JP5621190B2 - Modified polyimide resin composition - Google Patents

Description

  The present invention relates to a modified polyimide resin solution composition. The cured film obtained by heat-treating this modified polyimide resin solution composition is excellent in electrical insulation, heat resistance, flexibility and the like, and in particular, has improved surface hardness and bending resistance. It can be suitably used as an insulating film for a plate.

Patent Document 1 describes a modified polyimide resin into which a soft segment made of a polybutadiene segment is introduced.
Patent Document 2 describes a modified polyimide resin into which a soft segment composed of a polybutadiene segment is introduced and a solution composition composed of the modified polyimide resin.
Patent Document 3 describes a modified polyimide resin into which a soft segment composed of a polycarbonate segment is introduced and a solution composition composed of the modified polyimide resin.
The cured film made of these compositions may have insufficient surface hardness due to the soft segment, and there is room for improvement. For example, when used as a protective insulating film for a flexible substrate, fold resistance is required. Therefore, a cured film made of these compositions requires a high level of fold resistance together with sufficient surface hardness. .
Japanese Patent Laid-Open No. 7-113004 JP 2006-104462 A JP 2006-307183 A

  An object of the present invention is to provide a modified polyimide resin solution composition containing a modified polyimide resin into which a soft segment composed of a polybutadiene segment or a polycarbonate segment is introduced, and the surface hardness and fold resistance of a cured film obtained by heat treatment. It is providing the modified polyimide resin solution composition which can improve this. The cured film obtained by heat-treating this modified polyimide resin solution composition is excellent in electrical insulation, heat resistance, flexibility and the like, and in particular, has improved surface hardness and bending resistance. It can be suitably used as an insulating film for a plate.

  As a result of various investigations, the present inventors have conducted heating by adding acrylic resin beads in a modified polyimide resin composition comprising a modified polyimide resin into which a soft segment composed of a polybutadiene segment or a polycarbonate segment has been introduced. The present inventors have found that the surface hardness of the cured film obtained by the treatment can be improved and the folding resistance can be improved.

That is, the present invention relates to the following items.
1. A modified polyimide resin solution composition comprising an modified polyimide resin solution composition comprising a modified polyimide resin into which a soft segment comprising a polybutadiene segment or a polycarbonate segment is introduced. The modified polyimide resin solution composition comprises acrylic resin beads.

2． Item 10. The item 1, wherein acrylic resin beads are contained in an amount of 10 to 80 parts by mass, preferably 20 to 60 parts by mass, more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the modified polyimide resin. Modified polyimide resin solution composition.

3. Item 3. The modified polyimide resin solution composition according to any one of Items 1 to 2, wherein the acrylic resin beads have an average particle size of 10 µm or less, preferably 5 µm or less.

4). The modified polyimide resin solution composition according to any one of items 1 to 3, further comprising at least one curable compound selected from the group consisting of an epoxy compound, a polyvalent isocyanate compound, and an amino resin. object.

5. A cured film obtained by heat-treating the modified polyimide resin solution composition according to any one of Items 1 to 4.

6). Item 5. A solution composition for an insulating film comprising the modified polyimide resin solution composition according to any one of Items 1 to 4.

7). A cured insulating film obtained by subjecting the solution composition for an insulating film according to Item 6 to a heat treatment.

  According to the present invention, in a modified polyimide resin solution composition comprising a modified polyimide resin into which a soft segment composed of a polybutadiene segment or a polycarbonate segment is introduced, the surface hardness and fold resistance of a cured film obtained by heat treatment are improved. The modified polyimide resin solution composition which can be provided can be provided. The cured film obtained by heat-treating this modified polyimide resin solution composition is excellent in electrical insulation, heat resistance, flexibility and the like, and in particular, has improved surface hardness and bending resistance. It can be suitably used as an insulating film for a plate.

  The modified polyimide resin of the present invention is a modified polyimide resin in which a soft segment composed of a polybutadiene segment or a polycarbonate segment is introduced into a hard segment having an imide structure. The modified polyimide resin is not particularly limited as long as it has both the hard segment and the soft segment. For example, as described in Patent Document 1, it can be obtained by preparing a prepolymer having a terminal isocyanate group from diol and diisocyanate, and reacting the prepolymer with an aromatic tetracarboxylic acid component. Moreover, as described in Patent Documents 2 and 3, an alcoholic hydroxyl-terminated imide oligomer is prepared in advance, and obtained by reacting the alcoholic hydroxyl-terminated imide oligomer, polybutadiene diol or polycarbonate diol, and diisocyanate. Can do. The latter is more preferable because the resulting modified polyimide resin has better solubility and heat resistance.

  The present invention is characterized in that a modified polyimide resin solution composition comprising a modified polyimide resin into which a soft segment composed of a polybutadiene segment or a polycarbonate segment prepared as described above is introduced, and an acrylic resin bead as a filler Is to improve the surface hardness and fold resistance of the cured film obtained by heat treatment at the same time.

  Below, although the case of the modified polyimide resin prepared using the alcoholic hydroxyl-terminated imide oligomer is demonstrated, this invention is not limited to the case of the modified polyimide resin prepared in this way.

  The modified polyimide resin is preferably obtained by reacting a diisocyanate compound, polybutadiene diol or polycarbonate diol, and an alcoholic hydroxyl-terminated imide oligomer represented by the following chemical formula (1).

式中、Ｒは２価の炭化水素基を示し、Ｘはテトラカルボン酸のカルボキシル基を除いた４価の基を示し、Ｙはジアミンのアミノ基を除いた２価の基を示し、ｍは０〜５０の整数である。

In the formula, R represents a divalent hydrocarbon group, X represents a tetravalent group excluding the carboxyl group of tetracarboxylic acid, Y represents a divalent group excluding the amino group of diamine, and m represents It is an integer of 0-50.

  As the diisocyanate compound, 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 - can be exemplified bets like. In addition, as the diisocyanate compound, a blocked diisocyanate in which an isocyanate group is blocked with a blocking agent can be preferably used.

  The polybutadiene diol preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight is less than 500, it is difficult to obtain suitable flexibility, and when the number average molecular weight exceeds 10,000, the heat resistance and solvent resistance may be deteriorated. The polybutadiene diol may have a double bond in the molecule or may be a hydrogenated double bond in the molecule, but if the double bond remains in the molecule, a crosslinking reaction will occur. Therefore, hydrogenated polybutadiene diol with hydrogenated intramolecular double bonds is preferable. Preferred examples of the polybutadiene diol 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. it can.

  The polycarbonate diol preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight is less than 500, it is difficult to obtain suitable flexibility, and when the number average molecular weight exceeds 10,000, the heat resistance and solvent resistance may be deteriorated. Moreover, as polycarbonate diol used by this invention, UH-CARB, UD-CARB, UC-CARB by Ube Industries, Ltd., PLACEL CD-PL, PLACEL CD-H by Daicel Chemical Industries, Ltd., Kuraray Co., Ltd. The Kuraray polyol C series made by the company etc. can be illustrated suitably. These polybutadiene diols and polycarbonate diols are used alone or in combination of two or more.

  The alcoholic hydroxyl group-terminated imide oligomer represented by the chemical formula (1) is obtained from a tetracarboxylic acid component and an amine component composed of a diamine compound and a monoamine compound having one alcoholic hydroxyl group. In the formula, m represents an integer of 0 to 50, preferably 0 to 20, more preferably 0 to 10, particularly 1 to 5. When m is 50 or more, it takes time to dissolve, or the flexibility of the resulting cured film is inferior.

  As the tetracarboxylic acid component, aromatic tetracarboxylic acids, or their acid dianhydrides or esterified products of lower alcohols are suitable, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3 , 3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic 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-naphthalene Tetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,1-bis (2 Suitable examples include aromatic tetracarboxylic acids such as, 3-dicarboxyphenyl) ethane, or acid dianhydrides and esterified products of lower alcohols. Examples of the tetracarboxylic acid component include fats such as cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3-methyl-4-cyclohexene-1,2,4,5-tetracarboxylic acid. Cyclic tetracarboxylic acids, or acid dianhydrides or esterified products of lower alcohols can also be used.

  As the diamine compound, aromatic, alicyclic and aliphatic diamines can be used. Specifically, as the aromatic diamine, one benzene such as 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 1,4-diamino-2,5-dihalogenobenzene is used. Diamines containing, 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, tolidine Diamines containing two benzenes such as sulfonic 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-amino) Nopyl) fluorene, diamines containing four or more benzenes such as 5,10-bis (4-aminophenyl) anthracene, and the like, and cycloaliphatic diamines include isophorone diamine, norbornene diamine, 1,2-diaminocyclohexane, 1,3 Examples of aliphatic diamines such as -diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) include hexamethylenediamine and diaminododecane. Among these, alicyclic diamines are particularly suitable because they can provide an alcoholic hydroxyl-terminated imide oligomer having both heat resistance and solubility.

  The monoamine compound having one alcoholic hydroxyl group is a hydrocarbon compound having one alcoholic hydroxyl group and one amino group in the molecule, and preferably has a carbon number such as aminoethanol, aminopropanol, and aminobutanol. Examples thereof include an aliphatic monoamine compound having 1 to 10 alcoholic hydroxyl groups and an alicyclic monoamine compound having an alcoholic hydroxyl group having 3 to 20 carbon atoms such as aminocyclohexanol.

  The alcoholic 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, an acid anhydride group (or two adjacent carboxyl groups, etc.) of the tetracarboxylic acid component. ) And the number of equivalents of the amino group of the amine component so as to be approximately equal to each other, polymerization and imidization reaction can be performed 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. The oligomer having an amide-acid bond is obtained by reacting each component in an organic polar solvent at a reaction temperature of about 100 ° C. or less, particularly 80 ° C. or less. Then, the amide-acid oligomer (also referred to as an 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. for dehydration / imide 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 alcoholic hydroxyl-terminated imide oligomer include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam. Solvents, solvents containing sulfur atoms 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 Diglyme solvents such as dimethyl ether (triglyme) and tetraglyme, lactone solvents such as γ-butyrolactone, isophorone, cyclohexanone, 3,3,5-trimethyl Ketones solvents such as cyclohexanone, pyridine, ethylene glycol, dioxane, and the like tetramethylurea.

  The alcoholic hydroxyl-terminated imide oligomer produced as described above may be a mixture of a plurality of oligomers having different m in the chemical formula (1). In the present invention, a mixture composed of a plurality of imide oligomers having different m may be used separately for each imide oligomer, but can be suitably used as it is 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.

The modified polyimide resin may be obtained by reacting a diisocyanate compound, polybutadiene diol or polycarbonate diol, and an alcoholic hydroxyl-terminated imide oligomer at the same time. Preferably, the diisocyanate compound and polybutadiene diol or polycarbonate diol are converted into hydroxyl groups. It can react suitably so that it may become an excess amount, and it can obtain suitably by making a terminal isocyanate compound react, and then making an alcoholic hydroxyl group terminal imide oligomer react with the said terminal isocyanate compound. These reactions can be carried out without solvent or in an organic solvent, usually at a reaction temperature of 30 ° C. to 150 ° C., for a reaction time of 1 to 10 hours, preferably in an inert atmosphere. As the organic solvent, a solvent used for producing the above-mentioned alcoholic hydroxyl group-terminated imide oligomer can be preferably used. Details of the modified polyimide resin are as described in more detail in Patent Documents 1 to 3.
Moreover, in the modified polyimide resin of the present invention, a modified polyimide resin composition can be obtained by replacing a part of polybutadiene diol or polycarbonate diol (usually about 5 to 40 mol% in the diol component) with a reactive polar group-containing diol. Is suitable for curing by heating. As the reactive polar group-containing diol, 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 preferable, and the number of carbons having a carboxyl group or a phenolic hydroxyl group as a substituent is particularly preferred. A diol compound having 1 to 30 carbon atoms and 2 to 20 carbon atoms 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 modified polyimide resin solution composition of the present invention preferably comprises (A) 100 parts by mass of a modified polyimide resin into which a soft segment consisting of a polybutadiene segment or a polycarbonate segment is introduced, (B) an epoxy compound, a polyvalent isocyanate compound, and an amino resin. At least one curable compound selected from the group consisting of 1 to 100 parts by weight, preferably 2 to 80 parts by weight, particularly 10 to 60 parts by weight, (C) 1 to 80 parts by weight of acrylic resin beads, and (D) an organic solvent It is comprised including.
The curable compound (B) can be used alone or in combination of two or more, but a combination of an epoxy compound and a polyvalent isocyanate compound or a combination of an epoxy compound and an amino resin is particularly preferable. If the amount used is more than the above range, the electrical insulation properties of the insulating film after curing will be reduced or tackiness will appear, and if it is too small, the heat resistance and chemical resistance of the insulating film after curing will deteriorate. Said range is preferred.

  The epoxy compound is preferably a liquid or solid epoxy resin having an epoxy equivalent of about 100 to 4000 and a molecular weight of about 300 to 10,000. For example, bisphenol A type or bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: Epicoat 806, Epicoat 825, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1055AF, Epicoat 1004AF, Epicoat 1007, Epicoat 1009, Epicoat 1010, etc.) Trifunctional or higher 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 Corporation, etc., epoxidized polybutadiene (manufactured by Nippon Petrochemical Co., Ltd .: E-1000-8, E-1800-6.5, Daicel) Chemical Industry Co., Ltd .: Epolide PB3600, etc.), and alicyclic epoxy resins (Daicel Chemical Co., Ltd .: Celoxide 2021P, Celoxide 2080, Epolide GT400, EHPE) and the like can be mentioned. Of these, use of epoxidized polybutadiene or alicyclic epoxy resin is preferable because low warpage is easily obtained.

The isocyanate compound may be any compound as long as it has two or more isocyanate groups in one molecule. Examples of such isocyanate compounds include aliphatic, alicyclic or aromatic diisocyanates, such as 1,4-tetramethylene diisocyanate and 1,5-pentamethylene diisocyanate. 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5 , 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate Value - theft, etc. can be mentioned.
Further, the isocyanate compound is derived from an aliphatic, alicyclic or aromatic polyisocyanate, for example, isocyanurate-modified polyisocyanate, burette-modified polyisocyanate, urethane-modified. A polyvalent isocyanate may be used.
As the isocyanate compound, a block polyvalent isocyanate in which the isocyanate group of the polyvalent isocyanate is blocked with a blocking agent is preferably used.
Examples of the block polyvalent isocyanate include Vernock D-500 (tolylene diisocyanate blocked) manufactured by Dainippon Ink and Chemicals, Inc. and D-550 (1,6-hexamethylene diisocyanate). M-Takeda Chemical Co., Ltd. Takenate Takenate B-830 (tolylene diisocyanate blocked), B-815N (4,4'-methylenebis (cyclohexyl isocyanate) blocked), B -842N (1,3-bis (isocyanatemethyl) cyclohexane blocked), B-846N (1,3-bis (isocyanatemethyl) cyclohexane blocked), B-874N (isophorone diisocyanate blocked) B-882N (1,6-hexamethylene diisocyanate block ), Duranate MF-B60X (1,6-hexamethylene diisocyanate blocked) manufactured by Asahi Kasei Co., Ltd., Duranate MF-K60X (1,6-hexamethylene diisocyanate blocked), Duranate ME20-B80 (1, 6-hexamethylene diisocyanate blocked), Elastolon BN-P17 (4,4'-diphenylmethane diisocyanate block), manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -44, elastolone BN-45 (above, 3 to 5 functionals per molecule of urethane-modified polyisocyanate block, all can be used after drying and isolation in a water emulsion product) and the like.

  Examples of the amino resin include, but are not limited to, a lower alkyl etherified melamine resin or a lower alkyl etherified benzoguanamine resin obtained by etherifying a part or all of the methylol groups of a methylolated melamine resin or a methylolated benzoguanamine resin with a lower alcohol. Is preferred.

  Specific examples of the melamine resin include, for example, Uban 20SE, 225 (all manufactured by Mitsui Toatsu), Super Becamine J820-60, L-117-60, L-109-65, 437-508- 60, L-118-60, G821-60 (all manufactured by Dainippon Ink & Chemicals, Inc.), and the like; Cymel 300, 303, 325, 327, 350, 730, 736, 738 (all manufactured by Nihon Cytec Industries, Inc.), Melan 522, 523 (all manufactured by Hitachi Chemical Co., Ltd.), Nicarak MS001, MX 430, MX 650 (all manufactured by Sanwa Chemical Co., Ltd.), Sumimar M-55 M-100, M-40S (both manufactured by Sumitomo Chemical Co., Ltd.), Resimin 740, 747 (both Monsanto Methyl etherified melamine resins such as Cymel 232, 266, XV-514, 1130 (all manufactured by Nihon Cytec Industries), Nicalak MX500, MX600, MS95 (all manufactured by Sanwa Chemical) Resinmin 753, 755 (both manufactured by Monsanto Co., Ltd.), Summar M-66B (manufactured by Sumitomo Chemical Co., Ltd.), etc.

  Specific examples of the benzoguanamine resin include Cymel 1123 (mixed etherified benzoguanamine resin of methyl ether and ethyl ether) and Cymel 1123-10 (mixed etherified benzoguanamine resin of methyl ether and butyl ether) manufactured by Nippon Cytec Industries Co., Ltd. ), Cymel 1128 (butyl etherified benzoguanamine resin), Mycote 102 (methyl etherified benzoguanamine resin), Mycote 132 (methyl-butyl mixed etherified benzoguanamine / melamine co-condensation resin), Mycote 136 manufactured by Nihon Cytec Industries, Ltd. (Mixed etherified benzoguanamine resin of methyl ether and butyl ether).

The acrylic resin beads (acrylic resin fine powder) used in the present invention are preferably spherical particles that can be easily obtained by suspension polymerization of methyl methacrylate or the like. The acrylic resin beads used in the present invention are preferably contained as a filler in the solution composition, and are preferably spherical crosslinked acrylic resin beads.
The average particle diameter of the acrylic resin beads is not particularly limited, but is 1 to 20 μm, preferably 1 to 10 μm, more preferably 1 to 5 μm. Those having an average particle size of 1 μm or less are difficult to obtain, and when the average particle size is increased, the effect of improving the folding resistance is reduced or the insulating film for a flexible wiring board made of fine wiring is used. Since it cannot be performed, it is not suitable.

  Specific examples of the acrylic resin beads include Art Pearl G-400, G-800, GR-400, GR-800, J-4PY, J-4P, J-4PY, J-5P, J- manufactured by Negami Kogyo Co., Ltd. Preferred examples include 7P, J7PY, S-5P, and the like.

  The modified polyimide resin composition of the present invention has 2 or more phenolic hydroxyl groups of 1 to 50 parts by mass, preferably 2 to 40 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the modified polyimide resin. Compounds can be included. Examples of the compound having two or more phenolic hydroxyl groups include hydroquinone, 4,4′-dihydroxybiphenyl, and phenol resins such as 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.

  As the solvent for the modified polyimide resin composition, the organic solvent used for synthesizing the modified polyimide resin can be used as it is, but preferably a nitrogen-containing solvent such as N, N-dimethylacetamide, N, Sulfur-containing atomic solvents such as N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, For example, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfuramide and the like, oxygen-containing solvents such as phenolic solvents cresol, phenol, xylenol and the like, diglyme solvents diethylene glycol Rudimethyl ether (diglyme), triethylene glycol Cole dimethyl ether (triglyme), tetraglyme, etc., ketone solvents such as acetone, acetophenone, propiophenone, cyclohexanone, isophorone, ether solvents such as ethylene glycol, dioxane, tetrahydrofuran, etc., lactone solvents such as γ-butyrolactone, etc. Can be mentioned. 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.

  The modified polyimide resin composition of the present invention may contain a curing catalyst comprising a curing accelerating catalyst for accelerating the crosslinking reaction by heat treatment. Furthermore, the modified polyimide resin composition may contain fine fillers other than acrylic resin beads, pigments such as organic color pigments and inorganic color pigments, antifoaming agents and leveling agents. As fine fillers other than acrylic resin beads, conventionally known fine inorganic fillers such as silica, alumina, potassium carbonate, talc and barium sulfate can be preferably exemplified.

  The modified polyimide resin composition of the present invention is not particularly limited, but the screen has a solution viscosity at room temperature (25 ° C.) of 5 to 1000 Pa · s, particularly 10 to 100 Pa · s, more preferably 10 to 60 Pa · s. It is suitable in view of workability such as printing, solution 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 modified polyimide resin composition of the present invention provides strong adhesion to a sealing material or anisotropic conductive material in addition to improved surface hardness and fold resistance, and is less likely to warp and has flexibility. High, excellent electrical properties, good adhesion to conductive metal and substrate, heat resistance, solder heat resistance, solvent resistance (for example, acetone, isopropanol, methyl ethyl ketone, N-methyl-2-pyrrolidone) The cured insulating film (protective film) having excellent solvent resistance, chemical resistance, flex resistance, and the like can be formed.
The modified polyimide resin insulating film composition of the present invention can form an insulating film having the above-mentioned good performance by heat treatment at a relatively low temperature of about 160 ° C. Therefore, it can also be suitably used as an interlayer adhesive for a multilayer wiring board.

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

In the following examples, measurement and evaluation were performed by the following methods.
[MIT folding test]
After forming a circuit having a wiring width of 15 μm, an inter-wiring distance of 15 μm, and a circuit length of 20 cm on the surface of the base material using a two-layer CCL in which a 7 μm-thick copper layer is laminated on a 35 μm-thick polyimide layer, the circuit A flexible substrate having a surface plated with 3 μm thick Sn was prepared. A coating film of the modified polyimide resin composition of the sample is formed on the circuit area of the flexible substrate using a screen printing machine (manufactured by Neo Techno Japan, semi-automatic screen printing machine NT-15SS-U). Then, a test piece was prepared by heating and curing at 120 ° C. for 90 minutes to form a cured film having a thickness of 10 μm.
The fold resistance of this test piece was measured according to JIS P 8115 with a MIT type soft fatigue tester DA type (manufactured by Toyo Seiki Seisakusho). The measurement was performed under the conditions of 90 ° bending (R = 0.5) and a bending speed of 90 times / minute.

[Pencil hardness test]
A coating film of a modified polyimide resin composition as a sample is formed on the surface of a 50 μm thick copper foil using an applicator and cured by heating at 80 ° C. for 30 minutes and then at 120 ° C. for 90 minutes to obtain a cured film having a thickness of 20 μm. A specimen was formed as a test piece. The cured film of the obtained test piece was subjected to the procedure of JIS-K5600-5-4 using a pencil scratch coating film hardness tester (manufactured by Toyo Seiki Seisakusho) as a device and 4B to 2H (Mitsubishi UNI) as a pencil. Pencil hardness was measured.

[Tensile modulus, elongation]
A heat treatment was performed at 80 ° C. for 30 minutes and then at 120 ° C. for 90 minutes to prepare a 70 μm thick sheet-like cured film, which was cut into a width of 1 cm and a length of 7 cm to obtain a test piece. Tensile modulus and elongation were measured at a crosshead speed of 50 mm / min and a distance between chucks of 5 cm in an atmosphere of a temperature of 25 ° C. and a humidity of 50% RH.

〔warp〕
A coating film of a modified polyimide resin composition of a sample is formed on the surface of a polyimide film having a thickness of 25 μm using an applicator, and this is cured by heat treatment at 80 ° C. for 30 minutes and then at 120 ° C. for 90 minutes. A thick cured film was formed. A laminate of the polyimide film and the cured film was cut into a 5 cm square to obtain a test piece. The test piece was placed on a horizontal base with the cured film facing upward, and the gap between the four corners of the test piece and the horizontal base was measured with a caliper, and the average value of each gap was defined as the “warp” amount.

The compounds, curing agents, curing catalysts, and fillers used in the following examples will be described.
[Tetracarboxylic acid component]
2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (manufactured by Ube Industries, Ltd.)
[Diamine compound]
Isophoronediamine (manufactured by Wako Pure Chemical Industries, Ltd.)
[Monoamine compound having one alcoholic hydroxyl group]
3-Aminopropanol (Wako Pure Chemical Industries, Ltd.)
〔solvent〕
γ-Butyrolactone (Mitsubishi Chemical Corporation)
[Polycarbonate diol]
ETERNACOLL UH-200 (Ube Industries, Ltd., average molecular weight 1997)
(Reactive polar group-containing diol)
2,2-bis (hydroxymethyl) propionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
[Diisocyanate compound]
4,4'-diphenylmethane diisocyanate (Nippon Polyurethane Industry Co., Ltd.)
[Epoxy compound]
Celoxite 2021P (manufactured by Daicel Chemical Industries, Ltd.)
[Compounds having two or more phenolic hydroxyl groups (phenolic resin)]
H-1 (Maywa Kasei Co., Ltd., phenol novolak)
[Amino resin]
My Coat 136 (Nippon Cytec Industries, Ltd.)
[Curing catalyst]
Curesol 2E4MZ (Shikoku Chemicals Co., Ltd., 2-ethyl-4-methylimidazole)
Diazabicycloundecene (DBU: Aldrich)
[Fine powdered silica]
Aerosil R972 (Nippon Aerosil Co., Ltd., specific surface area (BET method): 110 m ² / g)
[Acrylic resin beads]
Art Pearl J4PY (Negami Kogyo Co., Ltd., average particle size 2.2μm)
Art Pearl J7PY (Negami Kogyo Co., Ltd., average particle size 6.6μm)
[Urethane resin beads]
Art Pearl C-800 (Negami Kogyo Co., Ltd., average particle size 6.6 μm)
Art Pearl JB-1000T (Negami Kogyo Co., Ltd., average particle size 3.5μm)
[Amino resin beads]
D poster M05 (Nippon Shokubai Co., Ltd., 4-6μm)
[Surfactant]
LF-1983 (Enomoto Kasei Co., Ltd.)

[Reference Example 1]
Method for producing alcoholic hydroxyl group-terminated imide oligomer solution 2,5,3 ', 4'-biphenyltetracarboxylic dianhydride was added to a 5 liter glass separable flask equipped with a stirrer, a nitrogen inlet tube, and a Dean-Star cleaver. 1471 g (5 mol), ethanol 507 g (11 mol), and γ-butyrolactone 2092 g were charged and stirred at 90 ° C. for 1 hour in a nitrogen atmosphere. Next, 376 g (5 mol) of 3-aminopropanol and 426 g (2.5 mol) of isophoronediamine were charged and heated at 120 ° C. for 2 hours and 180 ° C. for 2 hours in a nitrogen atmosphere to react with water generated by the imidization reaction. It was removed by blowing nitrogen into the liquid. This alcoholic hydroxyl group-terminated imide oligomer solution had a solid content of 51.6%.

[Reference Example 2]
Method for Producing Modified Polyimide Resin Solution In a 5 liter glass separable flask equipped with a stirrer and a nitrogen inlet tube, ETERNACOLL UH-200 1198.20 g (0.60 mol), an alcoholic hydroxyl group terminal synthesized in Reference Example 1 974.13 g of an imide oligomer solution, 80.48 g (0.60 mol) of 2,2-bis (4-hydroxymethyl) propionic acid and 2228.90 g of γ-butyrolactone were charged and stirred at 50 ° C. for 1 hour in a nitrogen atmosphere. . Subsequently, 429.00 g (1.71 mol) of 4,4′-diphenylmethane diisocyanate was added, and the mixture was stirred at 60 ° C. for 3 hours and at 80 ° C. for 10 hours. The resulting modified polyimide resin solution was a polymer solid concentration of 45.7% by weight and a viscosity of 389 Pa · s.

[Example 1]
In a glass container, in the modified polyimide resin solution obtained in Reference Example 2, with respect to 100 parts by mass of the modified polyimide resin, 3.5 parts by mass of epoxy resin ceroxide 2021P, 10 parts by mass of amino resin M136, phenol resin H- 2.5 parts by mass of 1 and 0.5 parts by mass of the amine-based curing catalyst 2E4MZ, 0.5 parts by mass of diazabicycloundecene, 7 parts by mass of Aerosil R972, 15 parts by mass of acrylic resin beads J4PY, 7.5 parts by mass of LF-1983 as a surfactant was added and stirred and kneaded to obtain a uniformly mixed modified polyimide resin composition. Moreover, about the cured film of this modified polyimide resin composition, tensile elasticity modulus, bendability, board | substrate curvature amount, and pencil hardness were evaluated. The results are shown in Table 1.

[Example 2]
A modified polyimide resin composition was obtained in the same manner as in Example 1 except that the acrylic resin beads (Art Pearl J4PY) were changed from 15 parts by mass to 20 parts by mass. This modified polyimide resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
A modified polyimide resin composition was obtained in the same manner as in Example 1 except that the acrylic resin beads (Art Pearl J4PY) were changed from 15 parts by mass to 30 parts by mass. This modified polyimide resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
A modified polyimide resin composition was obtained in the same manner as in Example 1 except that the acrylic resin beads (Art Pearl J4PY) were changed from 15 parts by mass to 50 parts by mass. This modified polyimide resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
A modified polyimide resin composition was obtained in the same manner as in Example 2 except that the acrylic resin beads (Art Pearl J4PY) were changed to acrylic resin beads (Art Pearl J7PY). This modified polyimide resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
A modified polyimide resin composition was obtained in the same manner as in Example 2 except that the acrylic resin beads (Art Pearl J4PY) were changed to amino resin beads (Eposter M05). This modified polyimide resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
A modified polyimide resin composition was obtained in the same manner as in Example 2 except that the acrylic resin beads (Art Pearl J4PY) were changed to urethane resin beads (Art Pearl JB-1000T). This modified polyimide resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3]
A modified polyimide resin composition was obtained in the same manner as in Example 2 except that the acrylic resin beads (Art Pearl J4PY) were changed to urethane resin beads (Art Pearl C-800). This modified polyimide resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  According to the present invention, in a modified polyimide resin solution composition comprising a modified polyimide resin into which a soft segment composed of a polybutadiene segment or a polycarbonate segment is introduced, the surface hardness and fold resistance of a cured film obtained by heat treatment are improved. The modified polyimide resin solution composition which can be provided can be provided. The cured film obtained by heat-treating this modified polyimide resin solution composition is excellent in electrical insulation, heat resistance, flexibility and the like, and in particular, has improved surface hardness and bending resistance. It can be suitably used as an insulating film for a plate.

Claims (7)

In a modified polyimide resin solution composition comprising a modified polyimide resin introduced with a soft segment consisting of a polybutadiene segment or a polycarbonate segment,
A modified polyimide resin solution composition comprising acrylic resin beads.   The modified polyimide resin solution composition according to claim 1, wherein acrylic resin beads are contained at a ratio of 10 to 80 parts by mass with respect to 100 parts by mass of the modified polyimide resin.   3. The modified polyimide resin solution composition according to claim 1, wherein an average particle diameter of the acrylic resin beads is 10 μm or less.   The modified polyimide resin solution composition according to any one of claims 1 to 3, further comprising at least one curable compound selected from the group consisting of an epoxy compound, a polyvalent isocyanate compound, and an amino resin. .   A cured film obtained by heat-treating the modified polyimide resin solution composition according to claim 1.   An insulating film solution composition comprising the modified polyimide resin solution composition according to claim 1.   A cured insulating film obtained by heat-treating the solution composition for an insulating film according to claim 6.