JP4650176B2 - Modified polyimide resin containing polybutadiene, composition thereof and cured insulating film - Google Patents

Description

  The present invention relates to a modified polyimide resin that is soluble in an organic solvent and excellent in heat resistance, flexibility, and adhesion to a sealing material, and a solution composition using the same. The solution composition of the present invention can be satisfactorily applied on a substrate such as a flexible wiring board by a method such as screen printing, and has low-temperature curability. The cured film obtained by applying the solution composition of the present invention to a substrate and then heat-treating is hardly warped (non-curl), flexible, excellent in heat resistance and solder resistance, and has a wiring pattern. In addition, it has good adhesion to polyimide film and sealing material, and also has excellent solvent resistance, chemical resistance, bending resistance and electrical properties, etc., so that insulating films such as electrical and electronic parts (protective film, solder resist, It can be suitably used as an interlayer insulating layer.

  In recent years, resin compositions such as polyimide resins, polyurethane resins, polyamideimide resins, and epoxy resins have been used as insulating protective films for flexible wiring boards and the like. In the resin component of these compositions, polybutadiene, polysiloxane, polycarbonate, or the like is introduced as a flexible oligomer component to impart flexibility, flexibility, and low warpage to the cured film. Among these, polyimide resin compositions (for example, Patent Documents 1 and 2) are known as resin compositions excellent in heat resistance, chemical resistance, solvent resistance, and the like.

  The polyimide resin composition is a composition in which a main component is a polyimide siloxane obtained from a tetracarboxylic acid component, a diaminopolysiloxane, and a diamine component composed of an aromatic diamine, and an epoxy resin is added to the polyimide siloxane, and is obtained by heat treatment. By the crosslinking reaction, in addition to the above properties, a cured insulating film having excellent flexibility, small warpage, excellent adhesion to the substrate and excellent electrical properties can be formed. However, this cured insulating film has a problem that the adhesiveness to the sealing material is inferior due to the polysiloxane component contained in the main component polyimidesiloxane.

  As a resin composition having excellent adhesion on the surface of a cured film, a polybutadiene-containing polyurethane resin composition containing a modified polyimide resin containing polybutadiene in the main chain is known (for example, Patent Document 3). This resin composition has adhesiveness with a polyimide film used as a substrate, a wiring pattern, and a sealing material, and is excellent in insulation reliability due to the high insulation inherent in polybutadiene. However, since this cured film is connected to the inner lead part of the wiring pattern using an electronic component such as an IC chip using a gold bump, a heat treatment of about 400 ° C. or more is performed in the connection part for a short time. There is a problem that the heat resistance of the cured film is low, such as swelling of the cured film at the connection part or connection of electronic parts using solder, such as swelling or peeling when immersed in a solder bath. There was a problem that warping remained after curing.

On the other hand, polyimide is excellent in heat resistance, but has a problem that a flexible film cannot be obtained because it is soluble in a solvent and the main chain is rigid. Hydroxyl-terminated imide oligomers that have been oligomerized to increase solubility and facilitate incorporation into compositions with other resin components, and by introducing hydroxyl groups at the ends of the oligomers to provide high reactivity with other resin components And the composition (for example, patent document 4) with an epoxy compound is known. However, the insulating film obtained by heat-treating this hydroxyl-terminated imide oligomer composition has a problem that it is rigid and inferior in flexibility and flexibility.
As described above, it is currently difficult to obtain a cured insulating film that has flexibility and further satisfies both heat resistance and surface adhesion, particularly adhesion to a sealing material. There has been a need for improved insulating film compositions that are all satisfactory.

JP-A-4-36321 JP 7-304950 A JP-A-11-199669 Japanese Patent Laid-Open No. 2-191623

  In the present invention, the cured insulating film (protective film) obtained by heat treatment is less likely to warp (non-curl), flexible, excellent in heat resistance and solder resistance, wiring pattern, polyimide Modified polyimide suitable as a resin component of an insulating film composition having good adhesion to a film and a sealing material and having excellent solvent resistance, chemical resistance, bending resistance and electrical properties, and the modified polyimide An object is to provide a composition for an insulating film using an epoxy compound, a cured insulating film thereof, and the like.

  The present invention reacts (a) a diisocyanate compound, (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene, and (c) a bifunctional hydroxyl-terminated imide oligomer represented by the following chemical formula (1). It relates to the modified polyimide resin obtained.

（式中、Ｒは２価の脂肪族又は芳香族炭化水素基を示し、Ｘはテトラカルボン酸のカルボキシル基を除いた残基を示し、Ｙはジアミンのアミノ基を除いた残基を示し、ｍは０〜２０の整数を示す。）

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 0 to 20.)

The present invention also provides that (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene comprise (b ₁ ) a bifunctional hydroxyl-terminated polybutadiene having a number average molecular weight of 500 to 10,000, ) One or more types of diol compounds containing a bifunctional hydroxyl-terminated polybutadiene comprise (b ₂ ) a reactive polar group-containing diol compound in addition to the bifunctional hydroxyl-terminated polybutadiene, and (b) bifunctional One or more kinds of diol compounds containing a hydroxyl group-terminated polybutadiene are composed of (b ₁ ) a bifunctional hydroxyl group-terminated polybutadiene having a number average molecular weight of 500 to 10,000 and (b ₂ ) a reactive polar group-containing diol. (B ₁ ) + (b ₂ )] / (a) is within a range of 0.5 to 2.5 and (b ₂ ) / (b ₁ ) is within 10 or less. And about.

  The present invention also relates to a modified polyimide resin represented by the following chemical formula (2).

（式中、Ｒは２価の脂肪族又は芳香族炭化水素基を示し、Ｘはテトラカルボン酸のカルボキシル基を除いた残基を示し、Ｙはジアミンのアミノ基を除いた残基を示し、ｍは０〜２０の整数を示し、Ｚは２官能性水酸基末端ポリブタジエンの水酸基を除いた残基を示し、Ｗは２官能性水酸基末端ポリブタジエン以外のジオール化合物の水酸基を除いた残基を示し、Ａはジイソシアネート化合物のイソシアネート基を除いた残基を示し、ｓ及びｕはそれぞれ独立に１〜１００の整数を示し、ｔは０〜１００の整数を示す。）

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 0 to 20, Z represents a residue obtained by removing the hydroxyl group of the bifunctional hydroxyl-terminated polybutadiene, W represents a residue obtained by removing a hydroxyl group of a diol compound other than the bifunctional hydroxyl-terminated polybutadiene, A represents a residue excluding the isocyanate group of the diisocyanate compound, s and u each independently represents an integer of 1 to 100, and t represents an integer of 0 to 100.)

  Furthermore, the present invention provides a diisocyanate compound represented by the following chemical formula (3) obtained by reacting (a) a diisocyanate compound with (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene, ) It relates to a method for producing a modified polyimide resin characterized by reacting with a bifunctional hydroxyl-terminated imide oligomer represented by the following chemical formula (4).

（式中、Ｚは２官能性水酸基末端ポリブタジエンの水酸基を除いた残基を示し、Ｗは２官能性水酸基末端ポリブタジエン以外のジオール化合物の水酸基を除いた残基を示し、Ａはジイソシアネート化合物のイソシアネート基を除いた残基を示し、ｓは１〜１００の整数を示し、ｔは０〜１００の整数を示す。）

(In the formula, Z represents a residue excluding the hydroxyl group of the bifunctional hydroxyl-terminated polybutadiene, W represents a residue excluding the hydroxyl group of a diol compound other than the bifunctional hydroxyl-terminated polybutadiene, and A represents an isocyanate of a diisocyanate compound. The residue except a group is shown, s shows the integer of 1-100, and t shows the integer of 0-100.)

（式中、Ｒは２価の脂肪族又は芳香族炭化水素基を示し、Ｘはテトラカルボン酸のカルボキシル基を除いた残基を示し、Ｙはジアミンのアミノ基を除いた残基を示し、ｍは０〜２０の整数を示す。）

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 0 to 20.)

  Furthermore, the present invention relates to a modified polyimide resin composition comprising (A) 100 parts by weight of the modified polyimide resin, (B) 1 to 50 parts by weight of an epoxy compound, and (C) an organic solvent, and the modified polyimide. The resin composition further relates to (D) containing a curing catalyst, and (E) containing a fine filler.

  Furthermore, the present invention provides a cured insulation film obtained by heat-treating the modified polyimide resin composition, and a cured insulation by heat-treating the modified polyimide resin composition at 50 to 210 ° C. after applying the substrate. The present invention relates to a method of forming a film.

  According to the present invention, it is possible to obtain a modified polyimide resin that is soluble in an organic solvent and excellent in heat resistance, flexibility, and adhesion to a sealing material, and a solution composition thereof. The solution composition of the present invention can be satisfactorily applied on a substrate such as a flexible wiring board by a method such as screen printing, and has low-temperature curability. The cured film obtained by applying the solution composition of the present invention to a substrate and then heat-treating is hardly warped (non-curl), flexible, excellent in heat resistance and solder resistance, and has a wiring pattern. In addition, it has good adhesion to polyimide film and sealing material, and also has excellent solvent resistance, chemical resistance, bending resistance and electrical properties, etc., so that insulating films such as electrical and electronic parts (protective film, solder resist, It can be suitably used as an interlayer insulating layer.

  The modified polyimide resin of the present invention comprises (a) a diisocyanate compound, (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene, and (c) a bifunctional hydroxyl-terminated imide represented by the following chemical formula (5) Obtained by reacting oligomers.

（式中、Ｒは２価の脂肪族又は芳香族炭化水素基を示し、Ｘはテトラカルボン酸のカルボキシル基を除いた残基を示し、Ｙはジアミンのアミノ基を除いた残基を示し、ｍは０〜２０の整数を示す。）

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 0 to 20.)

  As the (a) diisocyanate compound of the present invention, any compound may be used as long as it has two isocyanate groups in one molecule. For example, an aliphatic, alicyclic or aromatic diisocyanate, preferably an aliphatic, alicyclic or aromatic diisocyanate having 2 to 30 carbon atoms excluding an isocyanate group, specifically 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexame Thiylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanate methyl) ) -Cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphth Range diisocyanate - DOO, tolidine diisocyanate - DOO, xylylene diisocyanate - DOO etc. can be preferably exemplified.

The diisocyanate compound of the present invention may be a blocked diisocyanate in which an isocyanate group is blocked 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 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, acetic acid amide, ε-caprolactam, δ-valero Lactam, γ-Butirola Kutam, etc., acid imide series, succinimide, maleic imide, imidazole series, imidazole, 2-methylimidazole, urea series, urea, thiourea, ethylene urea etc., oxime series, Formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc., amine type, diphenylamine, aniline, carbazole, etc., imine type, ethyleneimine, polyethyleneimine, etc., bisulfite, bisulfite soda Examples of pyridine-based compounds include 2-hydroxypyridine and 2-hydroxyquinoline.

  The number average molecular weight of the bifunctional hydroxyl-terminated polybutadiene used in one or more kinds of diol compounds containing (b) the bifunctional hydroxyl-terminated polybutadiene of the present invention is preferably 500 to 10,000, and preferably 1,000 to 5,000. More preferred. When the number average molecular weight is less than 500, it is difficult to obtain suitable flexibility, and when the number average molecular weight exceeds 10,000, the heat resistance and solvent resistance may be deteriorated. The bifunctional hydroxyl-terminated polybutadiene may have a double bond in the molecule or may be a hydrogenated double bond in the molecule, but the double bond remains in the molecule. In this case, a cross-linking reaction may be caused and flexibility may be lost, and therefore, a double bond in a molecule is particularly preferably hydrogenated. Specific examples of the bifunctional hydroxyl-terminated polybutadiene used in the present invention include GI-1000 and GI-2000 manufactured by Nippon Soda Co., Ltd., R-45EPI manufactured by Idemitsu Petrochemical Co., Ltd., and Polytail H manufactured by Mitsubishi Chemical Co., Ltd. Etc. can be preferably mentioned.

The (b) one or more diol compounds containing the bifunctional hydroxyl-terminated polybutadiene of the present invention may be a bifunctional hydroxyl-terminated polybutadiene alone or a combination of a bifunctional hydroxyl-terminated polybutadiene and another diol compound. In the present invention, (b) the one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene are bifunctional hydroxyl-terminated polybutadienes in which the bifunctional hydroxyl-terminated polybutadiene has a (b ₁ ) number average molecular weight of 500 to 10,000. The other diol compound to be combined with the bifunctional hydroxyl-terminated polybutadiene is preferably a (b ₂ ) reactive polar group-containing diol compound.
In the present invention, (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene are (b ₁ ) a bifunctional hydroxyl-terminated polybutadiene having a number average molecular weight of 500 to 10,000 and (b ₂ ) a reactive polar group. It is preferable that it comprises a combination of (b ₁ ) a bifunctional hydroxyl-terminated polybutadiene having a number average molecular weight of 500 to 10,000 and (b ₂ ) a reactive polar group-containing diol compound. is there.

In the present invention, the reactive polar group-containing diol compound preferably used in combination with the bifunctional hydroxyl-terminated polybutadiene is a diol compound having a polar group having reactivity with an epoxy group or an isocyanate group in the molecule. is there. By introducing such a reactive polar group into the molecule of the modified polyimide, it is possible to effectively crosslink the modified polyimide resin composition, and the resulting cured insulating film has heat resistance and resistance. Solvent properties can be further increased.
The reactive polar group-containing diol compound is not particularly limited, but a diol compound having an active hydrogen as a substituent, for example, a diol compound having a carboxyl group or a phenolic hydroxyl group is preferred, and in particular, a carboxyl group as a substituent. A diol compound having 1 to 30 carbon atoms and further having 2 to 20 carbon atoms having a phenolic hydroxyl group is preferred. Specifically, examples of the diol compound having a carboxyl group include 2,2-bis (hydroxymethyl) propionic acid and 2,2-bis (hydroxymethyl) butyric acid. Examples of the diol compound having a phenolic hydroxyl group include 2,6-bis (hydroxymethyl) -phenol and 2,6-bis (hydroxymethyl) -p-cresol.

  The (c) bifunctional hydroxyl-terminated imide oligomer of the present invention can be represented by the following chemical formula (6).

（式中、Ｒは２価の脂肪族又は芳香族炭化水素基を示し、Ｘはテトラカルボン酸成分のカルボキシル基を除いた残基を示し、Ｙはジアミンのアミノ基を除いた残基を示し、ｍは０〜２０の整数を示す。）

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue obtained by removing the carboxyl group of the tetracarboxylic acid component, and Y represents a residue obtained by removing the amino group of the diamine. M represents an integer of 0 to 20.)

  This bifunctional hydroxyl-terminated imide oligomer is obtained from a tetracarboxylic acid component and an amine component composed of a diamine compound and a monoamine compound having one hydroxyl group. In the above formula, m represents an integer of 0 to 20, particularly 0 to 10, and more preferably 0 to 5. When m is 20 or more, the bending resistance of the obtained insulating film may be deteriorated.

As the tetracarboxylic acid component of the bifunctional hydroxyl-terminated imide oligomer, aromatic tetracarboxylic acids or acid dianhydrides or esterified products of lower alcohols are excellent in the heat resistance of the resulting modified polyimide resin. Therefore, it is preferable. Specifically, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic 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-naphthalenetetracarboxylic acid, 1,4 , 5,8-Naph Aromatic tetracarboxylic acids such as lentetracarboxylic acid, 1,1-bis (2,3-dicarboxyphenyl) ethane, or their acid dianhydrides and esterified products of lower alcohols, and cyclopentanetetracarboxylic acid 1,2,4,5-cyclohexanetetracarboxylic acid, alicyclic tetracarboxylic acids such as 3-methyl-4-cyclohexene-1,2,4,5-tetracarboxylic acid, or acid dianhydrides thereof And esterified products of lower alcohols. Among these, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, and 2,2 ′, 3,3′-biphenyl are particularly preferred. Tetracarboxylic acids or their acid dianhydrides or esterified products of lower alcohols are preferred because they have excellent solubility in organic solvents when used as modified polyimides.
In the present invention, the tetracarboxylic acid component is preferably a tetracarboxylic dianhydride that can be easily reacted with a diamine.

  In the present invention, the diamine compound in the amine component constituting the bifunctional hydroxyl-terminated imide oligomer is not particularly limited, and aromatic, alicyclic and aliphatic diamines can be used. The aromatic diamine specifically includes one benzene such as 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 1,4-diamino-2,5-dihalogenobenzene. Diamines, 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-tolidine, tolidinesulfo Diamines containing two benzenes such as acids, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, α, α′-bis (4-aminophenyl) -1,3- Diamines containing three benzenes such as 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-bis (4-aminophene) Nyl) fluorene, diamine compounds such as diamines containing 4 or more benzenes such as 5,10-bis (4-aminophenyl) anthracene. Specific examples of the alicyclic diamine include isophorone diamine, norbornene diamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, and bis (4- (Aminocyclohexyl) methane and the like. Specific examples of the aliphatic diamine include hexamethylene diamine and diaminododecane.

  Among these diamine compounds, modified polyimide resins obtained using alicyclic diamines have good solubility in solvents, making it easy to form a uniformly dissolved solution, and excellent heat resistance. In addition, the adhesiveness is good, which is preferable. As the alicyclic diamine, those having 4 to 20 carbon atoms are particularly suitable. The modified polyimide obtained using the aromatic diamine has a polybutadiene unit and an aromatic imide oligomer unit in the molecule, and the solvent species in which these units are easy to dissolve mutually contradict each other. May be difficult to do. In addition, when an aliphatic diamine is used, it is difficult to cause a problem in solubility, but heat resistance may be inferior.

  In the present invention, the monoamine compound having one hydroxyl group in the amine component constituting the bifunctional hydroxyl-terminated imide oligomer is not particularly limited as long as it is a compound having one hydroxyl group and one amino group in the molecule. An aliphatic monoamine compound having a hydroxyl group such as aminoethanol, aminopropanol, and aminobutanol, particularly an aliphatic monoamine compound having a hydroxyl group having 1 to 10 carbon atoms, and an alicyclic monoamine compound having a hydroxyl group such as aminocyclohexanol. Alicyclic monoamine compound having a hydroxyl group having 3 to 20 carbon atoms, aminophenol, aminocresol, 4-hydroxy-4'-aminodiphenyl ether, 4-hydroxy-4'-aminobiphenyl, aminobenzyl alcohol, aminophenethyl alcohol Water In particular carbon number aromatic monoamine compound having an group can be preferably exemplified an aromatic monoamine compound having 6-20 hydroxyl groups.

  In the bifunctional hydroxyl-terminated imide oligomer of the present invention, in particular, m in the chemical formula (6) is an integer of 0 to 20, particularly an integer of 1 to 20, X is a tetravalent aromatic group, and Y is 4 carbon atoms. Those having a divalent alicyclic hydrocarbon group of ˜20 and R being a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms are preferable because of good solubility and heat resistance.

  In the present invention, the bifunctional hydroxyl-terminated imide oligomer comprises a tetracarboxylic acid component and an amine component composed of a diamine compound and a monoamine compound having one hydroxyl group. The number of equivalents of the individual carboxylic groups and the like and the number of equivalents of the amino groups of the amine component can be obtained by polymerization and imidization reaction in an organic solvent. Specifically, a tetracarboxylic acid component (particularly tetracarboxylic dianhydride), an amine component composed of a diamine compound and a monoamine compound having a hydroxyl group, an acid anhydride group (or an adjacent dicarboxylic acid group) and an amine component Using each component in an organic polar solvent at a ratio such that the amino group is approximately equivalent, the reaction is carried out in an organic polar solvent at a reaction temperature of about 100 ° C. or less, particularly 80 ° C. or less to produce an oligomer having an amide-acid bond. Then, the amide-acid oligomer (also called amic acid oligomer) is added with an imidizing agent at a low temperature of about 0 ° C. to 140 ° C. or heated at a high temperature of 140 ° C. to 250 ° C. It can be obtained by the method of making it. In the dehydration / imidation reaction, toluene or xylene may be added and reacted while removing condensed water by azeotropy.

  Examples of the organic solvent used in producing the bifunctional hydroxyl-terminated imide oligomer include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and the like. Amide solvents, dimethyl sulfoxide, hexamethylphosphamide, dimethylsulfone, tetramethylenesulfone, dimethyltetramethylenesulfone-containing solvents such as sulfur atoms, cresol, phenol, xylenol and other phenolic solvents, diethylene glycol dimethyl ether (diglyme), Diglyme solvents such as triethylene glycol dimethyl ether (triglyme) and tetraglyme, lactone solvents such as γ-butyrolactone, isophorone, cyclohexanone, 3,3,5-tri Ketone solvents such as chill cyclohexanone, pyridine, ethylene glycol, dioxane, its other solvents such as tetramethylurea and benzene optionally toluene, aromatic hydrocarbon solvents such as xylene. These organic solvents may be used alone or in combination of two or more.

The bifunctional hydroxyl-terminated imide oligomer produced as described above may be a mixture of a plurality of bifunctional hydroxyl-terminated imide oligomers having different m in the chemical formula (2). Mixtures composed of a plurality of bifunctional hydroxyl-terminated imide oligomers having different suffices may be used separately for each imide oligomer, but can be suitably used as they are without separation. In addition, m (average value of m in the case of a mixture) of the bifunctional hydroxyl-terminated imide oligomer can be controlled by the charging ratio (molar ratio) of the diamine compound and the monoamine compound in the amine component at the time of production.
In addition, the bifunctional hydroxyl-terminated imide oligomer produced as described above may be used as a modified imide oligomer solution by directly or concentrating or diluting the reaction solution as it is. Alternatively, the reaction solution may be poured into a non-soluble solvent such as water and isolated as a powdery product, and the powder product may be dissolved in an organic polar solvent when necessary.

  The modified polyimide resin of the present invention is obtained by reacting (a) a diisocyanate compound, (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene, and (c) a bifunctional hydroxyl-terminated imide oligomer. . (A) (b) (c) The composition ratio of each component is the total number of hydroxyl groups / isocyanate groups, and the specific component indicates the molar ratio of ((b) + (c)] / (a). A ratio of 0.5 to 3.0, preferably 0.8 to 2.5, particularly 0.9 to 2.0 is suitable. If the amount of component (a) is too large, the polymerization solution may thicken, which is not preferable. Furthermore, it is preferable that (b) and (c) have a molar ratio of (b) / (c) of 100 to 0.01, preferably 10 to 0.1. When there are too many (b) components, it is inferior to heat resistance, and when there are too many (c) components, since it is inferior to a softness | flexibility, it is unpreferable.

In addition, (b) bifunctional hydroxyl-terminated polybutadiene having (b ₁ ) number average molecular weight of 500 to 10,000 is (b ₂₎ and (b ₂₎ And (a) and [(b ₁ ) + (b ₂ )] are in a molar ratio of [(b ₁ ) + (b ₂ )] / (a) when comprising a combination with a reactive polar group-containing diol compound. Is a ratio of 0.5 to 2.5, preferably 0.8 to 2.5, and (b ₁ ) and (b ₂ ) have a molar ratio of (b ₂ ) / (b ₁ ) of 0 to 0. 10 is preferably a ratio of 0 to 5. When the value of [(b ₁ ) + (b ₂ )] / (a) is too small, the content of the component (c) is increased and the flexibility is inferior, and [(b ₁ ) + (b ₂ )] / (a If the value of) is too large, the content of the component (c) decreases and the heat resistance is poor, so the ratio in the above range is preferred. Moreover, in the ratio of (b ₁ ) and (b ₂ ), if the ratio of the (b ₂ ) reactive polar group-containing diol compound is too large, the viscosity of the modified polyimide resin solution becomes too high, or the cured film obtained This is not preferable because the hygroscopicity may be excessively increased. On the other hand, if the ratio of the (b ₂ ) reactive polar group-containing diol compound is too small, the crosslinking density is lowered, and the heat resistance of the resulting cured film tends to be lowered, which is not preferable.

  The modified polyimide resin of the present invention is preferably a modified polyimide resin represented by the following chemical formula (7).

（式中、Ｒは２価の脂肪族又は芳香族炭化水素基を示し、Ｘはテトラカルボン酸のカルボキシル基を除いた残基を示し、Ｙはジアミンのアミノ基を除いた残基を示し、ｍは０〜２０の整数を示し、Ｚは２官能性水酸基末端ポリブタジエンの水酸基を除いた残基を示し、Ｗは２官能性水酸基末端ポリブタジエン以外のジオール化合物の水酸基を除いた残基を示し、好ましくはＷは反応性極性基含有ジオール化合物の水酸基を除いた残基を示し、Ａはジイソシアネート化合物のイソシアネート基を除いた残基を示し、ｓ及びｕはそれぞれ独立に１〜１００の整数を示し、ｔは０〜１００の整数好ましくは１〜１００の整数を示す。）
本発明の前記化学式（７）の変性ポリイミドは、とりわけ、Ｒが炭素数１〜１０の２価の脂肪族炭化水素基、Ｘが４価の芳香族基、Ｙが炭素数４〜２０の２価の脂環式炭化水素基、ｍが０〜２０の整数特に１〜２０の整数、Ｚが数平均分子量が５００〜１００００の２価の炭化水素基、Ｗがカルボキシル基を含有する炭素数が２〜２０の炭化水素基、且つＡが炭素数が２〜３０の炭化水素基であるものが、溶解性や耐熱性が良好なので好適である。
なお、化学式（７）は、ウレタン結合を介して、２官能性水酸基末端ポリブタジエンユニット、反応性極性基含有ジオール化合物ユニット、及び２官能性水酸基末端イミドオリゴマーユニットが共重合したものであり、ｓ、ｔ、及びｕは２官能性水酸基末端ポリブタジエンユニット、反応性極性基含有ジオール化合物ユニット、及び２官能性水酸基末端イミドオリゴマーユニットの重合度と構成比を示しているが、前記の各ユニットがブロック共重合していることを限定的に示しているのではない。化学式（７）では、２官能性水酸基末端ポリブタジエンユニット、反応性極性基含有ジオール化合物ユニット、及び２官能性水酸基末端イミドオリゴマーユニットがブロック共重合でもランダム共重合でも構わない。さらに、化学式（７）では、末端は明示していないが、末端は、そこに位置したジイソシアネート化合物又は前記各ユニットによって、イソシアネート基か又は水酸基になっている。

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 0 to 20, Z represents a residue obtained by removing the hydroxyl group of the bifunctional hydroxyl-terminated polybutadiene, W represents a residue obtained by removing a hydroxyl group of a diol compound other than the bifunctional hydroxyl-terminated polybutadiene, Preferably, W represents a residue excluding the hydroxyl group of the reactive polar group-containing diol compound, A represents a residue excluding the isocyanate group of the diisocyanate compound, and s and u each independently represents an integer of 1 to 100. T represents an integer of 0 to 100, preferably an integer of 1 to 100.)
In the modified polyimide of the chemical formula (7) of the present invention, R is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, X is a tetravalent aromatic group, and Y is 2 having 4 to 20 carbon atoms. A valent alicyclic hydrocarbon group, m is an integer of 0 to 20, particularly an integer of 1 to 20, Z is a divalent hydrocarbon group having a number average molecular weight of 500 to 10,000, and W is a carbon number containing a carboxyl group. A hydrocarbon group having 2 to 20 hydrocarbon groups and A being a hydrocarbon group having 2 to 30 carbon atoms is preferable because of good solubility and heat resistance.
The chemical formula (7) is obtained by copolymerizing a bifunctional hydroxyl-terminated polybutadiene unit, a reactive polar group-containing diol compound unit, and a bifunctional hydroxyl-terminated imide oligomer unit via a urethane bond, and s, t and u indicate the degree of polymerization and the composition ratio of the bifunctional hydroxyl-terminated polybutadiene unit, the reactive polar group-containing diol compound unit, and the bifunctional hydroxyl-terminated imide oligomer unit. It is not a limited indication of polymerization. In the chemical formula (7), the bifunctional hydroxyl-terminated polybutadiene unit, the reactive polar group-containing diol compound unit, and the bifunctional hydroxyl-terminated imide oligomer unit may be block copolymerized or random copolymerized. Furthermore, in Chemical formula (7), although the terminal is not specified, the terminal is an isocyanate group or a hydroxyl group by the diisocyanate compound or each unit located there.

  The modified polyimide resin of the present invention reacts (a) a diisocyanate compound, (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene, and (c) a bifunctional hydroxyl-terminated imide oligomer in an organic solvent. Obtained.

  In the present invention, the modified polyimide resin may react by dissolving all components in an organic solvent at the same time, but (c) when a molecular chain in which the bifunctional hydroxyl-terminated imide oligomer unit is continuous in a block form is generated. Since it is insoluble in a solvent and easily precipitates, (a) a diisocyanate compound and (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene are reacted in excess with respect to the hydroxyl group. Thus, it is preferable to synthesize both terminal isocyanate compounds represented by the following chemical formula (8) and then react with (c) a bifunctional hydroxyl-terminated imide oligomer to maintain solubility.

（式中、Ｚは２官能性水酸基末端ポリブタジエンの水酸基を除いた残基を示し、Ｗは２官能性水酸基末端ポリブタジエン以外のジオール化合物の水酸基を除いた残基を示し、好ましくはＷは反応性極性基含有ジオール化合物の水酸基を除いた残基を示し、Ａはジイソシアネート化合物のイソシアネート基を除いた残基を示し、ｓは１〜１００の整数を示し、ｔは０〜１００の整数好ましくは１〜１００の整数を示す。）
なお、化学式（８）は、ウレタン結合を介して、２官能性水酸基末端ポリブタジエンユニット及び反応性極性基含有ジオール化合物ユニットが共重合したものであり、ｓ及びｔは２官能性水酸基末端ポリブタジエンユニット及び反応性極性基含有ジオール化合物ユニットの重合度と構成比を示しているが、前記の各ユニットがブロック共重合していることを限定的に示しているのではない。化学式（８）では、２官能性水酸基末端ポリブタジエンユニット及び反応性極性基含有ジオール化合物ユニットがブロック共重合でもランダム共重合でも構わない。

(In the formula, Z represents a residue obtained by removing the hydroxyl group of the bifunctional hydroxyl-terminated polybutadiene, W represents a residue obtained by removing the hydroxyl group of a diol compound other than the bifunctional hydroxyl-terminated polybutadiene, and preferably W is reactive. The residue of the polar group-containing diol compound excluding the hydroxyl group is shown, A is the residue of the diisocyanate compound excluding the isocyanate group, s is an integer of 1 to 100, and t is an integer of 0 to 100, preferably 1. Represents an integer of ~ 100.)
The chemical formula (8) is obtained by copolymerizing a bifunctional hydroxyl-terminated polybutadiene unit and a reactive polar group-containing diol compound unit via a urethane bond, and s and t are a bifunctional hydroxyl-terminated polybutadiene unit and Although the polymerization degree and the composition ratio of the reactive polar group-containing diol compound unit are shown, it does not limit that the above units are block copolymerized. In the chemical formula (8), the bifunctional hydroxyl-terminated polybutadiene unit and the reactive polar group-containing diol compound unit may be block copolymerization or random copolymerization.

  The production method of the modified polyimide resin of the present invention will be specifically described. The reaction between (a) a diisocyanate compound and (b) one or more kinds of diol compounds containing a bifunctional hydroxyl-terminated polybutadiene is carried out in a solvent-free or organic solvent. It can be done by dissolving. The reaction temperature is 30 ° C to 150 ° C, preferably 30 ° C to 120 ° C, and the reaction time is usually 1 to 10 hours. This reaction is preferably performed in a nitrogen atmosphere in order to prevent the isocyanate from being deactivated by moisture.

  The reaction between the obtained diisocyanate compound represented by the general formula (4) and (c) the bifunctional hydroxyl-terminated imide oligomer is carried out in an organic solvent at a reaction temperature of 30 ° C to 150 ° C, preferably 30 ° C to 120 ° C. It can be suitably performed under a nitrogen atmosphere for 1 to 10 hours. In this reaction, the ratio of the number of hydroxyl groups in the (c) bifunctional hydroxyl-terminated imide oligomer to the number of isocyanate groups in the diisocyanate compound represented by the general formula (4) (the number of hydroxyl groups / the number of isocyanate groups) is 0.5-2. 5 is preferably 1.5 to 2.5. If it is 0.5 or less, the heat resistance of the resulting modified polyimide resin is low, and if it is 2.5 or more, it becomes too hard when it is used as a cured film.

  Examples of the organic solvent that can be suitably used in the reaction for producing the modified polyimide resin include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam. Solvents, sulfur-containing solvents such as dimethyl sulfoxide, hexamethylphosphamide, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, phenol solvents such as cresol, phenol, xylenol, diethylene glycol dimethyl ether (diglyme), triethylene Glycol dimethyl ether (triglyme), diglyme solvents such as tetraglyme, lactone solvents such as γ-butyrolactone, isophorone, cyclohexanone, 3,3,5-trime Ketone solvents such as Le cyclohexanone, pyridine, ethylene glycol, dioxane, its other solvents such as tetramethylurea and benzene optionally toluene, aromatic hydrocarbon solvents such as xylene. These solvents may be used alone or as a mixture of several solvents.

  Among these solvents, isophorone is highly soluble in both the bifunctional hydroxyl-terminated polybutadiene unit and the bifunctional hydroxyl-terminated imide oligomer unit contained in the modified polyimide resin. This is particularly suitable. Furthermore, when isophorone as a reaction solvent is used as it is as the solvent of the modified polyimide resin composition, it is suitable because it has a low hygroscopic property, a high boiling point and a low volatility, and is therefore excellent as a solvent for screen printing ink.

In the present invention, the modified polyimide resin can be dissolved in an organic solvent at a high concentration of at least 3% by weight, preferably 5 to 60% by weight, particularly about 5 to 50%. It is preferable that the solution viscosity (E-type rotational viscometer) is 1 to 10,000 poise, particularly 1 to 400 poise because the modified polyimide resin composition (solution composition) of the present invention can be suitably obtained.
If the molecular weight of the modified polyimide resin is too large, the viscosity becomes too high and stirring becomes difficult during synthesis. Moreover, workability | operativity at the time of manufacture of the modified polyimide resin composition of this invention and apply | coating the obtained resin composition by methods, such as screen printing, falls. Therefore, the number average molecular weight of the modified polyimide resin of the present invention is preferably 3000 to 50000, more preferably 4000 to 40000, and particularly preferably 4000 to 30000. When the number average molecular weight is 3000 or less, the heat resistance and mechanical properties of the cured insulating film tend to decrease.

The modified polyimide resin composition of the present invention comprises (A) the modified polyimide resin 100 parts by weight, (B) the epoxy compound 1 to 50 parts by weight, preferably 2 to 40 parts by weight, particularly 5 to 35 parts by weight, and (C). And an organic solvent.
The epoxy compound is preferably a liquid or solid epoxy resin having an epoxy equivalent of about 100 to 4000 and a molecular weight of about 300 to 10,000. For example, bisphenol A type or bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: Epicoat 806, Epicoat 825, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1055, Epicoat 1004AF, Epicoat 1007, Epicoat 1009, Epicoat 1010, etc.) Trifunctional or higher epoxy resin (Japan Epoxy Resins, Inc .: Epicoat 152, Epicoat 154, Epicoat 180 series, Epicoat 157 series, Epicoat 1032 series, manufactured by Sumitomo Chemical Co., Ltd.) : Sumiepoxy ELM100, manufactured by Daicel Chemical Industries, Ltd .: EHPE3150, manufactured by Ciba-Gaigi: MT0163, etc., terminal epoxidized oligomer (Ube) Hiker ETBN 1300 × 40 manufactured by Sangyo Co., Ltd., Denarex R-45EPT manufactured by Nagase Chemtex Co., Ltd.), epoxidized polybutadiene (manufactured by Nippon Petrochemical Co., Ltd .: polybutadiene E-1000-8, E-1800-6.5, Daicel Chemical Industries, Ltd .: Epolide PB3600 and the like).

  In addition to (A), (B), and (c), the modified polyimide resin composition of the present invention further comprises (F) a block polyvalent isocyanate compound of 1 to 50 parts by weight, preferably 2 to 40 parts by weight, particularly 5 to 35. You may be comprised including a weight part. If the amount of the epoxy compound and the block polyisocyanate compound used is too large, the electrical insulating properties of the cured insulating film will be lowered, and if it is too small, the heat resistance and chemical resistance of the cured insulating film will be deteriorated. Is preferred.

  As the block polyvalent isocyanate compound, in particular, Bernock D-500 (tolylene diisocyanate blocked product), D-550 (1,6-hexamethylene diisocyanate) manufactured by Dainippon Ink and Chemicals, Inc. -T-blocked product), Takenate Takenate B-830 (tolylene diisocyanate-blocked product) manufactured by Mitsui Takeda Chemical Co., Ltd., B-815N (4,4'-methylenebis (cyclohexyl isocyanate) blocked product), B-842N (1,3-bis (isocyanatemethyl) cyclohexane blocked), B-846N (1,3-bis (isocyanatemethyl) cyclohexane blocked), B-874N (isophorone diisocyanate blocked) ), B-882N (1,6-hexamethylene diisocyanate) Locked product), Duranate MF-B60X (1,6-hexamethylene diisocyanate blocked product) manufactured by Asahi Kasei Corporation, Duranate MF-K60X (1,6-hexamethylene diisocyanate blocked product), manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Elastolone BN-P17 (4,4'-diphenylmethane diisocyanate block), Elastolon BN-04, Elastolon BN-08, Elastolon BN-44, Elastolon BN-45 (above, urethane-modified polyisocyanate block) 3 to 5 functional groups per molecule, all of which are water emulsion products that can be used after drying and isolation) can be suitably used.

The modified polyimide resin composition of the present invention further comprises (G) a bifunctional hydroxyl-terminated polycarbonate in addition to the above (A), (B) and (c) in order to increase the adhesion to the sealing material. can do. The addition amount of the bifunctional hydroxyl-terminated polycarbonate is 1 to 20 parts by weight, preferably 1 to 15 parts by weight, particularly 1 to 10 parts by weight with respect to 100 parts by weight of the above-mentioned (A) modified polyimide resin. If the amount of the bifunctional hydroxyl-terminated polycarbonate is too much above the above range, the chemical resistance and tackiness of the insulating film after curing will decrease, and if it is too small, it will adhere to the amount of sealing material of the insulating film after curing. The above range is preferred because the properties are not improved.
The bifunctional hydroxyl-terminated polycarbonate preferably has a number average molecular weight of 500 to 10,000, more preferably 500 to 5,000. When the number average molecular weight is less than 500, tackiness tends to appear, and when the number average molecular weight exceeds 10,000, the solvent resistance may be deteriorated. The bifunctional hydroxyl-terminated polycarbonate used in the present invention is specifically made by Ube Industries, Ltd. Etanacol UH-CARB, Etanacol UN-CARB, Etanacol UD-CARB, Etanacol UC-CARB, manufactured by Daicel Chemical Industries, Ltd. Suitable examples include PLACEL CD-PL, PLACEL CD-H, and Kuraray polyol C manufactured by Kuraray Co., Ltd. These polycarbonate diols are used alone or in combination of two or more.

  The modified polyimide resin composition of the present invention further comprises (H) a phenolic hydroxyl group in addition to the above (A), (B) and (c) in order to increase adhesion to an anisotropic conductive material and the like. Compounds can be included. Examples of the compound having a phenolic hydroxyl group include phenol resins such as hydroquinone, 4,4′-dihydroxybiphenyl, phenol novolac, and cresol novolac. As phenol resin, Meiwa Kasei Co., Ltd. phenol novolak 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-7785, triphenol type R-3, bisphenol novolac type MEP-6309, MEP-6309E, liquid phenol novolac MEH-8000H, MEH-8005, MEH-8010, MEH-8015, MEH-8205, etc. can be mentioned. When adding a compound having two or more phenolic hydroxyl groups, 0.1 to 18 parts by weight, preferably 0.3 to 15 parts by weight, and more preferably 0 to 100 parts by weight of (A) modified polyimide resin. It is preferable to add about 5 to 10 parts by weight.

  It is preferable that the modified polyimide resin composition of the present invention further contains (D) a curing catalyst for promoting a crosslinking reaction between the modified polyimide resin and the epoxy compound. Examples of the curing accelerating catalyst include imidazoles 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 epoxy compound.

  Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-imidazole, and the like.

  Examples of the tertiary amine include 1,8-diazabicyclo [5.4.0] -7-undecene (abbreviated as DBU; the same shall apply hereinafter), N, N-dimethylbenzylamine, N, N, N ', N'-tetramethylhexanediamine, triethylenediamine (TEDA), 2-dimethylaminomethylphenol (DMP-10), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), dimorpholinodiethyl Examples include ether (DMDEE), 1,4-dimethylpiperazine, cyclohexyldimethylamine, and the like.

  As the organic solvent (C) constituting the modified polyimide resin composition of the present invention, the organic solvent used when synthesizing the modified polyimide resin can be used as it is, but preferably a nitrogen-containing solvent, for example, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N- Sulfur-containing atomic solvents such as methyl caprolactam, such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfuramide, etc. Oxygen-containing solvents such as phenolic solvents such as cresol, phenol, xyleno Diglyme solvents such as diethylene glycol dimethyl ether Ter (diglyme), triethylene glycol dimethyl ether (triglyme), tetraglyme, etc., ketone solvents such as acetone, acetophenone, propiophenone, cyclohexanone, isophorone, etc. Lactone solvents such as ethylene glycol, dioxane, tetrahydrofuran, etc. Examples thereof include γ-butyrolactone. 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 or the like can be preferably used.

  Furthermore, the modified polyimide resin composition of the present invention preferably contains (E) a fine filler. As long as it is a fine filler, any size and shape may be used, but those having an average particle diameter of 0.001 to 15 μm, particularly 0.005 to 10 μm are preferable. Use of a material outside this range is not preferable because a cured insulating film obtained may be cracked, a bent portion may be whitened, or a fine wiring may be short-circuited. Preferred examples of the fine filler include fine inorganic fillers such as finely divided silica, talc and barium sulfate, and fine organic fillers such as crosslinked NBR fine particles.

  The amount of fine filler used is 5 to 150 parts by weight, preferably 10 to 125 parts by weight, based on 100 parts by weight of the modified polyimide resin. 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. Further, a fine inorganic filler, particularly finely divided silica and at least one of talc, mica or barium sulfate are used in combination, and the finely divided silica is used in an amount of 1 to 50 parts by weight, especially 5 to 5 parts by weight based on 100 parts by weight of the modified polyimide resin. It is particularly preferred to use 5 to 130 parts by weight of 40 parts by weight, talc, mica or barium sulfate with respect to 100 parts by weight of the modified polyimide resin in view of printability and the performance of the obtained insulating film.

In the modified polyimide resin composition of the present invention, a predetermined amount of a pigment such as an organic color pigment or an inorganic color pigment may be used, for example, about 0.1 to 100 parts by weight with respect to 100 parts by weight of the modified polyimide resin. it can.
Moreover, in the modified polyimide resin composition of this invention, a defoaming agent can be used about 0.1-10 weight part with respect to predetermined amount, for example, 100 weight part of modified polyimide resin.

  The modified polyimide resin composition (solution composition) of the present invention can be easily obtained by uniformly stirring and mixing predetermined amounts of a modified polyimide resin, an epoxy compound, a fine filler, an organic solvent, and the like. A modified polyimide resin composition can be obtained by mixing a modified polyimide resin, an epoxy compound, a fine filler, and the like with an organic solvent. Moreover, an epoxy compound, a fine filler, etc. can be mixed with the reaction solution at the time of manufacturing a modified polyimide resin, or by diluting the reaction solution with an appropriate organic solvent to obtain a modified polyimide resin composition. . Examples of the organic solvent used in the modified polyimide resin composition include organic polar solvents that can be used when obtaining the modified polyimide resin, and those having a boiling point of 140 ° C. or higher and 220 ° C. or lower are preferably used. Especially when an organic solvent having a boiling point of 180 ° C. or higher, particularly 200 ° C. or higher, such as triglyme (boiling point 216 ° C.), γ-butyrolactone (boiling point 204 ° C.), isophorone (boiling point 213 ° C.) or the like, This is optimal because printing can be favorably performed without any trouble by screen printing using the printing ink. The organic solvent is used in an amount of about 30 to 500 parts by weight, preferably about 60 to 200 parts by weight, based on 100 parts by weight of the modified polyimide resin.

  The modified polyimide resin composition of the present invention is not particularly limited, but the solution viscosity at room temperature (25 ° C.) is 50 to 10000 poise, particularly 100 to 1000 poise, and further 100 to 600 poise, such as screen printing. It is appropriate in view of workability, solution physical properties, and characteristics of the obtained cured insulating film.

The modified polyimide resin 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. It is preferable to form a cured insulating film having an elastic modulus of 10 to 500 MPa. The composition for a modified polyimide resin of the present invention is less likely to warp, has high flexibility, and has good adhesion to a conductive metal, a base material and a sealing material, heat resistance, solder heat resistance, solvent resistance A cured insulating film (protective film) having excellent properties (for example, solvent resistance to acetone, isopropanol, methyl ethyl ketone, N-methyl-2-pyrrolidone), chemical resistance, flex resistance, and electrical characteristics may be formed. it can.
Furthermore, the modified polyimide resin insulating film composition of the present invention is cured by a relatively low temperature heat treatment of about 50 to 210 ° C., particularly 60 to 160 ° C., to form an insulating film having the above-mentioned good performance. can do.

  Moreover, the modified polyimide resin composition of the present invention can be used as a heat-resistant adhesive that can be subjected to low-temperature pressure bonding as described above, and can also be suitably used as an interlayer adhesive for multilayer wiring boards.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

In the following examples, measurement and evaluation were performed by the following methods.
[1H-NMR spectrum]
¹ H-NMR spectrum was measured by dissolving a sample in heavy dimethyl sulfoxide or heavy chloroform using a nuclear magnetic resonance spectrometer (AL-300 manufactured by JEOL Ltd.).

(Solution viscosity)
Using a viscometer TV-20 manufactured by Toki Sangyo Co., Ltd., it was measured at a temperature of 25 ° C. and a rotation speed of 10 rpm.

[GPC]
Using a LC-10 (GPC column KF-80M × 2, KF-802) manufactured by Shimadzu Corporation, measurement was performed using THF as a solvent, and a number average molecular weight was determined using a polystyrene standard sample.

[Tensile modulus]
A sheet-like sample cured to have a thickness of about 100 μm was cut into a width of 1 cm and a length of 7 cm and used for the test. The measurement was performed at a temperature of 25 ° C., a humidity of 50% RH, a cross head speed of 50 mm / min, and a distance between chucks of 5 cm.
Examples 6 to 20 and Comparative Examples 1 and 2 were cured by heat treatment at 80 ° C. for 30 minutes and then at 150 ° C. for 60 minutes, and Examples 21 to 22 were cured by heat treatment at 80 ° C. for 30 minutes and then at 120 ° C. for 90 minutes. A sheet sample sample was used.

[Evaluation of cured insulating film]
The modified polyimide composition is applied to the glossy surface of an electrolytic copper foil having a thickness of 35 μm, and the insulating film composition is applied to a thickness of about 50 μm. The heat treatment is performed at 80 ° C. for 30 minutes, then at 120 ° C. for 60 minutes, and at 80 ° C. for 30 minutes. Next, a heat treatment at 120 ° C. for 90 minutes, or a heat treatment at 80 ° C. for 30 minutes and then at 150 ° C. for 60 minutes, an insulating film having a thickness of about 20 μm was formed. Using this cured insulating film sample, bendability, adhesion to a sealing material, solder heat resistance and solvent resistance were evaluated by the following methods.

Evaluation of bendability:
The cured insulating film sample was folded and the insulating film surface at the bent portion was observed. The case where there was no abnormality was indicated by ○, and the case where a crack occurred was indicated by ×.
Examples 6 to 20 and Comparative Examples 1 and 2 were cured at 80 ° C. for 30 minutes and then at 150 ° C. for 60 minutes, and Examples 21 to 22 were heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 90 minutes. Was used.

Evaluation of adhesion to the sealing material:
An IC chip sealing material CEL-C-5020 (manufactured by Hitachi Chemical Co., Ltd.) was dropped onto the insulating film of the cured insulating film sample in a circular shape having a thickness of about 1 mm and a diameter of about 0.5 cm. The sealing material was cured by heat treatment for a period of time. Thereafter, the sample was bent by hand, and the degree of peeling of the sealing resin was observed. In the case of cohesive failure in the insulating film and in the case of interface film / copper foil interface peeling, the case of insulating film / sealing resin interface peeling is not allowed. The case of 70% is indicated by Δ, and the case of 30% or less is indicated by ×.
Examples 6 to 20 and Comparative Examples 1 and 2 were cured at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes, and Examples 21 to 22 were heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 90 minutes. Was used.

Evaluation of solder heat resistance:
After applying a rosin flux (SUNFLUX SF-270, manufactured by Sanwa Chemical Industry Co., Ltd.) on the insulating film of the cured insulating film sample, the sample insulating film was brought into contact with a 260 ° C. solder bath for 10 seconds. The state of the subsequent sample was observed and evaluated. A case where no abnormality occurred was indicated by ◎, a case where the surface was slightly rough was indicated by ○, and a case where the surface was swollen or melted was indicated by ×.
Examples 6 to 20 and Comparative Examples 1 and 2 were cured at 80 ° C. for 30 minutes and then at 150 ° C. for 60 minutes, and Examples 21 to 22 were heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 90 minutes. Was used.

Evaluation of solvent resistance:
The cured insulating film sample was immersed in acetone at 25 ° C. for 1 hour, and then rubbed (load 300-500 g, rubbing angle 45 °) with a cotton swab soaked in acetone. The number of rubbing until the copper foil was visible was measured.
Examples 6 to 20 and Comparative Examples 1 and 2 were cured at 80 ° C. for 30 minutes and then at 150 ° C. for 60 minutes, and Examples 21 to 22 were heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 90 minutes. Was used.

Measurement of electrical insulation (volume resistance):
A cured insulating film sample heat-treated at 80 ° C. for 30 minutes and then at 150 ° C. for 60 minutes was measured according to JIS C-2103.

The compound, epoxy resin, curing catalyst, and filler used in the following examples will be described.
[Tetracarboxylic acid]
2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (manufactured by Ube Industries, Ltd.)
[Diamine]
2,4-diaminotoluene (Wako Pure Chemical Industries, Ltd.)
Isophoronediamine (manufactured by Wako Pure Chemical Industries, Ltd.)
[Amino alcohol]
3-Aminopropanol (Wako Pure Chemical Industries, Ltd.)
(Reactive polar group-containing diol)
2,2-bis (hydroxymethyl) propionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
[Bifunctional hydroxyl-terminated polybutadiene]
Hydrogenated polybutadiene polyol GI-1000 (manufactured by Nippon Soda Co., Ltd., hydroxyl value: 68.72 KOHmg / g)
Hydrogenated polybutadiene polyol GI-2000 (manufactured by Nippon Soda Co., Ltd., hydroxyl value: 46.2 KOHmg / g)
[Diisocyanate compound]
4,4'-diphenylmethane diisocyanate (Nippon Polyurethane Industry Co., Ltd.)
〔solvent〕
Dimethylacetamide (Wako Pure Chemical Industries, Ltd.)
Toluene (Wako Pure Chemical Industries, Ltd.)
Cyclohexanone (Wako Pure Chemical Industries, Ltd.)
Isophorone (Wako Pure Chemical Industries, Ltd.)
γ-Butyrolactone (Wako Pure Chemical Industries, Ltd.)
〔Epoxy resin〕
Epicoat 157S70 (Japan Epoxy Resin Co., Ltd., epoxy equivalent: 200 to 220)
Epicoat 828EL (Japan Epoxy Resin Co., Ltd., epoxy equivalent: 184-194)
Epolide PB3600 (Daicel Chemical Industries, Epoxy equivalent: 194)
EHPE3150 (Daicel Chemical Industries, epoxy equivalent: 156)
Nisseki Polybutadiene E-1000-8 (manufactured by Nippon Petrochemical Co., Ltd., epoxy equivalent: 200)
SUMI Epoxy ELM100 (Sumitomo Chemical Co., Ltd., epoxy equivalent: 97)
[Block polyisocyanate compound]
Bernock D-550 (Dainippon Ink Chemical Co., Ltd., 1,6-hexamethylene diisocyanate blocked, blocking agent: methyl ethyl ketoxime)
[Bifunctional hydroxyl-terminated polycarbonate]
Etanacol UH-CARB200 (Ube Industries, Ltd., average molecular weight 2000)
Kuraray polyol C-2015 (Kuraray Co., Ltd., average molecular weight 2000)
[Compound having a phenolic hydroxyl group]
H-1 (Maywa Kasei Co., Ltd., phenol novolak)
H-3 (Maywa Kasei Co., Ltd., phenol novolak)
[Curing catalyst]
Curesol 2E4MZ (Shikoku Chemicals Co., Ltd., 2-ethyl-4-methylimidazole)
[Fine powder silica]
Aerosil 130 (Nippon Aerosil Co., Ltd., specific surface area (BET method): 130 m ² / g)
Aerosil R972: Nippon Aerosil Co., Ltd. Specific surface area (BET method): 110 m ² / g)
Aerosil R974: Nippon Aerosil Co., Ltd. Specific surface area (BET method): 170 m ² / g)
Aerosil R805: Nippon Aerosil Co., Ltd. Specific surface area (BET method): 150 m ² / g)
Aerosil R812S: Nippon Aerosil Co., Ltd. Specific surface area (BET method): 220 m ² / g)
Aerosil RX200: Nippon Aerosil Co., Ltd. Specific surface area (BET method): 140 m ² / g)

[Reference Example 1] Production of bifunctional hydroxyl-terminated imide oligomer A 2,3,3 ', 4'-biphenyl was placed in a 500 ml glass separable flask equipped with a nitrogen inlet tube, a Dean-Star cleaver and a cooling tube. Tetracarboxylic dianhydride (58.8 g, 0.20 mol), 3-aminopropanol (30 g, 0.40 mol), and dimethylacetamide (200 ml) were charged, and the mixture was stirred at 100 ° C. for 1 hour in a nitrogen atmosphere. Next, 50 ml of toluene was added and heated at 180 ° C. for 4 hours, and water generated by the imidization reaction was removed azeotropically with toluene. The reaction solution was poured into 2 liters of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 43.16 g of a bifunctional hydroxyl-terminated imide oligomer A powder. The ¹ H-NMR spectrum of this bifunctional hydroxyl-terminated imide oligomer A is shown in FIG. From FIG. 1, it was confirmed that the bifunctional hydroxyl-terminated imide oligomer A was a bifunctional hydroxyl-terminated imide oligomer in which m in the chemical formula (1) was 0.

[Reference Example 2] Production of bifunctional hydroxyl-terminated imide oligomer B In a 500 ml glass separable flask equipped with a nitrogen inlet tube, a Dean-Star cleaver and a cooling tube, 2,3,3 ', 4'-biphenyl Tetracarboxylic dianhydride 58.8 g (0.20 mol), isophoronediamine 17.0 g (0.10 mol), 3-aminopropanol 15.0 g (0.20 mol), and dimethylacetamide 200 ml were charged. The mixture was stirred at 100 ° C. for 1 hour under a nitrogen atmosphere. Next, 50 ml of toluene was added and heated at 180 ° C. for 4 hours, and water generated by the imidization reaction was removed azeotropically with toluene. The reaction solution was poured into 2 liters of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 78.8 g of a bifunctional hydroxyl-terminated imide oligomer B powder. The ¹ H-NMR spectrum of this bifunctional hydroxyl-terminated imide oligomer B is shown in FIG. From the integrated intensity ratio of the 2-position methylene proton (1.65 to 1.85 ppm) of propanol and the phenylene proton (7.50 to 8.20 ppm) of biphenyltetracarboxylic imide in FIG. 2, the bifunctional hydroxyl-terminated imide oligomer B Was confirmed to be a bifunctional hydroxyl-terminated imide oligomer having an m (average value) of 1 in chemical formula (1).

Reference Example 3 Production of bifunctional hydroxyl-terminated imide oligomer C 2,3,3 ′, 4′-biphenyl was placed in a 500 ml glass separable flask equipped with a nitrogen inlet tube, a Dean-Star cleaver and a cooling tube. Tetracarboxylic dianhydride 29.4 g (0.10 mol), 2,4-diaminotoluene 7.43 g (0.061 mol), 3-aminopropanol 5.89 g (0.078 mol), dimethylacetamide 100 ml And stirred at 100 ° C. for 1 hour under a nitrogen atmosphere. Next, 50 ml of toluene was added and heated at 180 ° C. for 4 hours, and water generated by the imidization reaction was removed azeotropically with toluene. The reaction solution was poured into 2 liters of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 38.5 g of a bifunctional hydroxyl-terminated imide oligomer C powder. The ¹ H-NMR spectrum of this bifunctional hydroxyl-terminated imide oligomer C is shown in FIG. From the integrated intensity ratio of the 2-position methylene proton (1.65 to 2.00 ppm) of propanol in FIG. 3 to the phenylene proton (7.35 to 8.30 ppm) of biphenyltetracarboxylic imide and tolylene, a bifunctional hydroxyl-terminated imide. It was confirmed that the oligomer C was a bifunctional hydroxyl-terminated imide oligomer having a chemical formula (1) m (average value) of 1.6.

[Example 1] (a) Diisocyanate compound is 4,4'-diphenylmethane diisocyanate, (b ₁ ) bifunctional hydroxyl-terminated polybutadiene is GI-1000, and (c) bifunctional hydroxyl-terminated imide oligomer is Reference Example 1. Manufacture of modified polyimide resin consisting of manufactured bifunctional hydroxyl-terminated imide oligomer A (m in chemical formula (1) is 0, R is a residue excluding amino group of 3-aminopropanol) Capacity 100 with nitrogen inlet tube GI-1000 10.0 g (6.4 mmol), 4,4′-diphenylmethane diisocyanate 3.20 g (12.8 mmol), and cyclohexanone 13.2 g were charged into a milliliter glass flask, and the mixture was heated at 80 ° C. in a nitrogen atmosphere. For 1.5 hours. Subsequently, 2.61 g (6.4 mmol) of the bifunctional hydroxyl-terminated imide oligomer A produced in Reference Example 1 and 23.7 g of cyclohexanone were added and stirred at 80 ° C. for 1.5 hours. The obtained modified polyimide resin solution was a polymer solid content concentration of 40% by weight and a solution viscosity of 2.4 Pa · s. The number average molecular weight determined from GPC was 20,400. The ¹ H-NMR spectrum of this modified polyimide resin is shown in FIG.

[Example 2] (a) Diisocyanate compound is 4,4′-diphenylmethane diisocyanate, (b ₁ ) bifunctional hydroxyl-terminated polybutadiene is GI-1000, (b ₂ ) reactive polar group-containing diol is 2,2-bis (Hydroxymethyl) propionic acid, and (c) bifunctional hydroxyl-terminated imide oligomer B prepared in Reference Example 2 (m (average value) in chemical formula (1) is 1, Y is isophorone) Production of Modified Polyimide Resin Composed of Residue Excluding Amino Group of Diamine, Residue Excluding Amino Group of 3-Aminopropanol) In a glass flask having a capacity of 100 ml equipped with a nitrogen introduction tube, GI-1000 7.86 g (5.0 mmol), 2,2-bis (hydroxymethyl) propionic acid 0.168 g (1.25 mm) 4), 4,4′-diphenylmethane diisocyanate (2.56 g, 10.2 mmol) and isophorone (10 g) were charged, and the mixture was stirred at 80 ° C. for 1.5 hours in a nitrogen atmosphere. Subsequently, 4.17 g (5.0 mmol) of the bifunctional hydroxyl-terminated imide oligomer B synthesized in Reference Example 2 and 12.1 g of isophorone were added and stirred at 80 ° C. for 1.5 hours. The obtained modified polyimide resin solution was a solution having a polymer solid content concentration of 40% by weight and a viscosity of 6.3 Pa · s. The number average molecular weight determined from GPC was 11,000. The ¹ H-NMR spectrum of this modified polyimide resin is shown in FIG.

[Example 3] (a) Diisocyanate compound is 4,4′-diphenylmethane diisocyanate, (b ₁ ) bifunctional hydroxyl-terminated polybutadiene is GI-1000, (b ₂ ) reactive polar group-containing diol is 2,2-bis (Hydroxymethyl) propionic acid, and (c) a bifunctional hydroxyl-terminated imide oligomer A produced in Reference Example 1 in which the m is 0 and R is 3-aminopropanol. Production of Modified Polyimide Resin Consisting of Residue Excluding Amino Group) In a 100 mL glass flask equipped with a nitrogen inlet tube, 15.71 g (10.0 mmol) of GI-1000, 2,2-bis (hydroxy) Methyl) propionic acid 1.34 g (10.0 mmol), 4,4′-diphenylmethane diisocyanate10. 1 g (40.0 mmol) was charged with isophorone 27.1 g, under a nitrogen atmosphere and stirred at 80 ° C. 1.5 hours. Next, 8.16 g (20.0 mmol) of the bifunctional hydroxyl-terminated imide oligomer A synthesized in Reference Example 1 and 25.8 g of isophorone were added, and the mixture was stirred at 80 ° C. for 1.5 hours. The obtained modified polyimide resin solution was a solution having a polymer solid content concentration of 40% by weight and a viscosity of 190 Pa · s. The number average molecular weight determined from GPC was 20,500. The ¹ H-NMR spectrum of this modified polyimide resin is shown in FIG.

[Example 4] (a) Diisocyanate compound is 4,4'-diphenylmethane diisocyanate, (b ₁ ) bifunctional hydroxyl-terminated polybutadiene is GI-2000, (b ₂ ) reactive polar group-containing diol is 2,2-bis (Hydroxymethyl) propionic acid, and (c) bifunctional hydroxyl-terminated imide oligomer B prepared in Reference Example 2 (m (average value) in chemical formula (1) is 1, Y is isophorone) Production of Modified Polyimide Resin Consisting of Residue Excluding Amino Group of Diamine, Residue Excluding Amino Group of 3-Aminopropanol) Into a glass flask with a capacity of 100 ml equipped with a nitrogen inlet tube, GI-2000 11.0 g (5.0 mmol), 2,2-bis (hydroxymethyl) propionic acid 0.335 g (2.50 mm) ), 4,4′-diphenylmethane diisocyanate (3.33 g, 13.3 mmol) and isophorone (10 g) were charged and stirred at 80 ° C. for 1.5 hours in a nitrogen atmosphere. Subsequently, 6.26 g (7.5 mmol) of the bifunctional hydroxyl-terminated imide oligomer B synthesized in Reference Example 2 and 21.4 g of isophorone were added and stirred at 80 ° C. for 1.5 hours. The obtained modified polyimide resin solution was a polymer solid concentration of 40% by weight and a viscosity of 5.5 Pa · s. The number average molecular weight determined from GPC was 7400. The ¹ H-NMR spectrum of this modified polyimide resin is shown in FIG.

[Example 5] (a) Diisocyanate compound is 4,4′-diphenylmethane diisocyanate, (b ₁ ) bifunctional hydroxyl-terminated polybutadiene is GI-1000, and (c) bifunctional hydroxyl-terminated imide oligomer bifunctional hydroxyl-terminated terminal The bifunctional hydroxyl-terminated imide oligomer C produced in Reference Example 3 by the imide oligomer (m (average value) of chemical formula (1) is 1.6, Y is a residue obtained by removing the amino group of 2,4-diaminotoluene, Production of Modified Polyimide Resin Composed of R is Residue Excluding Amino Group of 3-Aminopropanol) In a glass flask with a capacity of 100 ml equipped with a nitrogen introduction tube, 10.0 g (6.4 mmol) of GI-1000, 4.20 g (12.8 mmol) of 4,4′-diphenylmethane diisocyanate was charged, and 1.5 ° C. at 80 ° C. in a nitrogen atmosphere. During the mixture was stirred. Subsequently, 6.46 g (6.4 mmol) of the bifunctional hydroxyl-terminated imide oligomer C synthesized in Reference Example 3 and 29.5 g of γ-butyrolactone were added and stirred at 80 ° C. for 1.5 hours. The obtained modified polyimide resin solution was a polymer solid concentration of 40% by weight and a viscosity of 1.7 Pa · s. The number average molecular weight determined from GPC was 6300. The ¹ H-NMR spectrum of this modified polyimide resin is shown in FIG.

Example 6
To the glass container, 10 parts by weight of the epoxy resin Epicoat 157S70 and 0.4 parts by weight of the amine-based curing catalyst 2E4MZ with respect to 100 parts by weight of the modified polyimide resin solution obtained in Example 1, The modified polyimide resin composition was obtained by stirring and mixing uniformly. The tensile elasticity modulus at the time of hardening of this modified polyimide resin composition was measured. Moreover, this modified polyimide composition was applied to a copper foil and heat-treated to prepare a cured insulating film sample, which was evaluated for bendability, adhesion to a sealing material, solder heat resistance, solvent resistance, and electrical insulation. The results are shown in Table 2.

[Examples 7 to 20]
A modified polyimide resin composition was obtained in the same manner as in Example 6 except that the types and amounts of the composition components shown in Table 1 were blended. About these modified polyimide resin compositions, it carried out similarly to Example 6, and measured about the elasticity modulus, the bendability, the adhesiveness with a sealing material, solder heat resistance, solvent resistance, and electrical insulation. The results are shown in Table 2.

[Comparative Example 1]
GI-1000 40.0 g (25.5 mmol) and 4,4′-diphenylmethane diisocyanate 12.8 g (51.0 mmol) were charged into a 300-ml glass separable flask equipped with a nitrogen inlet tube. The mixture was stirred at 120 ° C. for 1.5 hours under an atmosphere. Next, 7.50 g (25.5 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 87.1 g of cyclohexanone were added and stirred at 180 ° C. for 4 hours. In the obtained modified polyimide resin solution, the modified polyimide resin used a diisocyanate compound and a bifunctional hydroxyl-terminated polybutadiene, but the bifunctional hydroxyl-terminated imide oligomer represented by the chemical formula (1) was not used. This was a solution having a polymer solid content concentration of 40% by weight and a viscosity of 130 Pa · s. The number average molecular weight determined from GPC was 9400. In the same way as in Example 6, 10 parts by weight of epoxy resin Epicoat 157S70 and 0.4 parts by weight of amine-based curing catalyst 2E4MZ were added to this modified polyimide resin solution to 100 parts by weight of the modified polyimide solids. A modified polyimide resin composition was obtained by stirring and mixing. Table 2 shows the results of measurement / evaluation similar to Example 6 for this modified polyimide resin composition.

[Comparative Example 2]
In a glass container, add 100 parts by weight of the bifunctional hydroxyl-terminated imide oligomer A synthesized in Reference Example 1, 60 parts by weight of phenol / formaldehyde resin H-3 and 80 parts by weight of γ-butyrolactone as a curing material, and heat to 80 ° C. And then cooled to room temperature. Furthermore, 200 parts by weight of epoxy resin Epicoat 828EL and 2 parts by weight of 2E4MZ were added and stirred and mixed uniformly to obtain a bifunctional hydroxyl-terminated imide oligomer composition. Table 2 shows the results of measurement / evaluation similar to Example 6 for this bifunctional hydroxyl-terminated imide oligomer composition.

Example 21
In a glass container, 10 parts by weight of epoxy resin Epolide PB3600, 20 parts by weight of polyisocyanate Vernock D-550, 100 parts by weight of the modified polyimide resin solution obtained in Example 2 and 100 parts by weight of modified polyimide resin, polycarbonate diol A modified polyimide resin composition was added by adding 2.5 parts by weight of Kuraray polyol C-2015, 0.8 part by weight of amine-based curing catalyst 2E4MZ and 20 parts by weight of finely divided silica Aerosil R972, and stirring and mixing uniformly. I got a thing. The tensile elasticity modulus at the time of hardening of this modified polyimide resin composition was measured. Moreover, this modified polyimide composition was applied to a copper foil and heat-treated to prepare a cured insulating film sample, which was evaluated for bendability, adhesion to a sealing material, solder heat resistance, solvent resistance, and electrical insulation. The results are shown in Table 3.

[Example 22]
In a glass container, 10 parts by weight of epoxy resin Epolide PB3600, 20 parts by weight of polyisocyanate Vernock D-550, 100 parts by weight of the modified polyimide resin solution obtained in Example 2 and 100 parts by weight of modified polyimide resin, polycarbonate diol 2.5 parts by weight of etanacol UH-CARB200, 2.5 parts by weight of H-1 which is a compound having a phenolic hydroxyl group, 0.8 parts by weight of 2E4MZ which is an amine curing catalyst, and 20 parts of Aerosil R972 of finely divided silica Part by weight was added, and stirred and mixed uniformly to obtain a modified polyimide resin composition. The tensile elasticity modulus at the time of hardening of this modified polyimide resin composition was measured. Moreover, this modified polyimide composition was applied to a copper foil and heat-treated to prepare a cured insulating film sample, which was evaluated for bendability, adhesion to a sealing material, solder heat resistance, solvent resistance, and electrical insulation. The results are shown in Table 3.

  In the present invention, the cured insulating film (protective film) obtained by heat treatment is less likely to warp (non-curl), flexible, excellent in heat resistance and solder resistance, wiring pattern, polyimide Modified polyimide suitable as a resin component of an insulating film composition having good adhesion to a film and a sealing material, and having excellent solvent resistance, chemical resistance, bending resistance, and electrical characteristics, and modification thereof A composition for an insulating film using polyimide and an epoxy compound, a cured insulating film thereof, and the like can be provided.

2 is a ¹ H-NMR spectrum of a bifunctional hydroxyl-terminated imide oligomer A obtained in Reference Example 1. 2 is a ¹ H-NMR spectrum of a bifunctional hydroxyl-terminated imide oligomer B obtained in Reference Example 2. 2 is a ¹ H-NMR spectrum of a bifunctional hydroxyl-terminated imide oligomer C obtained in Reference Example 3. 1 is a ¹ H-NMR spectrum of a modified polyimide resin obtained in Example 1. 2 is a ¹ H-NMR spectrum of a modified polyimide resin obtained in Example 2. 2 is a ¹ H-NMR spectrum of a modified polyimide resin obtained in Example 3. 2 is a ¹ H-NMR spectrum of a modified polyimide resin obtained in Example 4. 2 is a ¹ H-NMR spectrum of a modified polyimide resin obtained in Example 5.

Claims (11)

A modification obtained by reacting (a) a diisocyanate compound, (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene, and (c) a bifunctional hydroxyl-terminated imide oligomer represented by the following chemical formula (1) Polyimide resin.

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 1 to 20.) (B) The one or more diol compounds containing a bifunctional hydroxyl group-terminated polybutadiene comprise (b ₁ ) a bifunctional hydroxyl group-terminated polybutadiene having a number average molecular weight of 500 to 10,000. The modified polyimide resin as described. (B) The one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene comprise (b ₂ ) a reactive polar group-containing diol compound in addition to the bifunctional hydroxyl-terminated polybutadiene. The modified polyimide resin according to any one of -2. (B) One or more kinds of diol compounds containing a bifunctional hydroxyl group-terminated polybutadiene are obtained from (b ₁ ) a bifunctional hydroxyl group-terminated polybutadiene having a number average molecular weight of 500 to 10,000 and (b ₂ ) a reactive polar group-containing diol. And [(b ₁ ) + (b ₂ )] / (a) is in the range of 0.5 to 2.5 and (b ₂ ) / (b ₁ ) in the range of 0 to 10 in terms of molar ratio. The modified polyimide resin according to any one of claims 1 to 3. A modified polyimide resin represented by the following chemical formula (2).

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 1 to 20, Z represents a residue excluding the hydroxyl group of the bifunctional hydroxyl-terminated polybutadiene, W represents a residue excluding the hydroxyl group of a diol compound other than the bifunctional hydroxyl-terminated polybutadiene, A represents a residue excluding the isocyanate group of the diisocyanate compound, s and u each independently represents an integer of 1 to 100, and t represents an integer of 0 to 100.) A diisocyanate compound represented by the following chemical formula (3) obtained by reacting (a) a diisocyanate compound and (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene; and (c) the following chemical formula (4): A method for producing a modified polyimide resin, which comprises reacting with a bifunctional hydroxyl-terminated imide oligomer represented by the formula:

(In the formula, Z represents a residue excluding the hydroxyl group of the bifunctional hydroxyl-terminated polybutadiene, W represents a residue excluding the hydroxyl group of a diol compound other than the bifunctional hydroxyl-terminated polybutadiene, and A represents an isocyanate of a diisocyanate compound. The residue except a group is shown, s shows the integer of 1-100, and t shows the integer of 0-100.)

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 1 to 20.) (A) (a) a diisocyanate compound, (b) one or more diol compounds containing a bifunctional hydroxyl-terminated polybutadiene, and (c) a bifunctional hydroxyl-terminated imide oligomer represented by the following chemical formula (1) 100 parts by weight of the resulting modified polyimide resin,

(In the formula, R represents a divalent aliphatic or aromatic hydrocarbon group, X represents a residue excluding the carboxyl group of tetracarboxylic acid, Y represents a residue excluding the amino group of diamine, m represents an integer of 0 to 20.)
(B) A modified polyimide resin composition comprising 1 to 50 parts by weight of an epoxy compound and (C) an organic solvent.   The modified polyimide resin composition according to claim 7, further comprising (D) a curing catalyst.   The modified polyimide resin composition according to claim 7, further comprising (E) a fine filler.   The cured insulating film obtained by heat-processing the modified polyimide resin composition in any one of Claims 7-9.   A method for forming a cured insulating film by applying a heat treatment at 50 to 210 ° C. after applying the modified polyimide resin composition according to claim 7 to a substrate.

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