion of a certain amount or more, it cannot be easily removed at a normal heat treatment temperature for curing the coating film, and the certain amount remains. When the remaining amount in the cured insulating film exceeds 1000 ppm, solder heat resistance (for example, at 260 ° C. for 10 seconds) cannot be satisfied as described above. When the residual amount in the cured insulating film is 1000 ppm or less, there is almost no influence of the residual solvent, preferably 500 ppm or less, more preferably 100 ppm or less, which can be ignored in practice.

  Glymes used in the mixed organic solvent are ether group-containing compounds such as ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), and tetraethylene glycol dimethyl ether (tetraglyme). Amides are amide group-containing compounds such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, and pyrrolidones are exemplified by N-methyl- A compound having a pyrrolidone skeleton such as 2-pyrrolidone or N-vinyl-2-pyrrolidone. Anones include, for example, carbons such as cyclopentanone, cyclohexanone, and cyclooctanone. An alkenyl group-containing cyclic compound.

Each component of these mixed solvents preferably has a boiling point of 140 ° C. or higher, more preferably a boiling point of 160 to 240 ° C. If the boiling point is too low, the solvent is likely to evaporate in the mixing step or the like, and it is difficult to adjust the concentration and viscosity. If the boiling point is too high, it remains in the cured insulating film and lowers the heat resistance and mechanical performance. In the present invention, the solvent (A) is preferably triglyme, diglyme or a mixture thereof, and the solvent (B) is preferably dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, cyclohexanone or any of them. A mixture of these.
In addition, although these mixed solvents are not specifically limited, 50 mass parts-500 mass parts are normally used with respect to 100 mass parts of organic solvent soluble polyimidesiloxane.

Furthermore, it is preferable that the polyimidesiloxane solution composition of this invention contains a fine inorganic filler. As the fine inorganic filler, those having an average particle diameter of 0.001 to 15 μm, particularly 0.005 to 10 μm are preferable. Use of a material outside this range is not preferable because a cured insulating film obtained is cracked and a bent portion is whitened. As the fine filler, for example, fine inorganic fillers such as Aerosil, talc, mica, barium sulfate, which are fine powdered silica, can be preferably cited. In the present invention, a combination of at least one of aerosil and talc, mica and barium sulfate, particularly a combination of aerosil, talc and barium sulfate is preferably used as the fine inorganic filler.
These fine fillers are used to adjust the viscosity when forming a coating film by screen printing or the like and to improve the properties of the cured insulating film. However, when such a fine filler is added, the solution composition has a high viscosity and particularly thixotropic properties, so that the defoaming property is inevitably lowered, and the solution composition is produced by a process or screen printing. In the process of forming a coating film, workability is significantly reduced. The polyimide siloxane solution composition of the present invention has good foam removal properties even when it contains a fine inorganic filler. Therefore, the workability in the process of producing a solution composition or the process of forming a coating film by screen printing, etc. Is good.

  The amount of the fine inorganic filler used is preferably 20 to 150 parts by weight, particularly 40 to 125 parts by weight in total with respect to 100 parts by weight of polyimidesiloxane. If the amount used is less than the above range, the printability, tin dipping and tin foil discoloration at the time of tin plating cannot be improved, and if the amount used is more than the above range, cracks may occur due to bending of the coating film. The above range is preferable because it tends to occur.

Furthermore, the polyimidesiloxane solution composition of the present invention includes at least one selected from the group consisting of a dissociation catalyst that dissociates the blocking agent of the block polyvalent isocyanate at a certain temperature or higher, and an epoxy compound and a polyvalent isocyanate compound. It is preferable to contain the curing catalyst which consists of a curing acceleration catalyst which accelerates | stimulates the curing reaction of the curable component of this, and the polar group of polyimidesiloxane.
Examples of the dissociation catalyst for the block polyvalent isocyanate compound include dibutyltin dilaurate and tertiary amines. The amount of the dissociation catalyst is preferably 0.01 to 25 parts by mass, particularly preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the block polyvalent isocyanate compound.
Examples of the curing accelerating catalyst include imidazoles such as 2-methyl-4-methylimidazole and tertiary amines. The amount of the curing accelerating catalyst is preferably about 0.01 to 25 parts by mass, particularly preferably about 0.1 to 15 parts by mass with respect to 100 parts by mass of the block polyvalent isocyanate.

When the polyimidesiloxane solution composition of the present invention contains an epoxy compound and a blocked polyvalent isocyanate compound, it contains a tertiary amine that can exhibit both functions of a dissociation catalyst and a curing acceleration catalyst as a curing catalyst. It is particularly preferred that
Examples of the tertiary amine include 1,8-diazabicyclo [5.4.0] -7-undecene (abbreviated as DBU; the same shall apply hereinafter), N, N-dimethylbenzylamine, N, N, N ', N'-tetramethylhexanediamine, triethylenediamine (TEDA), 2-dimethylaminomethylphenol (DMP-10), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), dimorpholinodiethyl Examples include ether (DMDEE), 1,4-dimethylpiperazine, cyclohexyldimethylamine, and the like. In particular, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), dimethylbenzylamine, N, N, N ′, N′-tetramethylhexanediamine is suitable as a blocking agent from blocked isocyanate. It can be dissociated at a suitable temperature, and the crosslinking reaction of the polyimide siloxane with the epoxy compound and the polyvalent isocyanate compound can be promoted to an appropriate rate.

  The usage-amount of a tertiary amine is 0.5-20 mass parts with respect to 100 mass parts of organic solvent soluble polyimide siloxane, Preferably it is 1-10 mass parts. When the amount used is more than the above range, the solvent resistance and electrical properties are deteriorated, and when it is too small, it takes a long time for curing at a low temperature, so the above range is preferable.

  Furthermore, in the polyimidesiloxane solution composition of the present invention, the organic coloring pigment and the inorganic coloring pigment can be used in a predetermined amount, for example, about 0.1 to 100 parts by mass with respect to 100 parts by mass of the organic solvent-soluble polyimidesiloxane. .

  The polyimidesiloxane solution composition of the present invention comprises an organic solvent-soluble polyimidesiloxane, at least one curable component selected from the group consisting of an epoxy compound and a polyvalent isocyanate compound, a silicone antifoaming agent, and, if necessary, a fine filler A weight ratio of (A) a solvent consisting of glymes and (B) a solvent selected from the group consisting of amides, pyrrolidones, anones and any mixture thereof ((A) / (B)) can be easily obtained by uniformly dissolving in a mixed organic solvent mixed at a ratio of 85/15 to 99/1. In preparing a solution composition by dissolving in an organic mixed solvent, a polyimide siloxane prepared in advance with a predetermined mixed solvent and the solution as it is or diluted may be used. Although not particularly limited, workability such as screen printing and physical properties of the solution can be obtained when the solution viscosity at room temperature (25 ° C.) is 50 to 10000 poise, particularly 100 to 1000 poise, and further 100 to 600 poise. This is appropriate in view of the characteristics of the cured insulating film.

  The polyimide siloxane solution composition of the present invention is as described above, and can be satisfactorily applied on a substrate such as a flexible wiring board by a method such as screen printing, and is cured and insulated by heat treatment at a relatively low temperature. Films can be formed, and the resulting cured insulating film has excellent adhesion to the substrate, is less likely to warp, has heat resistance, solvent resistance, chemical resistance (small tin sunk), and bending resistance In particular, the cured insulating film has excellent properties and electrical characteristics, and particularly has good bubble removal properties as a solution composition (the bubble removal time is preferably 100 seconds or less, more preferably 50 seconds or less in the measurement method of the present invention). The workability at the time of forming can be remarkably improved. More preferably, repelling that causes adhesion failure is suppressed in the peripheral portion of the cured insulating film obtained by applying the solution composition to the substrate and then heat-treating (preferably the repelling distance is measured by the measurement method of the present invention). A highly reliable electrical joint can also be obtained by an anisotropic conductive material such as an anisotropic conductive film or an anisotropic conductive paste. Preferably, the cured insulating film obtained in the present invention has good adhesion to a sealing material such as an underfill material.

  Next, a method for mounting a wiring board according to the present invention will be described. A wiring board mounting method according to the present invention includes a step of forming a cured insulating film partially covering the electric circuit wiring portion on the surface of the wiring board on which the electric circuit wiring portion is formed. In particular, a cured insulating film partially covering the electric circuit wiring part is formed on the surface of the wiring substrate on which the electric circuit wiring part is formed, and then anisotropic to the electric circuit wiring part not covered with the cured insulating film. In the method for mounting a wiring board comprising a step of forming an electrical junction with a conductive material, the cured insulating film is selected from the group consisting of an organic solvent-soluble polyimide siloxane, an epoxy compound, and a polyvalent isocyanate compound in an organic solvent. At least one curable component and a silicone antifoaming agent, wherein the organic solvent is a solvent comprising (A) a glyme and (B) an amide, pyrrolide Polysiloxane having a mixed organic solvent in which a weight ratio ((A) / (B)) is mixed in a ratio of 85/15 to 99/1 with a solvent selected from the group consisting of alkanols, anones, and mixtures thereof It is formed using a solution composition. The mounting method of the present invention is based on a conventionally well-known wiring board mounting method except for the above features.

FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a wiring board mounted such that an inner lead part is joined to a chip component and an outer lead part is joined to an electrode of a liquid crystal device by ACF or ACP. .
Such wiring board mounting is generally performed by the following procedure.
1) A wiring board made of a polyimide film insulating substrate 1 having an electric circuit wiring 2 formed on the surface is prepared. If necessary, the surface of the electric circuit wiring 2 is tin-plated.
2) A polyimide siloxane solution composition is applied to a predetermined portion of the surface of the wiring board by screen printing, and the resulting coating film is heat-treated at 50 ° C. to 210 ° C. to form the cured insulating film 3. This heat treatment is usually performed at a temperature of about 160 ° C. However, when tin is already plated, the heat treatment is performed at a relatively low temperature of about 120 ° C.
3) The tin plating layer 4 is formed on the surface of the wiring not covered with the cured insulating film. If tin has already been plated, this step may be omitted.
4) The chip component 5 is electrically joined to the wiring part (inner lead part) not covered with the cured insulating film by the gold bumps 6 or the like.
5) An underfill material 7 made of a curable resin such as an epoxy resin is injected into the gap between the insulating substrate 1 of the polyimide film and the chip component 5 and is usually cured by heat treatment at a temperature of about 150 ° C. to 160 ° C.
6) The electrode 9 of the substrate 10 of the liquid crystal panel is bonded by thermocompression bonding to the wiring portion (outer lead portion) not covered with the cured insulating film of the wiring substrate using ACF or ACP8.

  The wiring board mounting method of the present invention is characterized in that the polyimidesiloxane solution composition of the procedure 2) is the polyimidesiloxane solution composition of the present invention. In the present invention, the polyimide siloxane solution composition has good defoaming property (defoams in a short time), and therefore it does not require a long time for defoaming of the screen-printed coating film. Workability is remarkably improved and a uniform cured insulating film can be easily obtained. Preferably, the cured insulating film has good adhesion to the underfill material used in the procedure 5), and the electrode 9 of the liquid crystal panel substrate 10 and the cured insulating film of the wiring substrate formed in the procedure 6). Bonding with the wiring portion not covered with the wire has sufficient adhesive force and is highly reliable electrical bonding.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. In addition, this invention is not limited to a following example.

  In the present invention, the defoaming property is determined by using a screen mask (SUS # 180, emulsion thickness 20 μm, mesh thickness 150 μm) on a transparent PET film (Lumilar S105 manufactured by Toray Industries, Inc.) having a size of 5 mm × 15 mm. Hardness: 70, Material: Silicone rubber) was used to print a polyimide siloxane solution composition with a Neolong printing machine to form a coating film, and the coating film was observed with a 10 × optical microscope under transmitted light. . By forming the coating film with a printing machine, fine bubbles are generated in the coating film, but the time until the fine bubbles are completely eliminated by the transmitted light from the transparent film was measured. The measurement was performed three times, and the average value was taken as the bubble removal time.

In the present invention, a sample for evaluating repelling is a 35 μm thick electrolytic copper foil (Fukuda metal foil powder) using a screen mask (SUS # 180, emulsion thickness 20 μm, mesh thickness 150 μm) and a squeegee (hardness: 70, material: silicone rubber). A polyimide siloxane solution composition was applied on the mirror surface of CF-T8) manufactured by Kogyo Co., Ltd., then cured by heating for 1 hour at a temperature of 150 ° C., followed by tin plating to prepare a sample for evaluation of repelling.
Evaluation of repellency was performed by Wako Pure Chemical Industries, Ltd., a mixed solution No. for wet tension test. Use 35.0 to drop 0.1 mL about 1 cm from the edge of the cured insulating film with a dropper, bring the wet tension test mixture near the edge of the cured insulating film with the tip of the dropper, and cure with the edge of the cured insulating film in between. Wet the copper foil surface from the insulating film surface. Then, the distance of the copper foil surface in which the liquid mixture for a wet tension test was repelled from the case of the cured insulating film was measured. The greater the repelled distance, the greater the degree of repelling.

  In the present invention, the residual solvent ratio is determined by precisely weighing a predetermined amount of the cured insulating film obtained by heat treatment at a temperature of 150 ° C. for 60 minutes and enclosing it in a vial, and after heat treatment at a temperature of 230 ° C. for 2 hours. The gas in the bottle was extracted with a 0.5 mL syringe and measured by GC-MS analysis. The residual solvent ratio was expressed by (unit: mass of residual solvent) / (mass of cured insulating film sample) in ppm.

  In the present invention, the adhesion of the cured insulating film to the sealing material was evaluated as follows. A polyimide siloxane solution composition is applied onto the mirror surface of 35 μm thick electrolytic copper foil (CF-T8 manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.), and heat-treated at 80 ° C. for 30 minutes and then at 150 ° C. for 60 minutes to form a cured insulating film. Obtained. An IC chip sealing material CEL-C-5020 (manufactured by Hitachi Chemical Co., Ltd.) is dropped onto the cured insulating film so as to form a circle having a thickness of about 1 mm and a diameter of about 6 mm, and heated at 160 ° C. for 2 hours. It processed and hardened and it was set as the sample. This sample was bent by hand, and the peeling of the sealing material was observed. The evaluation is based on the observation result, when the entire surface is cohesive fractured with the cured insulating film and when the cured insulating film / copper foil interface peeling is good, and the entire surface is the cured insulating film / sealing material interface peeling , And the entire surface was determined to be 4/4, the entire surface was determined to be 0/4, and in other cases, it was determined to be 1/4 to 3/4 according to the good area and the defective area.

The materials used in the following examples are as follows.
[Epoxy compound]
Epicoat 828: manufactured by Japan Epoxy Resin Co., Ltd., epoxy resin, epoxy equivalent: 190
Epicoat 157S70: manufactured by Japan Epoxy Resin, epoxy resin, epoxy equivalent: 210
[Polyisocyanate compound]
B-882N: Takenate B-882N, manufactured by Mitsui Takeda Chemical Co., Ltd., 1,6-hexamethylene diisocyanate blocked, blocking agent: methyl ethyl ketoxime [antifoaming agent]
KS538: Silicone defoaming agent manufactured by Shin-Etsu Chemical Co., Ltd. (self-emulsifying compound type silicone defoaming agent containing polysiloxane in which about 90% of the substituents are methyl groups and about 10% are hydrophilic polyoxyalkylene groups)
TSA-750: manufactured by Toshiba Silicone Co., Ltd., silicone antifoaming agent (compound type silicone antifoaming agent comprising dimethylpolysiloxane)
[Curing catalyst]
2E4MZ: manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-ethyl-4-methylimidazole DBU: manufactured by Aldrich, 1,8-diazabicyclo [5.4.0] -7-undecene [inorganic filler]
Aerosil # 50: Nippon Aerosil Co., Ltd., average particle size 30 nm
Aerosil # 130: Nippon Aerosil Co., Ltd., average particle size 16 nm
Talc P-3: Talc manufactured by Nippon Talc, Microace P-3, average particle size 5.1 μm
Barium sulfate B-30: Barium sulfate manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.3 μm

[Reference Example 1]
Production of polyimide siloxane solution:
In a glass flask having a volume of 500 mL, 47.1 g (0.16 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 90 g of a solvent triglyme (hereinafter sometimes abbreviated as TG) Was stirred at 180 ° C. under a nitrogen atmosphere. 125.1 g (0.136 mol) of α, ω-bis (3-aminopropyl) polydimethylsiloxane (amino equivalent 460) and 40 g of TG were added, and the mixture was heated and stirred at 180 ° C. for 60 minutes. Further, 6.9 g (0.024 mol) of 3,3′-carboxy-4,4′-diaminodiphenylmethane (MBAA) and 39 g of TG were added to this reaction solution, followed by heating and stirring at 180 ° C. for 10 hours, followed by filtration. . The resulting polyimidesiloxane reaction solution was a solution having a polymer solid content concentration of 67% by weight and ηinh of 0.20. The imidization rate was substantially 100%.

[Example 1]
In a glass container, 30.0 g of the polyimidesiloxane solution obtained in Reference Example 1 is added to 8 g of TG and 2 g of cyclohexanone (resulting in 90 parts by mass of TG and 10 parts by mass of cyclohexanone with respect to 100 parts by mass of polyimidesiloxane solids. The same applies hereinafter. ), Epoxy resin Epicoat 157S70 0.38 g (2 parts by mass), curing catalyst 2E4MZ 0.04 g (0.2 parts by mass), DBU 0.16 g (0.8 parts by mass), 0.9 g (5 parts by mass) of KS531 as a foaming agent, 0.8 g (4 parts by mass) of Aerosil 50 as an inorganic filler, 3.3 g (16.5 parts by mass) of Aerosil 130, and Microace P of talc -3 (9.1 g (45.5 parts by mass)) and barium sulfate B-30 (4.5 g (22.5 parts by mass)) were charged and stirred uniformly at 25 ° C. for 2 hours. To obtain a combined polyimide siloxane solution composition.
Table 1 shows the measurement results of the composition of the polyimide siloxane solution composition, the foam removal property, the residual solvent ratio of the cured insulating film, and the repelling distance.

[Examples 2 to 7]
A polyimidesiloxane composition having the composition shown in Table 1 was obtained in the same manner as in Example 1. Table 1 shows the measurement results of the composition of these polyimide siloxane compositions, foam removal properties, residual solvent ratio of the cured insulating film, and repelling distance.

[Comparative Examples 1-4]
A polyimidesiloxane composition having the composition shown in Table 1 was obtained in the same manner as in Example 1. Table 1 shows the measurement results of the composition of these polyimide siloxane compositions, foam removal properties, residual solvent ratio of the cured insulating film, and repelling distance. In Comparative Examples 1 to 3, there was room for further improvement in the foamability of the solution composition. In Comparative Example 4, the residual solvent ratio of the effect insulating film was extremely high.

  The present invention is an improved method for mounting a wiring board comprising a step of forming a cured insulating film partially covering the electric circuit wiring part on the surface of the wiring board on which the electric circuit wiring part is formed. Provided are an improved mounting method for mounting an electronic component with an anisotropic conductive material on a wiring board having a cured insulating film formed of a polyimidesiloxane solution composition, and a polyimidesiloxane solution composition suitable for such a mounting method. can do. According to this mounting method, since the bubble-removing property is improved, the process of forming a coating film by screen printing or the like and then obtaining a cured insulating film by heat treatment becomes very easy, and the work efficiency can be improved and homogeneous. A hardened insulating film can be easily formed.

FIG. 5 is a schematic cross-sectional view of a wiring board mounted with an inner lead portion bonded to a chip component and an outer lead portion bonded to an electrode of a liquid crystal device by ACF or ACP.

Explanation of symbols

1: Insulating substrate made of polyimide 2: Electric circuit wiring formed of copper foil 3: Cured insulating film (protective film)
4: Tin plating 5: IC chip component 6: Gold bump 7: Underfill 8: Anisotropic conductive film or anisotropic conductive paste 9: Electrode 10 of liquid crystal panel substrate: Liquid crystal panel substrate

Claims (8)

In the mounting method of the wiring board, comprising a step of forming a cured insulating film partially covering the electric circuit wiring part on the surface of the wiring board on which the electric circuit wiring part is formed.
The cured insulating film comprises an organic solvent-soluble polyimide siloxane in an organic solvent, at least one curable component selected from the group consisting of an epoxy compound and a polyvalent isocyanate compound, and a silicone antifoaming agent. (A) Polyimidesiloxane composed of a mixed organic solvent in which a solvent composed of glymes and a solvent composed of (B) anones are mixed at a weight ratio ((A) / (B)) of 85/15 to 99/1. A method for mounting a wiring board, wherein the wiring board is formed using a solution composition. A cured insulating film partially covering the electric circuit wiring part is formed on the surface of the wiring board on which the electric circuit wiring part is formed, and then anisotropic conductive is applied to the electric circuit wiring part not covered with the cured insulating film. In a method for mounting a wiring board, including a step of forming an electrical junction by a material,
The cured insulating film comprises an organic solvent-soluble polyimide siloxane in an organic solvent, at least one curable component selected from the group consisting of an epoxy compound and a polyvalent isocyanate compound, and a silicone antifoaming agent. (A) Polyimidesiloxane composed of a mixed organic solvent in which a solvent composed of glymes and a solvent composed of (B) anones are mixed at a weight ratio ((A) / (B)) of 85/15 to 99/1. The wiring board mounting method according to claim 1, wherein the wiring board is formed using a solution composition. Organic Solvent soluble polyimide siloxane polyimide siloxane solution composition, (a) a tetracarboxylic acid compound, diamino polysiloxane 30-95 mol% represented by general formula (1), the aromatic diamine 0.5 having a polar group The organic solvent-soluble polyimide siloxane obtained from -40 mol% and a diamine compound consisting of 0 to 69.5 mol% of a diamine compound other than the diamine, according to any one of the preceding claims. Wiring board mounting method.

(In the formula, R ₁ represents a divalent hydrocarbon group or an aromatic group, R ₂ independently represents a monovalent carbon hydrogen group or an aromatic group, and n 1 represents an integer of 1 to 50.) Wherein the polyimide siloxane solution composition, the organic Solvent-soluble polyimide siloxane 100 parts by weight of an epoxy compound and contain 1 to 50 parts by weight of the curable component of at least one member selected from the group consisting of polyvalent isocyanate compound The method for mounting a wiring board according to any one of claims 1 to 3. Polyimide siloxane solution composition according to any one of the preceding claims, characterized in organic Solvent-soluble polyimide siloxane 100 parts by weight, in that it contains 0.1 to 10 parts by weight of a silicone antifoam Wiring board mounting method.   The method for mounting a wiring board according to any one of claims 1 to 5, wherein the solvent comprising the (A) glyme of the mixed solvent of the polyimidesiloxane solution composition is triglyme, diglyme, or a mixture thereof. . The wiring board according to any one of claims 1 to 6, wherein the solvent consisting of (B) anones of the mixed solvent of the polyimidesiloxane solution composition is cyclopentanone, cyclohexanone, or a mixture thereof. Implementation method. A cured insulating film partially covering the electric circuit wiring part is formed on the surface of the wiring board on which the electric circuit wiring part is formed, and then anisotropic conductive is applied to the electric circuit wiring part not covered with the cured insulating film. In a method for mounting a wiring board, including a step of forming an electrical junction by a material,
The cured insulating film is made of an organic solvent-soluble polyimide siloxane in an organic solvent, at least one curable component selected from the group consisting of an epoxy compound and a polyvalent isocyanate compound, and dimethylpolysiloxane and hydrophilic in the side chain or at the end. A silicone antifoaming agent that does not contain a polysiloxane compound having a group , and the organic solvent is (A) a solvent composed of glymes, and (B) amides, pyrrolidones, anones, and any mixture thereof. A polyimide siloxane solution composition comprising a mixed organic solvent in which a weight ratio ((A) / (B)) is mixed with a solvent selected from the group consisting of 85/15 to 99/1. A wiring board mounting method characterized by the above.

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