JP2006152017A - Composition for polyimide siloxane insulating film, insulating film and method for forming insulating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an insulating film being a solution composition, excellent in storage stability and printability, capable of forming an insulating film obtained by applying the composition to, for instance, a flexible wiring board or the like and drying and curing the composition, substantially free from curl and excellent in bending resistance, an electric insulation property, heat/moisture resistance (PCT), resistance to soldering and adhesiveness, etc., to a base material or a sealing material, and particularly improved in tin-plating resistance. <P>SOLUTION: The composition for polyimidesiloxane insulating film comprises (a) 100 pts.wt. polyimidesiloxane being soluble in organic solvents and obtained from a diamine component composed of 30-95 mol% diaminopolysiloxane, 0.5-40 mol% aromatic diamine having a polar group and 0-69.5 mol% aromatic diamine other than the diamine, (b) 1-50 pts.wt. epoxy compound and/or polyvalent isocyanate compound, (c) 1-70 pts.wt. calcium carbonate and (d) organic solvent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a polyimide siloxane insulating film composition comprising a soluble polyimide siloxane, an epoxy compound and / or a polyvalent isocyanate compound, calcium carbonate, and an organic solvent, an insulating film, and a method for forming the insulating film.
The composition for polyimide siloxane insulating film of the present invention has good storage stability (relatively low viscosity is maintained almost constant for a long time) and printability, and the solution composition is applied to, for example, a flexible wiring board. When the insulating film is formed by drying and curing, the insulating film does not substantially cause curling, and is flexible, electrically insulating, heat and humidity resistant (PCT), solvent resistant, The present invention relates to an electrically insulating protective film having good solderability, adhesion to a base material, and the like, and particularly improved tin plating resistance (tin submergence).

Conventionally, the use of an aromatic polyimide, an epoxy resin, or the like as an electrically insulating protective film is known for use in insulating films such as solid element insulating films, semiconductor integrated circuits, and flexible wiring boards.
The epoxy resin has plating resistance and good adhesion to the substrate, but the insulating film formed by thermosetting has a problem that it is rigid, has low flexibility, and is inferior in flexibility.
Aromatic polyimide is difficult to dissolve in organic solvents, so a coating film is formed as an aromatic polyimide precursor (aromatic polyamic acid) solution, and then heat-treated at high temperature for a long time to dry and imidize the aromatic polyimide insulation. There is a problem that it is necessary to form a film, and the electrical or electronic member itself to be protected is thermally deteriorated.

  Patent Document 1 discloses an aromatic polyimide that is soluble in an organic solvent obtained by polymerizing and imidizing a biphenyltetracarboxylic acid component and a diamine compound in an organic polar solvent. The polyimide includes a silicon wafer, a glass plate, Since adhesion (adhesiveness) with a flexible substrate or the like was not sufficient, it was necessary to treat the substrate with an adhesion promoter in advance.

Patent Document 2 is a polyimide siloxane composition composed of polyimide siloxane, epoxy resin, fine inorganic filler, and high boiling point solvent, and Patent Document 3 is a polyimide siloxane composition composed of polyimide siloxane, a polyvalent isocyanate compound, and an organic solvent. Is disclosed. Further, Patent Document 4 discloses a polyimide siloxane composition comprising a polyimide siloxane, an epoxy compound and / or a polyvalent isocyanate compound, an organized clay favorite, and an organic solvent.
However, these compositions have room for improvement in tin plating resistance (tin submergence). In particular, in Patent Document 4, although tin plating resistance (tin diving) is improved, there is room for improvement in solvent resistance, and there is room for further improvement in tin plating resistance (tin diving). In the electronic component field, miniaturization, thinning, and improvement of the mounting process are rapidly progressing, and high reliability can be secured even when downsizing, thinning, and improvement of the mounting process are performed. There has been a demand for a composition for high performance insulating films having improved tin plating resistance (tin submergence).

Japanese Examined Patent Publication No. 57-41491 JP-A-11-310754 JP 2001-240650 A JP 2004-79415 A

  An object of the present invention is a solution composition, which has good storage stability (relatively low viscosity is maintained almost constant for a long time) and printability, and is applied to, for example, a flexible wiring board and dried. The insulating film obtained by curing does not cause curling substantially, and has good flexibility, electrical insulation, heat and moisture resistance (PCT), solvent resistance, and adhesion to the substrate. In particular, it is to provide a composition for an insulating film having improved tin-plating resistance (tin diving), an insulating film obtained from the composition, and a method for forming the insulating film.

  The present invention includes (a) a tetracarboxylic acid component, 30 to 95 mol% of a diaminopolysiloxane represented by the general formula (1), 0.5 to 40 mol% of an aromatic diamine having a polar group, and other than the diamine. 100 parts by weight of an organic solvent-soluble polyimide siloxane obtained from 0 to 69.5 mol% of an aromatic 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１〜４０の整数を示す。）
（ｂ）エポキシ化合物及び／又は多価イソシアネート化合物１〜５０重量部
（ｃ）炭酸カルシウム１〜７０重量部、及び
（ｄ）有機溶媒
を含んでなり、加熱処理して得られる絶縁膜が改良された耐スズメッキ性を有することを特徴とするポリイミドシロキサン絶縁膜用組成物に関する。
また、本発明は、加熱処理して得られる絶縁膜が、スズ潜りが３０μｍ未満の耐スズメッキ性を有することを特徴とする前記ポリイミドシロキサン絶縁膜用組成物に関する。

(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 40.)
(B) 1-50 parts by weight of an epoxy compound and / or polyvalent isocyanate compound (c) 1-70 parts by weight of calcium carbonate, and (d) an organic solvent, and an insulating film obtained by heat treatment is improved. The present invention relates to a composition for a polyimide siloxane insulating film, characterized by having a tin plating resistance.
The present invention also relates to the above-mentioned composition for polyimide siloxane insulating film, wherein the insulating film obtained by heat treatment has tin plating resistance with a tin dive of less than 30 μm.

  Furthermore, the present invention relates to a polyimide siloxane insulating film obtained by applying the polyimide siloxane insulating film composition to a substrate and then heat-treating, and applying the polyimide siloxane insulating film composition to the substrate. Thereafter, the present invention relates to a method for forming a polyimidesiloxane insulating film which is heat-treated at 50 to 200 ° C., preferably 70 to 170 ° C.

  The composition for polyimide siloxane insulating film of the present invention has good storage stability and printability. For example, when an insulating film is formed by applying it to a silicon wafer, a flexible wiring board, etc., and drying and curing it, the insulating film is insulated. The film does not substantially cause curling and has good flexibility, electrical insulation, heat and moisture resistance (PCT), solvent resistance, solder resistance, and adhesion to the substrate, etc. In particular, tin plating resistance (tin submergence) is improved.

Preferred embodiments of the composition for polyimide siloxane insulating film of the present invention are shown below.
1) The aromatic diamine having a polar group is a diamine having a hydroxyl group or a carboxyl group.
2) An aromatic diamine other than diaminosiloxane and an aromatic diamine having a polar group is a diamine represented by the general formula (3).
3) The logarithmic viscosity (0.5 g / 100 ml) of polyimidesiloxane is 0.05-3.
4) The maximum particle size of calcium carbonate is less than 10 μm and the average particle size is 5 μm or less.
5) The insulating film obtained by applying heat treatment after coating on the copper foil surface has tin plating resistance with a tin dive of less than 30 μm, preferably less than 20 μm.
6) 2 to 40 parts by weight of epoxy compound and polyvalent isocyanate compound, preferably 0.5 to 20 parts by weight of epoxy compound, or 0.5 to 10 parts by weight of epoxy compound and more than 100 parts by weight of polyimidesiloxane Contains 5 to 25 parts by weight of a polyvalent isocyanate compound.
7) Only an epoxy compound is contained as an epoxy compound and / or a polyvalent isocyanate compound.
8) The epoxy compound and / or the polyvalent isocyanate compound contains both an epoxy compound and a polyvalent isocyanate compound, and further contains a tertiary diamine as a curing catalyst.
9) The organic solvent is a glyme solvent.

The polyimidesiloxane in the present invention is composed of a tetracarboxylic acid component, diaminopolysiloxane 30 to 95 mol%, preferably 50 to 95 mol%, particularly 60 to 90 mol%, aromatic diamine having a polar group 0.5 to 40 mol%, And a diamine component composed of 0 to 69.5 mol% (usually 0 to 30 mol%) of an aromatic diamine other than the diamine, a tetracarboxylic acid component and a diamine component being approximately equimolar, preferably 1 mol of the diamine component The tetracarboxylic acid component can be used in a molar ratio of about 1.0 to 1.2 mol and reacted in an organic solvent. When the ratio of the molar ratio of the tetracarboxylic acid component is larger than the above, the viscosity of the polyimidesiloxane becomes too small, and the printability of the resulting composition for polyimidesiloxane insulating film is lowered, which is not preferable.
As the polyimidesiloxane, one having a logarithmic viscosity (0.5 g / 100 ml) of 0.05 to 3, particularly 0.1 to 1 is preferable.

The reaction can be obtained, for example, by reacting at a relatively low temperature of about 10 ° C. to 80 ° C. to obtain a polyamic acid, and then thermal imidization or chemical imidization of the polyamic acid. Or it can obtain by the one-step reaction which superposes | polymerizes and imidizes at the comparatively high temperature of about 130 to 250 degreeC in an organic solvent, omitting the process made into polyamic acid.
The reaction between the tetracarboxylic acid and the diamine may be a random reaction or a block reaction. For example, you may mix the homoreactant which reacted separately for every diamine seed | species. (In some cases, a recombination reaction may be accompanied.) In addition, an acid component and a diamine component are approximately equimolar with an acid-terminated oligomer prepared in advance with an excess of tetracarboxylic acid and an amine-terminated oligomer prepared with an excess of diamine. It may be mixed and further reacted.
The produced polyimide siloxane can be used as it is without being isolated from the solution.

  Examples of the tetracarboxylic acid component of the polyimide siloxane in the present invention include 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, and 2,3,3. ', 4'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, pyromellitic acid, 2,3,6,7-naphthalene Tetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,2-bis (2 , 5-dicarboxyphenyl) propane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) sulfone, etc. Tetracarboxylic acid, acid dianhydride or ester derivative thereof, alicyclic tetracarboxylic acid such as cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, methylcyclohexenetetracarboxylic acid, acid dianhydride or ester thereof Preferable examples include derivatives.

The said tetracarboxylic acid component may be used individually by 1 type, or may be used in combination of 2 or more type.
2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, and bis (3 When 4-dicarboxyphenyl) ether, their acid dianhydrides or their ester derivatives are used, a high concentration polyimidesiloxane solution can be obtained due to high solubility in a solvent, and an insulating film with high heat resistance can be obtained. Since it can obtain, it is especially suitable.

As the tetracarboxylic acid component of the polyimidesiloxane in the present invention, it is preferable to use a tetracarboxylic dianhydride that can be easily reacted with a diamine.
Further, when the amount of tetracarboxylic dianhydride used is 1.05 times mol or more with respect to the diamine and an unreacted anhydrous ring remains, it may be used as it is, but an esterifying agent may be used. Ring-opening half esterification may be performed. The amount of alcohol used as the esterifying agent is preferably 1.1 to 20 times equivalent, more preferably 1.5 to 5 times equivalent of the excess tetracarboxylic dianhydride. When the proportion of alcohols is small, unreacted anhydrous rings remain, resulting in poor storage stability when the composition of the present invention is used, and excessive alcohols become poor solvents and lower the solid content concentration. In particular, the formation of a coating film by printing is not easy, which is not preferable.
When an esterifying agent is used, the reaction solution may be used as it is, but excess alcohols can be used by heating or distillation under reduced pressure.

  In the present invention, the diamine component of the polyimidesiloxane is 30 to 95 mol%, preferably 50 to 95 mol%, particularly 60 to 90 mol%, 0.5 to 40 mol% of the aromatic diamine having a polar group, and the diamine. It is preferable that it consists of 0-69.5 mol% (usually 0-30 mol%) other than aromatic diamine. If one of the components is too much or too little to fall out of this range, for example, the solubility of the resulting polyimide siloxane in an organic solvent decreases, the compatibility with other organic components deteriorates, and further Insulation film composition using polyimide siloxane is applied to flexible wiring boards and then heat-treated, resulting in a smaller radius of curvature of the insulation film, which tends to cause curling, flex resistance, adhesion, heat resistance, Or it is not preferable because the moisture resistance is lowered.

The diaminopolysiloxane constituting the diamine acid component of the polyimidesiloxane in the present invention is a compound represented by the following general formula (1). Preferably, R ₁ is a divalent hydrocarbon having 1 to 5 carbon atoms. A group or a phenyl group, particularly a propylene group, wherein R2 is an alkyl group or a phenyl group having 1 to 5 carbon atoms, and n1 is 1 to 40, particularly 3 to 30, more preferably 4 to 20. In addition, when diaminopolysiloxane consists of 2 or more types of mixtures, n1 is calculated from an amino equivalent.

（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１〜４０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 40.)

  Specific examples of the diaminopolysiloxane include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4 -Aminophenyl) polydimethylsiloxane, α, ω-bis (4-amino-3-methylphenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis (4- (Aminobutyl) polydimethylsiloxane and the like.

  In the present invention, the aromatic diamine having a polar group constituting the diamine acid component of polyimidesiloxane is preferably a compound represented by the general formula (2).

（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ＣＯＯＨ又はＯＨ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 , r 1 represents COOH or OH; 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 aromatic diamine compound having a polar group include diaminophenol compounds such as 2,4-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′- Hydroxy such as diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-2,2′-dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl Biphenyl compounds, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxy Diphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydro Hydroxydiphenylalkane compounds such as cyphenyl] 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 ′ Hydroxydiphenylsulfone compounds such as diamino-2,2′-dihydroxydiphenylsulfone, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylsulfone, 2,2-bis [4- ( Bis (hydroxyphenoxy) biphenyl compounds such as bis (hydroxyphenoxyphenyl) alkane compounds such as 4-amino-3-hydroxyphenoxy) phenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl And diamine compounds having an OH group such as bis (hydroxyphenoxyphenyl) sulfone compounds such as bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone.

  Furthermore, examples of the aromatic diamine compound having a polar group 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 ′, 5,5′- Carboxybiphenyl compounds such as 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-3 Carboxydiphenylalkane compounds such as carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxybiphenyl 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4,4′-diamino-2,2 Carboxydiphenyl ether compounds such as '-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 Carboxydiphenylsulfone compounds such as 2 ′, 5,5′-tetracarboxydiphenylsulfone, and bis (carboxyphenoxyphenyl) alkanes such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane Compounds, bis (carboxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-carboxyphenoxy) biphenyl, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, etc. Examples thereof include diamine compounds having a COOH group such as bis (carboxyphenoxyphenyl) sulfone compounds.

  An aromatic diamine other than the diaminopolysiloxane and the aromatic diamine having the polar group may be used for the diamine acid component of the polyimidesiloxane of the present invention. The aromatic diamine other than the diaminopolysiloxane and the aromatic diamine having the polar group is preferably a compound represented by the general formula (3).

（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 aromatic diamine compounds other than the diaminopolysiloxane and the aromatic diamine having a polar group include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, Aromatic diamine having two benzene rings such as o-tolidine and m-tolidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis Aromatic diamines having three benzene rings such as (3-aminophenoxy) benzene and 1,4-bis (4-aminophenyl) benzene, or bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 1,4-bis (4-aminophenyl) bifu And aromatic diamines having four benzene rings, such as sulfonyl and the like.

  In the present invention, the organic solvent used in the reaction for preparing polyimidesiloxane includes nitrogen-containing solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethyl. Sulfur-containing atomic solvents such as formamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfol Oxygenated solvents such as amides, such as phenolic solvents such as cresol, phenol, xylenol, diglyme solvents such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme) ), Such Toraguraimu, acetone, ethylene glycol, dioxan, tetrahydrofuran and the like. If necessary, an aromatic hydrocarbon solvent such as benzene, toluene or xylene, or another organic solvent such as solvent naphtha or benzonitrile may be used in combination. N-methyl-2-pyrrolidone, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, γ-butyrolactone, triethyleneglycol -Didimethyl ether, diethylene glycol dimethyl ether and the like can be preferably used. In particular, diglyme solvents are preferred because they have high solubility and low hygroscopicity, and thus have excellent drying characteristics such as not whitening during printing.

  The epoxy compound used in the present invention 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 807, Epicoat 825, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1055, Epicoat 1004AF, Epicoat 1007, Epicoat 1009, Epicoat 1010), tri- or higher functional epoxy resin (manufactured by Japan Epoxy Resin: 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., and Denarex R-45EP manufactured by Nagase ChemteX Corporation And the like.

The polyvalent isocyanate compound used in the present invention may be any compound 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 - door, and the like can be given.
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.

The polyvalent isocyanate used in the present invention is preferably a block polyvalent isocyanate obtained by blocking the isocyanate group of the polyvalent isocyanate with a blocking agent.
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, acetic acid amide, ε-caprolactam, δ-valero Lactam, γ-petitola 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.

  As the block polyvalent isocyanate used in the present invention, in particular, Bernock D-500 (tolylene diisocyanate blocked) manufactured by Dainippon Ink and Chemicals, Inc., D-550 (1,6-hexamethylene diester) Isocyanate blocked), 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 block) ), B-882N (1,6-hexamethylene diisocyanate) Diblockate MF-B60X (1,6-hexamethylene diisocyanate blocked form) manufactured by Asahi Kasei Co., Ltd., duranate MF-K60X (1,6-hexamethylene diisocyanate blocked form), Elastolone BN-P17 (4,4′-diphenylmethane diisocyanate block), manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Urethane-modified polyvalent isocyanate-blocked product having 3 to 5 functional groups per molecule, both of which can be used after drying and isolation in a water emulsion product, can be suitably used.

  In this invention, the usage-amount of an epoxy compound and / or a polyvalent isocyanate compound is 1-50 weight part with respect to 100 weight part of polyimidesiloxane, Preferably it is 2-40 weight part, Especially 2-30 weight part. 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 the sealing material is lowered, or the bending resistance or heat resistance is lowered, which is too small. The above range is preferred because the heat resistance and chemical resistance of the insulating film after curing deteriorate.

  In this invention, only an epoxy compound, the combination of an epoxy compound and a polyvalent isocyanate compound, or only a polyvalent isocyanate compound may be used as an epoxy compound and / or a polyvalent isocyanate compound. When only an epoxy compound is used or a combination of an epoxy compound and a polyvalent isocyanate compound is used, low temperature curability of about 120 ° C. can be secured, which is preferable. In addition, when a combination of an epoxy compound and a polyvalent isocyanate compound is used or only a polyvalent isocyanate compound is used, the adhesiveness with the sealing material is improved, which is preferable. The amount of the epoxy compound used depends on the epoxy equivalent. When an epoxy compound with a small epoxy equivalent is used, it is preferable that the amount used is relatively small. When an epoxy compound with a large epoxy equivalent is used, the amount used may be relatively large. Specifically, the epoxy compound having an epoxy equivalent of 100 to 800 is particularly preferably used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the polyimide siloxane, and the epoxy compound having an epoxy equivalent of more than 800 is polyimide siloxane. It is particularly preferable to use 0.5 to 30 parts by weight with respect to 100 parts by weight. Moreover, in the combination of an epoxy compound and a polyvalent isocyanate compound, the epoxy compound is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight and the polyvalent isocyanate compound is 2 to 30 parts by weight with respect to 100 parts by weight of the polyimidesiloxane. It is particularly preferable to use a combination of 3 to 20 parts by weight.

The composition for polyimide siloxane insulating film of the present invention includes a dissociation catalyst that dissociates the blocking agent of the block polyvalent isocyanate at a certain temperature or higher, a polyvalent isocyanate compound, an epoxy compound, and polyimide siloxane. It is preferable to contain a curing catalyst comprising a curing accelerating catalyst for accelerating the crosslinking reaction between the two.
Examples of the dissociation catalyst for the blocked polyvalent isocyanate include dibutyltin dilaurate and tertiary amines. The amount of the dissociation catalyst is preferably about 0.01 to 25 parts by weight, particularly preferably about 0.1 to 15 parts by weight with respect to 100 parts by weight of the block polyvalent isocyanate.
Examples of the curing accelerating catalyst include imidazoles such as 2-ethyl-4-methylimidazole and tertiary amines. The amount of the curing accelerating catalyst is preferably about 0.01 to 25 parts by weight, particularly preferably about 0.1 to 15 parts by weight with respect to 100 parts by weight of the block polyvalent isocyanate.
In the present invention, a composition added with a tertiary amine capable of exhibiting both the action of a curing accelerating catalyst and a dissociation catalyst is particularly excellent in low-temperature curability and can easily obtain a cured insulating film. Useful.

  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), dimorpholino Preferred examples include diethyl ether (DMDEE), 1,4-dimethylpiperazine, cyclohexyldimethylamine and the like. These tertiary amines dissociate the blocking agent from the blocked polyvalent isocyanate at an appropriate temperature, and accelerate the crosslinking reaction between the polar group in the polyimidesiloxane and the epoxy compound or the polyvalent isocyanate compound at an appropriate rate. Therefore, it can be used very suitably in the composition for polyimide siloxane insulating film of the present invention.

  The amount of the tertiary amine used is 0.3 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyimidesiloxane. If the amount used exceeds the above range, the solvent resistance and electrical properties may deteriorate, and if the amount used is less than the above range, the effect of promoting curing may not be obtained.

The composition for an insulating film of polyimide siloxane of the present invention contains 1 to 70 parts by weight, preferably 2 to 30 parts by weight, particularly 3 to 20 parts by weight of calcium carbonate with respect to 100 parts by weight of polyimide siloxane. By containing calcium carbonate, the composition for polyimide siloxane insulating film of the present invention improves the tin plating resistance (tin tinting) of the resulting insulating film. When the calcium carbonate is less than 1 part by weight, the tin plating resistance is not sufficiently improved. If it exceeds 70 parts by weight, it is difficult to adjust the viscosity, and printability in screen printing or the like is deteriorated.
The calcium carbonate used in the present invention has a maximum particle size of less than 10 μm, preferably less than 7 μm, and an average particle size of 5 μm or less, preferably 3 μm or less, particularly 0.001 to 2.5 μm, more preferably 0.01 to 2 μm. Is preferred. When the maximum particle size is 10 μm or more, it is difficult to obtain a uniform insulating film having a small thickness. On the other hand, if the average particle diameter exceeds 5 μm, tin submergence may not be sufficiently improved.
As such calcium carbonate, for example, A-30 (maximum particle diameter 2 μm, average particle diameter 0.17 μm) manufactured by Ube Material Co., Ltd. and B (maximum particle diameter 5 μm, average particle diameter 1.58 μm) manufactured by Ube Material Co., Ltd. A (manufactured by Ube Material Co., Ltd.) (maximum particle size: 5 μm, average particle size: 0.36 μm).

As the organic solvent used in the composition for polyimide siloxane insulating film of the present invention, the organic solvent used in preparing the polyimide siloxane can be used. Preferably, a nitrogen-containing solvent 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 Sulfur-containing atomic solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfuramide and the like, oxygen-containing solvents such as phenolic solvents such as cresol, phenol, xylenol, etc. Glyme solvents such as diethylene glycol dimethyl ether Diglyme), triethylene glycol - ethyleneglycol dimethyl - ether (triglyme), and tetraglyme, acetone, ethylene glycol, dioxane, tetrahydrofuran and the like. In particular, N-methyl-2-pyrrolidone, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, γ-butyrolactone, tri Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like can be preferably used.
N-methyl-2-pyrrolidone, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, γ-butyrolactone, triethyleneglycol -Didimethyl ether, diethylene glycol dimethyl ether and the like can be preferably used. In particular, diglyme solvents are preferred because they have high solubility and low hygroscopicity, and thus have excellent drying characteristics such as not whitening during printing.

  The composition for polyimide siloxane insulating films of the present invention can be easily obtained by uniformly stirring and mixing predetermined amounts of polyimide siloxane, epoxy compound and / or polyvalent isocyanate compound, calcium carbonate, and organic solvent. When mixed to obtain a polyimidesiloxane solution composition, the polyimidesiloxane reaction solution may be used as it is, or the reaction solution diluted with an appropriate organic solvent may be used. As the organic solvent, use of an organic solvent having a boiling point of 140 ° C. or higher and 210 ° C. or lower, particularly 180 ° C. or higher and further 200 ° C. or higher, such as triglyme, is preferable because dissipation due to evaporation of the organic solvent is extremely reduced. In addition, such an organic solvent is optimal also in performing printing suitably without trouble by screen printing etc.

  In the composition for polyimide siloxane insulating film of the present invention, the amount of the organic solvent used is 50 to 200 parts by weight of the organic solvent with respect to 100 parts by weight of the polyimide siloxane, and the solution viscosity at room temperature is 10 to 600 poise. It is appropriate from the viewpoint of workability as a composition, physical properties of a solution, and characteristics when an insulating film is formed.

  The polyimide siloxane insulating film composition of the present invention may further contain a fine filler other than calcium carbonate, a pigment, an anti-sagging agent, a leveling agent, an adhesion improver, an antifoaming agent, and the like as necessary. The fine filler other than calcium carbonate may have any form, but those having an average particle diameter of 0.001 to 10 μm, particularly 0.005 to 5 μm are preferable. Use of a material outside this range is not preferable because the obtained insulating film is cracked when bent or the bent portion is whitened. Examples of the fine filler include fine inorganic fillers such as aerosil, talc, mica and barium sulfate, and fine organic fillers such as crosslinked NBR fine particles.

The composition for polyimide siloxane insulating film of the present invention is applied to the surface of the substrate by screen printing or the like, and then heat-treated at a temperature of 50 to 210 ° C., preferably about 70 to 170 ° C. for about 5 to 120 minutes, to obtain an elastic modulus. Of 0.1 to 20 kgf / mm ² can be suitably formed. This heat treatment is performed in multiple stages, for example, at a temperature of 50 to 130 ° C., preferably about 70 to 130 ° C. for about 5 to 60 minutes, and then 120 to 210 ° C., preferably about 120 to 170 ° C. for 5 to 120 minutes. You don't mind.

The composition for polyimide siloxane insulating film of the present invention can be suitably used for forming an insulating film for protecting a circuit pattern comprising a conductor on a flexible wiring board.
For example, on the pattern surface of a flexible wiring board in which a circuit pattern made of a conductor such as copper foil is formed on the surface of an insulating film such as polyimide, the thickness of the dry film is about 5 to 60 μm, particularly 5 to 30 μm. After printing by screen printing or the like, it is heat-treated at a temperature of 50 to 210 ° C. for about 5 to 120 minutes to form a protective insulating film. Next, the lead portion of the circuit pattern that is not covered with the protective insulating film is tin-plated. Bumps are formed on the inner lead portion where the surface of the conductor is tin-plated, and an IC chip is mounted so that the conductor and the IC chip are connected via the bump, and the IC chip and the connection portion are for protecting them. It is sealed with a sealing material or an underfill material. Further, the outer lead portion whose surface of the conductor is tin-plated is used for connection with other components.
1 and 2 show an example of an embodiment of a tape carrier package in which the composition for polyimide siloxane insulating film of the present invention is used as an insulating film for protecting a circuit pattern on a flexible wiring board such as a TAB method or COF. .

In such applications, in addition to electrical properties such as electrical insulation, the insulation film is heat and moisture resistant (PCT), solvent resistant, solder resistant, flexible, copper foil and other conductors, IC sealants, etc. Adhesion with other materials and tin plating resistance are required.
In addition to the usual tin resistance (the insulating film does not change with tin), the tin plating resistance includes so-called “tin diving” that occurs when tin penetrates at the edge of the insulating film when tin plating is performed. It is required to be sufficiently small even if it does not occur or occurs. “Tin diving” means that the surface of a metal conductor such as a copper foil is ionized and eroded, and as the degree of further progresses, the surface is eroded and pitting corrosion is formed. If tin submergence occurs, if the metal conductor is formed of a thin foil, it easily breaks, and the reliability as an electronic component is significantly impaired. Therefore, such a circuit cannot be used for an electronic component corresponding to downsizing and fine pitch.
As a countermeasure against tin dive, there is a two-color coating method in which an epoxy dam is formed by an epoxy resin in the periphery of a portion that is covered with an insulating film in advance, and then an insulating film is formed. This two-color coating requires a complicated process and takes a long time, and hinders downsizing of parts. The smaller the tin depth of the insulating film, the smaller the component.
In the insulating film, if tin submergence does not occur or is sufficiently small even if it occurs, an epoxy dam is not necessary, so-called one-color coating that only forms an insulating film is possible, and the process can be simplified and facilitated. This is extremely useful because the parts can be made smaller and thinner.

  The composition for polyimide siloxane insulating film of the present invention has good storage stability (relatively low viscosity is maintained almost constant for a long time) and printability, and is applied to, for example, a silicon wafer or a flexible wiring board. The insulating film obtained by drying and curing does not substantially cause curling, and has good flexibility, electrical insulation, heat and moisture resistance (PCT), and adhesion to the substrate, etc. Furthermore, it has improved tin plating resistance, preferably tin plating resistance of less than 30 μm, particularly tin sinking of less than 20 μm. For this reason, when the composition for polyimide siloxane insulating film of the present invention is used, the reliability is high even when the thickness of a circuit pattern made of a conductor of a flexible wiring board is as thin as 15 μm or less, preferably 10 μm or less, for example, about 9 μm. It becomes possible to obtain the protective insulating film by painting with one color.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.

Measurement methods and evaluation methods in the following examples were performed by the following methods.
(viscosity)
An E type viscometer (manufactured by Tokyo Keiki Co., Ltd.) and an ST rotor were used, and the rotation was performed at 10 rpm and at a temperature of 25 ° C.
(Tin solder resistance (tin diving))
35 μm thick electrolytic copper foil (manufactured by Mitsui Kinzoku Mining Co., Ltd.) A test piece coated with an insulating film composition on a glossy surface to a thickness of 30 μm, heated at 80 ° C. for 30 minutes and then heated at 120 ° C. for 1 hour to cure Using electroless tin plating solution (manufactured by Shipley Far East Co., Ltd., LT-34), tin plating was performed at a temperature of 70 ° C. for 4 minutes. The distance from the part was measured.
(Sealant adhesion)
The insulating film composition was applied to a glossy surface of 35 μm thick electrolytic copper foil to a thickness of 30 μm, heated at 80 ° C. for 30 minutes, and then heated at 120 ° C. for 1 hour to be cured. On this cured film, IC sealing material CEL-C-5020 (manufactured by Hitachi Chemical Co., Ltd.) was dropped in a circular shape with a thickness of about 1 to 2 mm and a diameter of about 0.5 cm, and cured by heating at 160 ° C. for 2 hours. A test piece was obtained. This test piece was bent by hand to observe the peeling of the IC sealing material. ○ when cohesive failure occurs in the cured film and the copper foil surface is exposed, △ when cohesive failure of the cured film and interfacial debonding coexist, and when the interfacial delamination between the cured film and the sealing material occurs and the cured film remains as it is Is indicated by x.
(Solvent resistance)
A composition for an insulating film was applied to a glass plate coated with a polyfluorinated ethylene resin and cured by heat treatment at 120 ° C. for 1 hour to obtain a cured film having a thickness of about 80 μm. The cured film was peeled off from the glass plate and cut into a 10 cm × 15 cm shape to obtain a test piece. This test piece was immersed in acetone for 10 minutes, and the weight reduction rate (%) of the sample before and after immersion was measured.
(Solder resistance)
The composition for an insulating film was applied to a glossy surface of 35 μm thick electrolytic copper foil to a thickness of 30 μm and cured by heating at 120 ° C. for 1 hour. The dimension of the test piece was 3 cm × 4 cm. After applying a rosin-based flux (Sanwa Chemical Industrial: SUNFLUX SF-270) on the cured film of the test piece, the cured film of the test piece was brought into contact with a solder bath at 260 ° C. for 10 seconds. The surface of the cured film of the test piece was observed, and indicated by ◯: no change at all, Δ: partial bulge, ×: overall bulge.

The compounds used in the following examples will be described.
Epicoat 157S70: Epoxy resin Takenate B882N manufactured by Japan Epoxy Resin Co., Ltd., 1,6-hexamethylene diisocyanate blocked, manufactured by Mitsui Takeda Chemical Co., Ltd., blocking agent: methyl ethyl ketoxime 2E4MZ: manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-ethyl-4 -Methylimidazole DBU: manufactured by Aldrich, 1,8-diazabicyclo [5.4.0] -7-undecencazole DB-100: manufactured by Dow Corning Asia, silicone antifoaming agent Aerosil 50: manufactured by Nippon Aerosil Co., Ltd. Average particle size 30nm
Aerosil 130: Nippon Aerosil Co., Ltd., average particle size 16 nm
Calcium carbonate A-30: manufactured by Ube Material Co., Ltd., maximum particle size 2 μm, average particle size 0.17 μm
Calcium carbonate A: manufactured by Ube Material Co., Ltd., maximum particle size 5 μm, average particle size 0.36 μm
Calcium carbonate B: manufactured by Ube Material Co., Ltd., maximum particle size 5 μm, average particle size 1.58 μm
Microace P-3: manufactured by Nippon Talc Co., Ltd., average particle size 5.1 μm
Barium sulfate B-30: manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 0.3 μm

[Reference Example 1] Production of polyimide siloxane In a glass flask having a capacity of 500 ml, 47.1 g (0.16 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, a solvent triglyme (hereinafter, (It may be abbreviated as TG.) 100 g was charged and heated and stirred at 80 ° C. in 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 bis (3-carboxy-4-aminophenyl) methane and 39 g of TG were added to this reaction solution, and the mixture was heated and stirred at 180 ° C. for 15 hours, followed by filtration. The resulting polyimidesiloxane reaction solution was a solution having a polymer solid concentration of 50% by weight and ηinh of 0.20. The imidization rate was substantially 100%.

[Example 1]
In a glass container, 40.8 g of the polyimidesiloxane solution obtained in Reference Example 1 and 0.20 g of epoxy resin Epicoat 157S70 (1 part by weight with respect to 100 parts by weight of polyimidesiloxane solids, the same shall apply hereinafter), polyisocyanate Takenate B882N (2.04 g, 10.0 parts by weight), 2E4MZ as a curing catalyst (0.04 g, 0.2 parts by weight) and DBU (0.16 g, 0.8 parts by weight) 0.9 g (4.4 parts by weight) of DB-100, 0.83 g (4 parts by weight) of Aerosil 50 of finely divided silica, 3.7 g (18 parts by weight) of Aerosil 130, and 4 of calcium carbonate A-30 0.7 g (23 parts by weight) and 9.4 g (46 parts by weight) of talc microace P-3 were added and stirred at 25 ° C. for 2 hours to mix uniformly. To obtain an edge coating composition. Table 1 shows the results of evaluation of this insulating film composition.

[Examples 2-3]
In the same manner as in Example 1, a polyimidesiloxane insulating film composition having the composition shown in Table 1 was obtained. Table 1 shows the results of evaluation of this insulating film composition.

[Comparative Example 1]
In the same manner as in Example 1, a polyimidesiloxane insulating film composition having the composition shown in Table 1 was obtained. Table 1 shows the results of evaluation of this insulating film composition.

  The polyimidesiloxane insulating film composition of the present invention has good storage stability (relatively low viscosity is maintained substantially constant for a long period of time) and printability, and the solution composition is applied to, for example, a flexible wiring board. When the insulating film is formed by drying and curing, the insulating film does not substantially cause curling, and is flexible, electrically insulating, heat and humidity resistant (PCT), solvent resistant, Solderability, adhesion to the substrate, etc. are good, and tin plating resistance (tin submergence) is particularly improved, so that it can be suitably used as an electrically insulating protective film.

It is a conceptual diagram which shows an example of embodiment of the tape carrier package which uses the polyimide siloxane type insulating film composition of this invention as a protective insulating film. It is a conceptual diagram which shows another example of embodiment of the tape carrier package which uses the polyimide siloxane type insulating film composition of this invention as a protective insulating film.

Explanation of symbols

1: Insulating film (polyimide film)
2: Circuit pattern (wiring made of copper foil)
3: Tin-plated inner lead part of the circuit pattern 4: Tin-plated outer lead part of the circuit pattern 5: IC chip component 6: IC sealing material (underfill material)
7: Bump 8: Bending part protective resin 9: Insulating film 10: Tin plating

Claims (4)

(A) tetracarboxylic acid component, diaminopolysiloxane represented by general formula (1) 30 to 95 mol%, aromatic diamine having a polar group 0.5 to 40 mol%, and aromatic diamine other than the diamine 0 100 parts by weight of an organic solvent-soluble polyimidesiloxane obtained from a diamine component consisting of ˜69.5 mol%

(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 40.)
(B) 1-50 parts by weight of an epoxy compound and / or polyvalent isocyanate compound (c) 1-70 parts by weight of calcium carbonate, and (d) an organic solvent, and an insulating film obtained by heat treatment is improved. A composition for a polyimide siloxane insulating film, characterized by having a tin plating resistance.   The composition for a polyimide siloxane insulating film according to claim 1, wherein the insulating film obtained by the heat treatment has tin plating resistance with a tin dive of less than 30 µm.   A polyimide siloxane insulating film obtained by applying the composition for a polyimide siloxane insulating film according to claim 1 to a base material, followed by heat treatment.   A method for forming a polyimidesiloxane insulating film, wherein the composition for polyimidesiloxane insulating film according to any one of claims 1 and 2 is applied to a substrate and then heat-treated at 50 to 200 ° C, preferably 70 to 170 ° C.

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