JP2006257357A - Polyimide siloxane composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an improved polyimide siloxane composition characterized as having good adhesiveness to the resultant sealing material of a cured insulating film even when heated at any temperature of about 120-160°C after coating a substrate therewith. <P>SOLUTION: The polyimide siloxane composition is obtained by including a compound having ≥2 phenolic hydroxy groups in an amount of 0.1-18 pts.wt. based on 100 pts.wt. of a polyimide siloxane in the polyimide siloxane composition comprising 100 pts.wt. of the organic solvent-soluble polyimide siloxane, 2-40 pts.wt. of a polyvalent isocyanate compound and 0.1-20 pts.wt. of an epoxy compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a solution composition containing an organic solvent-soluble polyimide siloxane, a polyvalent isocyanate compound, an epoxy compound, and a compound having two or more phenolic hydroxyl groups. The cured film obtained by heating and curing this solution composition has good adhesion to the sealing material regardless of the curing temperature.

  A cured film that has been heat-treated after applying a solution composition containing polyimidesiloxane and epoxy resin to the base material has excellent adhesion to the base material, small warpage, heat resistance, solvent resistance, and insulation reliability. It is already known to be superior. However, since this cured insulating film has a polysiloxane component having low adhesion to an organic material in the main component polyimidesiloxane, the cured insulating film is used for a sealing material made of an epoxy resin or the like. There is a problem that the adhesion is not sufficient.

  Patent Document 3 proposes a solution composition containing polyimide siloxane and a polyvalent isocyanate. The cured insulating film made of this composition has improved adhesion to the sealing material, but has a practical problem because of its low solvent resistance.

Patent Document 4 proposes a solution composition containing a polyimidesiloxane that is soluble in an organic solvent, a polyvalent isocyanate compound, and an epoxy compound. This composition can be cured even at a low temperature of about 120 ° C., and the cured insulating film cured at such a low temperature has improved adhesion to the sealing material. However, when cured at a high temperature of about 160 ° C., there is a problem that the adhesion to the sealing material is lowered, and there is room for further improvement.
JP-A-4-36321 JP 7-304950 A JP 2001-240650 A JP 2004-211064 A

  The object of the present invention is that the adhesiveness of the obtained cured insulating film to the sealing material is good even if it is heated at any temperature of about 120 ° C. to 160 ° C. after being applied to the substrate. An improved polyimide siloxane composition is provided.

  The present invention relates to a polyimide siloxane solution composition containing 100 parts by weight of an organic solvent-soluble polyimide siloxane, 2 to 40 parts by weight of a polyvalent isocyanate compound, and 0.1 to 20 parts by weight of an epoxy compound. It is related with the polyimidesiloxane solution composition characterized by containing 0.1-18 weight part of compounds which have 2 or more with respect to 100 weight part of polyimidesiloxane.

  Further, the present invention is a polyimide siloxane solution composition containing at least a polyimide siloxane, a blocked polyvalent isocyanate compound, an epoxy compound, a compound having two or more phenolic hydroxyl groups, and a curing catalyst, Acetone-soluble matter after immersing a cured film obtained by heat-treating the composition at 80 ° C. for 30 minutes and then at 150 ° C. for 1 hour in acetone at 25 ° C. is 10% by weight or less. To a polyimidesiloxane solution composition.

  The present invention also relates to a cured insulating film obtained by applying a heat treatment after applying the polyimidesiloxane solution composition to a substrate.

  The polyimide siloxane composition of the present invention can obtain a cured insulating film by heat treatment at any temperature of about 120 ° C. to 160 ° C., and the cured insulating film has good adhesion to a sealing material. It is. Preferably, the cured insulating film is excellent in non-curling property, adhesion to a substrate, heat resistance, solder flux resistance, solvent resistance, chemical resistance, bending resistance, and insulation reliability. Furthermore, since the polyimidesiloxane solution composition of the present invention can be satisfactorily applied on a flexible wiring board by a method such as screen printing, a printing ink for forming an insulating cured film (protective film) for electrical and electronic parts and the like. Or it is a solution composition suitable as a coating varnish.

The preferable aspect of the polyimidesiloxane solution composition of this invention is shown.
(1) The compound having two or more phenolic hydroxyl groups is 18 parts by weight or less, preferably 15 parts by weight or less, and further 10 parts by weight or less based on 100 parts by weight of polyimidesiloxane.
(2) The ratio of the compound having two or more phenolic hydroxyl groups to the epoxy compound [(compound having two or more phenolic hydroxyl groups) / (epoxy compound)] is 0.75 to 11, preferably 0.00. 8-8.
(3) The organic solvent-soluble polyimide siloxane, polyvalent isocyanate compound, and epoxy compound are contained in a weight comparison in the relationship of polyimidesiloxane> polyvalent isocyanate compound> epoxy compound.
(4) Organic solvent-soluble polyimide siloxane is a tetracarboxylic acid component, diaminopolysiloxane 30 to 95 mol%, aromatic diamine having a polar group 0.5 to 40 mol%, and other diamines 0 to 69.5 It is a polysiloxane obtained from a diamine component consisting of mol%.
(5) Further, it contains a curing catalyst, preferably a tertiary diamine.
(6) Further, it contains an inorganic filler, preferably at least one inorganic filler selected from the group consisting of silica, talc, mica, barium sulfate, and calcium carbonate.
(7) A solution composition comprising at least a polyimidesiloxane, a blocked polyvalent isocyanate compound, an epoxy compound, a compound having two or more phenolic hydroxyl groups, and a curing catalyst, wherein the composition Acetone-soluble matter after immersing a cured film obtained by heating the product at 80 ° C. for 30 minutes and then at 150 ° C. for 1 hour in 100 mL of acetone at 25 ° C. for 30 minutes becomes 10% by weight or less of the cured film. It is a solution composition characterized in that it can be sufficiently cured to an extent. However, the acetone-soluble component was measured using a sample having a cured film thickness of 75 μm and a weight of 0.5 g.

  Next, polyimide siloxane, a polyvalent isocyanate compound, an epoxy compound, a compound having two or more phenolic hydroxyl groups, and the like used in the polyimide siloxane solution composition of the present invention will be described. In addition, this invention improves the polyimidesiloxane solution composition based on the said patent document 4, and the patent document 4 has detailed description about a polyimidesiloxane, a polyvalent isocyanate compound, an epoxy compound, etc.

  The organic solvent-soluble polyimide siloxane in the present invention comprises a tetracarboxylic acid component, a diamine component containing diaminopolysiloxane and a diamine having a polar group, and the tetracarboxylic acid component is preferably approximately equimolar, preferably 1 mol of the diamine component. It can be obtained by reacting in an organic solvent at a ratio of about 1.0 to 1.2 mol.

  Examples of the tetracarboxylic acid component include 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, and 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 Arocarboxylic tetracarboxylic acids such as tracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,1-bis (2,3-dicarboxyphenyl) ethane, or their acid dianhydrides or lower Alcohol esterified products and fats such as cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3-methyl-4-cyclohexene-1,2,4,5-tetracarboxylic acid Preferable examples include cyclic tetracarboxylic acids, or acid dianhydrides and esterified products of lower alcohols. In this invention, it is preferable to contain an aromatic tetracarboxylic acid component as a tetracarboxylic acid component in an amount of 80 mol% or more, particularly 85% to 100%. Also, 2,3,3 ′, 4′-biphenyltetracarboxylic acid and 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, or their acid dianhydrides and lower alcohols Use of an esterified product is preferable because the resulting polyimidesiloxane has excellent solubility in organic solvents.

  As the tetracarboxylic acid component of the polyimidesiloxane in this 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 mol or more with respect to diamine and an unreacted anhydrous ring remains, it may be left as it is, but it may be ring-opened half-esterified with an esterifying agent. May be.

  In this invention, the diamine component of the polyimidesiloxane is preferably diaminopolysiloxane 30 to 95 mol%, particularly 50 to 95 mol%, more preferably 60 to 95 mol%, aromatic diamine having a polar group 0.5 to 40 mol%, and The diaminopolysiloxane and the diamine other than the aromatic diamine having the polar group are used in a proportion of 0 to 69.5 mol% (usually 0 to 30 mol%).

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

一般式（１）において、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３〜５０の整数を示す。但し、一般式（１）中、Ｒ_１は炭素数１〜６の２価の炭化水素基又はフェニレン基、特にプロピレン基が好ましく、Ｒ_２は独立に炭素数１〜５のアルキル基又はフェニル基が好ましく、ｎ１は３〜５０、特に３〜２０が好ましい。尚、ジアミノポリシロキサンが２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 general formula (1), 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 3 to 50. . However, in general formula (1), R ₁ is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms or a phenylene group, particularly a propylene group, and R ₂ is independently an alkyl group having 1 to 5 carbon atoms or a phenyl group. N1 is preferably 3 to 50, particularly preferably 3 to 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 diamine having a polar group constituting the diamine component of polyimidesiloxane is preferably an aromatic diamine having a polar group having reactivity with an epoxy resin or isocyanate in the molecule, and preferably represented by the following general formula (2). Is the diamine indicated.

In the general formula (2), 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 r1 is 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 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 Hydroxybiphenyl compounds such as 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) biphenyl such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl Examples thereof include diamine compounds having an OH group such as 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) And diamine compounds having a COOH group such as bis (carboxyphenoxyphenyl) sulfone compounds such as phenyl] sulfone.

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

In the general formula (3), 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-dihalogenobenzene. Diamines containing one benzene such as 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-to Diamines containing two benzenes such as gin 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-bi Examples thereof include diamine compounds such as diamines containing 4 or more benzenes such as su (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.

Polyimidesiloxane can be obtained, for example, by the following method.
(A) A method in which a tetracarboxylic acid component and a diamine component are used in approximately equimolar amounts, and polymerized and imidized continuously in an organic polar solvent at 15 to 250 ° C. to obtain polyimidesiloxane.
(B) A tetracarboxylic acid component and a diamine component are separated from each other, and an excess amount of a tetracarboxylic acid component and a diamine component (for example, diaminopolysiloxane) are first polymerized and imidized at 15 to 250 ° C. in an organic polar solvent. An imidosiloxane oligomer having an acid anhydride group (or acid, esterified product thereof) at the terminal having an average degree of polymerization of about 1 to 10 is prepared, and a tetracarboxylic acid component and an excess amount of a diamine component are separately added in an organic polar solvent 15 Polymerize and imidize at ˜250 ° C. to prepare an imide oligomer having an amino group at an average degree of polymerization of about 1 to 10, and then mix the two so that the acid component and the diamine component are approximately equimolar. Then, the reaction is carried out at 15 to 60 ° C., and the temperature is further raised to 130 to 250 ° C. for reaction to obtain polyimide siloxane.
(C) A tetracarboxylic acid component and a diamine component are used in approximately equimolar amounts, and after first polymerizing at 20 to 80 ° C. in an organic polar solvent to obtain a polyamic acid, the polyamic acid is imidized to obtain a polyimide siloxane. Method.

  Examples of the organic polar solvent used in obtaining the polyimidesiloxane by the above-described method include nitrogen-containing solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N- Solvents containing sulfur atoms such as diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexa Methylsulfuramide and the like, phenolic solvents such as cresol, phenol and xylenol, diglyme solvents such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraglyme Etc., solvents having oxygen atoms in the molecule, such as acetone, methanol, ethanol, ethylene glycol, dioxane, tetrahydrofuran, and other pyridine, tetramethyl urea. Moreover, you may use together other organic solvents, such as aromatic hydrocarbon type solvents, such as benzene, toluene, and xylene, solvent naphtha, and benzonitrile, as needed.

  The polyimide siloxane may be obtained by any method such as the above (a) to (c), but at least 3% by weight or more in an organic solvent, preferably at a high concentration of about 5 to 60% by weight. It can be dissolved, and the solution viscosity at 25 ° C. (E-type rotational viscometer) is preferably 1 to 10000 poise, particularly 1 to 100 poise. Polyimidesiloxane preferably has a high molecular weight and further preferably has a high imidization rate. The 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 product. Further, the imidation ratio obtained from the infrared absorption spectrum is preferably 90% or more, particularly 95% or more, and substantially 100%.

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 polyvalent isocyanate compounds include aliphatic, alicyclic or aromatic diisocyanates, such as 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diester. Isocyanate, 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 Isocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene Isocyanate - door, and the like can be given.
Further, as the polyvalent isocyanate compound, those derived from aliphatic, alicyclic or aromatic polyvalent isocyanate, such as isocyanurate-modified polyvalent isocyanate, burette-modified polyvalent isocyanate, Examples thereof include urethane-modified polyvalent isocyanate.

  As the polyvalent isocyanate compound used in the present invention, a blocked polyvalent isocyanate obtained by blocking the isocyanate group of the polyvalent isocyanate 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 compounds. And pyridine compounds, 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, succinimide, maleic imide, imidazole, imidazole, 2-methylimidazole, urea, urea, thiourea, ethylene urea, etc., oxime, Formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc., amine type, diphenylamine, aniline, carbazole, etc., imine type, ethyleneimine, polyethyleneimine, etc., bisulfite, sodium 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) -Glucose), Duranate MF-B60X (1,6-hexamethylene diisocyanate blocked), Asahi Kasei Corporation, Duranate MF-K60X (1,6-hexamethylene diisocyanate blocked), Daiichi Kogyo Seiyaku Co., Ltd. Elastolon BN-P17 (4,4'-diphenylmethane diisocyanate block), Elastolon BN-04, Elastolon BN-08, Elastolon BN-44, Elastolon BN-45 (above, urethane-modified polyisocyanate) 3 to 5 functional groups per one molecule of a blocked compound, both of which can be used after being isolated by drying as a water emulsion product) can be preferably used.

  The amount of the polyvalent isocyanate compound used is preferably 2 to 40 parts by weight and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polyimidesiloxane. When the amount of the polyvalent isocyanate compound used is out of the above range, the solvent resistance of the insulating film obtained by heat-treating the polyimide insulating composition may be deteriorated or the heat resistance may be deteriorated.

  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 825, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1055, Epicoat 1004AF, Epicoat 1007, Epicoat 1009, Epicoat 1010, etc.) Trifunctional or higher epoxy resin (manufactured by 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.

  The amount of the epoxy compound used is preferably 0.1 parts by weight or more, further 0.3 parts by weight or more, particularly 0.5 parts by weight or more, and 20 parts by weight or less and further 15 parts by weight or less with respect to 100 parts by weight of the polyimidesiloxane. In particular, it is 7 parts by weight or less. If the amount used is more than the above range, the adhesiveness of the cured insulating film to the substrate or the sealing material is lowered, and if it is too small, the heat resistance and chemical resistance of the cured insulating film may be deteriorated. . More specifically, an appropriate amount of the epoxy compound is determined by its 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 use amount of the epoxy compound having an epoxy equivalent of 100 to 800 is 0.1 to 10 parts by weight, and further 0.5 to 7 parts by weight of the base of the insulating film after curing is 100 parts by weight of polyimidesiloxane. The epoxy compound having an epoxy equivalent of more than 800 is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of polyimidesiloxane. 15 parts by weight is particularly suitable for maintaining the adhesion of the cured insulating film to the base material and sealing material.

  The solution composition of the present invention is mainly composed of an organic solvent-soluble polyimide siloxane, and the content of the polyimide siloxane, the polyvalent isocyanate compound, and the epoxy compound is, in weight comparison, the order of the polyimide siloxane, the polyvalent isocyanate compound, and the epoxy compound. It is preferable to contain in a large amount. If the epoxy compound is contained in a larger amount than the polyvalent isocyanate compound, the resulting cured insulating film is not flexible, and the adhesion to the sealing material is deteriorated.

  As the compound having two or more phenolic hydroxyl groups used in the present invention, any compound having two or more phenolic hydroxyl groups in the molecule may be used. Examples thereof include phenol resins such as hydroquinone, 4,4'-dihydroxybiphenyl, phenol novolac, and cresol novolac. As phenol resins, Meiwa Kasei Co., Ltd. phenol novolac resins H-1, H-2, H-3, H-4, H-5, orthocresol novolac MER-130, triphenolmethane type MEH-7500, tetrakisphenol Type MEH-7600, naphthol type MEH-7700, phenol aralkyl type MEH-7800, MEH-7851, triphenol type R-3, bisphenol novolac type MEP-6309, MEP-6309E, liquid phenol novolac MEH-8000H, MEH-8005 , MEH-8010, MEH-8015, MEH-8205, and the like.

  In the present invention, the compound having two or more phenolic hydroxyl groups is 0.1 parts by weight or more, preferably 0.3 parts by weight or more, particularly 0.5 parts by weight or more, and 18 parts by weight with respect to 100 parts by weight of polyimidesiloxane. It is suitable to use in a proportion of not more than 15 parts by weight, preferably not more than 15 parts by weight, especially less than 10 parts by weight. When the amount used is more than the above range, the solvent resistance and chemical resistance of the resulting cured insulating film are lowered, which is not preferable. Moreover, since the adhesiveness with respect to the sealing material of a hardening insulating film will become low when there are too few, the said range is preferable.

  Furthermore, in this invention, it is preferable to use a compound having two or more phenolic hydroxyl groups in a weight ratio of 0.75 to 11, preferably 0.8 to 8, with respect to the epoxy compound. If a compound having two or more phenolic hydroxyl groups at a ratio outside this range is used, it is difficult to sufficiently improve the adhesion of the resulting cured insulating film to the sealing material.

  Furthermore, the solution composition of the present invention has a dissociation catalyst that dissociates the blocking agent of the blocked polyvalent isocyanate at a certain temperature or higher, a polyvalent isocyanate compound, an epoxy compound, and two or more phenolic hydroxyl groups. It is preferable to contain a curing catalyst composed of a compound and a curing accelerating catalyst for accelerating the crosslinking reaction between the polyimide siloxane and the like. 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. Further, as the curing accelerating catalyst, imidazoles such as 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1,8-diazabicyclo [5.4.0] -7-undecene (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 ether (DMDEE), 1,4-dimethylpiperazine, cyclohexyldimethylamine, and other 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. Tertiary amines are extremely suitable because they have both an action as a dissociation catalyst for blocked polyvalent isocyanate and an action as a curing acceleration catalyst for accelerating the crosslinking reaction.

  In this invention, it is preferable to preserve the solution composition by combining a polyimide siloxane, a blocked polyvalent isocyanate compound, an epoxy compound, a compound having two or more phenolic hydroxyl groups, and a curing catalyst. Stability and suitable curing characteristics can be exhibited. That is, a solution composition comprising at least a polyimide siloxane, a blocked polyvalent isocyanate compound, an epoxy compound, and a compound having two or more phenolic hydroxyl groups is further added with a curing catalyst to obtain a solution composition. The storage stability is good, and a sufficiently cured film can be obtained by relatively mild heating conditions, for example, heat treatment at 80 ° C. for 30 minutes and then at 150 ° C. for 1 hour. By sufficiently curing in this manner, the solvent resistance and solder heat resistance of the cured film can be satisfactorily exhibited.

  Furthermore, it is preferable that the solution composition of this invention contains an inorganic filler. The inorganic filler may be of any size and form, but preferably has an average particle size of 0.001 to 15 μm, particularly 0.005 to 10 μm. 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 inorganic filler, fine powdery silica, talc, mica, barium sulfate, calcium carbonate and the like can be preferably exemplified.

  The amount of inorganic filler used is 20 to 150 parts by weight, preferably 40 to 125 parts by weight, based on 100 parts by weight of polyimidesiloxane. If the amount used is too large or too small, cracks may occur due to bending of the coating film, and the printability and solder heat resistance are affected, so the above range is preferred. These inorganic fillers may be used alone, but it is particularly preferable to use a combination of a plurality of types in consideration of printability and performance of the obtained insulating film.

As the organic solvent used in the solution composition of the present invention, the organic solvent used in the reaction for preparing the polyimidesiloxane can be used as it is, but a nitrogen-containing solvent such as N, N-dimethyl is preferable. Acetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, etc. Sulfur atom solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfuramide and the like; oxygen-containing solvents such as ether solvents such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether ( Triglyme), Tet Glyme and the like; and acetone, acetophenone, mention may be made of propiophenone, 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, tetraglyme and the like can be preferably used.

  In the solution composition of the present invention, a predetermined amount of a pigment such as an organic color pigment or an inorganic color pigment can be used, for example, about 0 to 100 parts by weight with respect to 100 parts by weight of polyimidesiloxane. Moreover, in order to improve the foam removal property when a coating film is formed by screen printing, a defoaming agent, particularly a silicone-based antifoaming agent, is added in a predetermined amount, for example, 0.1 to 10 weights with respect to 100 parts by weight of polyimidesiloxane. It is preferable to use about 1 part.

  The solution composition of the present invention uniformly stirs and mixes predetermined amounts of polyimide siloxane, polyvalent isocyanate compound, epoxy compound, compound having two or more phenolic hydroxyl groups, inorganic filler, curing catalyst, organic solvent, etc. Can be easily obtained. In preparing a solution composition by mixing in an organic solvent, the polyimidesiloxane polymerization solution may be used as it is, or a solution obtained by diluting the polymerization solution with an appropriate organic solvent may be used. Examples of the organic solvent include the above-mentioned organic polar solvents, and those having a boiling point of 140 ° C. or higher and 210 ° C. or lower are preferably used. In particular, when an organic solvent having a boiling point of 180 ° C. or higher, particularly 200 ° C. or higher is used, dissipation due to evaporation of the solvent is remarkably reduced, and printing with screen printing using the printing ink is not hindered. Since it can be suitably performed, it is optimal. The organic solvent is used in an amount of about 60 to 200 weights per 100 weight parts of polyimidesiloxane.

  Further, the solution composition of the present invention is not particularly limited, but the screen has a solution viscosity of 5 to 1000 Pa · s, particularly 10 to 100 Pa · s, more preferably 10 to 60 Pa · s at room temperature (25 ° C.). Considering workability such as printing, physical properties of the solution, and characteristics of the obtained cured insulating film, it is preferable.

The polyimidesiloxane solution composition of the present invention can be suitably used for forming an insulating film (protective film) for electrical and electronic parts on which chip parts such as IC chips are mounted. For example, on the pattern surface of an insulating film having a wiring pattern formed of conductive metal foil, it is applied by printing by screen printing or the like so that the thickness of the dry film is about 3 to 60 μm. Thereafter, the solvent is removed by heat treatment at a temperature of about 50 to 100 ° C. for about 5 to 60 minutes, and then about 100 to 210 ° C., preferably about 110 to 200 ° C. for 5 to 120 minutes, preferably about 10 to 60 minutes. By heat-treating with and curing, an insulating film having an elastic modulus of 10 to 500 MPa can be suitably formed. The obtained cured insulating film preferably does not easily warp, has good adhesion to a conductive metal foil or an insulating film, and has heat resistance, solder flux resistance, solvent resistance (for example, acetone , Solvent resistance to isopropanol and methyl ethyl ketone), chemical resistance, flex resistance, electrical properties, and insulation reliability. Furthermore, the cured insulating film obtained from the solution composition of the present invention can be obtained by heat treatment at any temperature of about 120 ° C. to 160 ° C., and the cured insulating film is sealed. Good adhesion to materials (including underfill material).
In an electronic component application, after protecting the wiring pattern with an insulating film, a chip component or the like is mounted on an inner lead portion or the like that is not protected by the insulating film, and the chip component is further protected with a sealing material or the like. A schematic cross-sectional view of an example of mounting is shown in FIG. As can be seen from this figure, since the insulating film and the sealing material are in direct contact when mounted, the insulating film is required to have higher adhesion to the sealing material.
The cured insulating film obtained by heat-treating the solution composition of the present invention can obtain a cured insulating film by heat treatment at any temperature of about 120 ° C. to 160 ° C., and the cured insulating film Is very suitable for forming an insulating film (protective film) for electronic parts because it has good adhesion to a sealing material (including an underfill material).

  Further, the polyimidesiloxane solution composition of the present invention can be used at low temperature and can be suitably used as a heat-resistant adhesive.

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

In each example, measurement and evaluation were performed by the following methods.
(Solution viscosity)
Using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), measurement was performed at a temperature of 25 ° C. and a rotation speed of 10 rpm.

[Evaluation of cured film]
Evaluation of the cured insulating film was performed on a sample heat-treated at 80 ° C. for 30 minutes and then at 150 ° C. for 1 hour. However, since the sample for evaluating the adhesion to the sealing material was applied by dropping the sealing material on the sample surface, the sealing material was cured by heat treatment at 160 ° C. for 1 hour. In addition, it was heat-treated at 160 ° C. for 1 hour.

Evaluation of solvent resistance:
0.5 g of the sheet-like cured film cured so as to have a thickness of 75 μm was used as a sample, and it was expressed as weight% of acetone-soluble matter after being immersed in 100 mL of acetone at 20 ° C. for 30 minutes. In addition, that there are few acetone soluble parts means that hardening has fully progressed, and 100 weight% of acetone soluble parts means that the sample melt | dissolved completely, ie, it is uncured.

Evaluation of adhesion to the sealing material:
The solution composition is applied to a glossy surface of 35 μm thick electrolytic copper foil to a thickness of 30 μm and cured, and an IC chip sealing material CEL-C-5020 (manufactured by Hitachi Chemical Co., Ltd.) is about 1 mm thick on this cured film. The sample was dropped into a circular shape having a diameter of about 0.5 cm, applied, heated at 160 ° C. for 1 hour, and cured to obtain a sample. The sample was folded by hand and the sealing material was observed for peeling. ○ when the cohesive failure occurs in the cured film and when the cured film / copper foil interface peels, △ when the cohesive failure of the cured film and the cured film / sealing material interface coexist, △, cured film / sealing material interface The case of peeling was indicated by x.

Measurement of electrical insulation (volume resistance):
It was measured according to JIS C-2103.

Measurement of tensile modulus:
A sheet-like cured film cured to a thickness of 75 μm was cut into a width of 1 cm and a length of 15 cm and used for the test. Measured by ASTM D882.

Evaluation of solder heat resistance:
The solution composition was applied to a glossy surface of an electrolytic copper foil having a thickness of 35 μm to a thickness of 30 μm and cured to form a cured film. Using this as a sample, rosin-based flux (SUNFLUX SF-270, manufactured by Sanwa Chemical Industry Co., Ltd.) was applied on the cured film, and then the cured film was brought into contact with a solder bath at 260 ° C. for 10 seconds. The state of the subsequent sample was observed and evaluated. A case where no abnormality occurred was indicated by ○, and a case where abnormality such as blistering occurred was indicated by ×.

warp:
A sample obtained by applying the solution composition to an area of 30 mm × 40 mm on a central portion of a polyimide film (Upilex 75S) manufactured by Ube Industries, Ltd. cut to 50 mm × 70 mm and curing it was used as a sample. The thickness of the cured film was 15 μm. The maximum height of the four sides of the sample polyimide film was measured with the cured film on the upper surface.

Tin diving measurement:
An electroless tin plating solution (LT-34, manufactured by Shipley Far East Co., Ltd.) was used for a sample obtained by applying a solution composition to a thickness of 30 μm on a glossy surface of an electrolytic copper foil having a thickness of 35 μm and curing it, at a temperature of 70 ° C. Tin plating was performed for 4 minutes, and the width (distance from the end of the cured film) of the portion where tin penetrated at the end of the cured film and tin sublimation occurred was measured.

The epoxy compound, polyvalent isocyanate compound, compound having two or more phenolic hydroxyl groups, inorganic filler, and curing catalyst used in the following examples will be described.
[Epoxy compound]
Epicoat 157S70: Epoxy resin [polyvalent isocyanate compound] manufactured by Japan Epoxy Resin Co., Ltd.
Bernock D-550: Dainippon Ink Co., Ltd., 1,6-hexamethylene diisocyanate blocked, blocking agent: methyl ethyl ketoxime [compound having two or more phenolic hydroxyl groups]
H-1: Phenol novolac MER-130 manufactured by Meiwa Kasei Co., Ltd .: Orthocresol novolak MEH-7500 manufactured by Meiwa Kasei Co., Ltd. Triphenolmethane type MEH-7600 manufactured by Meiwa Kasei Co., Ltd. Meiwa Kasei Co., Ltd. phenol aralkyl resin [fine powdered silica]
Aerosil 50: Nippon Aerosil Co., Ltd., average particle size 30 nm
Aerosil 130: manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm
[Barium sulfate]
Barium sulfate B-30: manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 0.3 μm
〔talc〕
Microace P-3: manufactured by Nippon Talc Co., Ltd., average particle size 5.1 μm
Ultra fine talc SG95: manufactured by Nippon Talc Co., Ltd., average particle size 2.5 μm
[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

[Reference Example 1] Production of polyimide siloxane A In a glass flask having a capacity of 500 ml, 58.84 g (0.2 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 170 g of triglyme as a solvent were added. The mixture was heated and stirred at 80 ° C. in a nitrogen atmosphere. 127.4 g (0.14 mol) of α, ω-bis (3-aminopropyl) polydimethylsiloxane (amino equivalent 455) and 50 g of triglyme were added, and the mixture was heated and stirred at 180 ° C. for 60 minutes. Further, after cooling to near room temperature, 13.52 g (0.03 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 4.56 g of 3,5-diaminobenzoic acid ( 0.03 mol) and 79 g of triglyme were added, and the mixture was heated and stirred at 180 ° C. for 5 hours, followed by filtration. The resulting polyimidesiloxane reaction solution was a solution having a polymer solid content concentration of 40 wt% and η _inh 0.20. The imidization rate was substantially 100%.

[Reference Example 2] Production of polyimide siloxane B In a glass flask having a capacity of 500 ml, 61.79 g (0.21 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 100 g of triglyme solvent were added. The mixture was heated and stirred at 80 ° C. in a nitrogen atmosphere. 107.10 g (0.126 mol) of α, ω-bis (3-aminopropyl) polydimethylsiloxane (amino equivalent 425) and 40 g of triglyme were added, and the mixture was heated and stirred at 180 ° C. for 60 minutes. Further, this reaction solution was mixed with 22.41 g (0.055 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 8.42 g (0 of bis (3-carboxy-4-aminophenyl) methane. 0.029 mol) and 63 g of triglyme were added, 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 η _inh 0.20. The imidization rate was substantially 100%.

[Example 1]
In a glass container, in the polyimidesiloxane solution obtained in Reference Example 1, 1.7 parts by weight of an epoxy compound Epicoat 157S70 and 10 parts by weight of a polyvalent isocyanate compound Vernoc D-550 with respect to 100 parts by weight of polyimidesiloxane. Further, as a compound having two or more phenolic hydroxyl groups, 1.5 parts by weight of phenolic resin H-1, 0.2 part by weight of 2E4MZ as a curing catalyst, 0.8 part by weight of DBU, and Aerosil 50 of finely divided silica are used. 11.5 parts by weight, Aerosil 130 16 parts by weight, Talc Microace P-30 45 parts by weight, Barium Sulfate B-30 23 parts by weight, and stirred and uniformly mixed polyimide siloxane composition A product (solution viscosity 30 Pa · s) was obtained.

Even when this polyimidesiloxane composition was allowed to stand at about 5 ° C. for 2 weeks, the viscosity change was small and screen printing was possible.
Table 1 shows the results of creating and evaluating a cured film sample for this solution composition.

[Examples 2 to 9]
A polyimide siloxane solution composition was produced in the same manner as in Example 1 except that the types and amounts shown in Table 1 were blended. Even when this polyimidesiloxane composition was allowed to stand at about 5 ° C. for 2 weeks, the viscosity change was small and screen printing was possible. Table 1 shows the results of creating and evaluating a cured film sample for this solution composition.

[Comparative Example 1]
Example 1 except that a polyisocyanate compound and a compound having two or more phenolic hydroxyl groups were not used, 18 parts by weight of Epicoat 157S70 of an epoxy compound was used, and 0.3 part by weight of 2E4MZ was used as a curing catalyst. In the same manner as above, a polyimidesiloxane composition was obtained. About this polyimidesiloxane composition, when the cured film was evaluated like Example 1, sealing agent adhesiveness was x and there existed a problem.

[Comparative Example 2]
A compound having two or more phenolic hydroxyl groups was not used, and the same procedure as in Example 1 was carried out except that 10 parts by weight of the polyisocyanate compound D-550 and 1.7 parts by weight of the epoxy compound Epicoat 157S70 were used. A polyimidesiloxane composition was obtained. About this polyimidesiloxane composition, when the cured film was evaluated like Example 1, sealing agent adhesiveness was (triangle | delta) and the improvement was needed.

[Comparative Example 3]
Similar to Example 1, except that no epoxy compound was used and 10 parts by weight of Vernock D-550, a polyvalent isocyanate compound, and 3 parts by weight of phenolic resin H-1, which is a compound having two or more phenolic hydroxyl groups, were used. Thus, a polyimidesiloxane composition was obtained. When this cured film was evaluated in the same manner as in Example 1 for this polyimidesiloxane composition, the solvent resistance was inferior at 16.6% and the solder heat resistance was also x.

[Comparative Example 4]
The same as Example 1 except that the polyisocyanate compound was not used, and 1.7 parts by weight of Epicoat 157S70 of epoxy compound and 3 parts by weight of phenol resin H-1 of a compound having two or more phenolic hydroxyl groups were used. Thus, a polyimidesiloxane composition was obtained. With respect to this polyimidesiloxane composition, the cured film was evaluated in the same manner as in Example 1. As a result, the solvent resistance was inferior at 12.2% and the solder heat resistance was also x.

[Comparative Example 5]
A polyimidesiloxane composition was obtained in the same manner as in Example 1 except that 20 parts by weight of phenol novolak H-1 as a compound having two or more phenolic hydroxyl groups was used. When this cured film was evaluated in the same manner as in Example 1 for this polyimidesiloxane composition, the solvent resistance was inferior at 14.3% and the solder heat resistance was also x.

The polyimidesiloxane composition of the present invention can be suitably used as an insulating protective film or insulating layer for electronic parts.

Claims (7)

In a polyimide siloxane solution composition comprising 100 parts by weight of an organic solvent-soluble polyimide siloxane, 2 to 40 parts by weight of a polyvalent isocyanate compound, and 0.1 to 20 parts by weight of an epoxy compound,
Furthermore, 0.1-18 weight part of compounds which have 2 or more phenolic hydroxyl groups are contained with respect to 100 weight part of polyimide siloxane, The polyimidesiloxane solution composition characterized by the above-mentioned.   2. The polyimidesiloxane solution composition according to claim 1, wherein the compound having two or more phenolic hydroxyl groups has a weight ratio of 0.75 to 11 with respect to the epoxy compound.   The organic solvent-soluble polyimide siloxane is a polyimide siloxane obtained from a tetracarboxylic acid component, a diaminopolysiloxane, an aromatic diamine having a polar group, and a diamine component other than those diamines. 2. The polyimidesiloxane solution composition according to 1.   Furthermore, a curing catalyst is contained, The polyimidesiloxane solution composition in any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, an inorganic filler is contained, The polyimidesiloxane solution composition in any one of Claims 1-3 characterized by the above-mentioned.   A polyimide siloxane solution composition containing at least a polyimide siloxane, a blocked polyvalent isocyanate compound, an epoxy compound, a compound having two or more phenolic hydroxyl groups, and a curing catalyst, wherein the composition is heated to 80 ° C. A polyimide siloxane solution composition characterized by having an acetone soluble content of 10% by weight or less after immersing a cured film obtained by heat treatment at 150 ° C. for 30 minutes at 150 ° C. for 30 minutes in acetone at 25 ° C. object.   A cured insulating film obtained by applying the polyimide siloxane solution composition according to claim 1 to a base material, followed by heat treatment.