KR20130097688A - Polyimide-based adhesive composition, cured product, adhesive sheet, laminate, and flexible printed circuit board - Google Patents

Abstract

PURPOSE: A polyimide-based adhesive composition is usable as a solution uniformly dissolved in an organic solvent and has excellent initial adhesion and heat resistant adhesion to an inorganic substrate and an organic substrate. CONSTITUTION: A polyimide-based adhesive composition is obtained by dissolving at least one polyimide resin, a thermosetting resin, and a flame retardant in an organic solvent. The thermosetting resin is at least one selected from an epoxy resin, a benzoxazine resin, a bismaleimide resin, and a cyanatoester resin. The flame retardant is at least one selected from a phosphorus-based flame retardant and inorganic fillers. The amounts of the thermosetting resin and the flame retardant are 1-150 parts by weight and 0.1-200 parts by weight respectively, to 100.0 parts by weight of the polyimide resin.

Description

Polyimide adhesive composition, cured product, adhesive sheet, laminate, flexible printed circuit board {Polyimide-based adhesive composition, cured product, adhesive sheet, laminate, and flexible printed circuit board}

The present invention is obtained using a polyimide adhesive composition, a cured product obtained by including the adhesive composition, an adhesive sheet containing the cured product, a laminate obtained by using the adhesive sheet, and the laminate The present invention relates to a flexible printed circuit board.

BACKGROUND ART [0002] Aromatic polyimide resins having excellent heat resistance, flexibility, adhesiveness to a circuit board, and the like have been commonly used as adhesives for the production of printed circuit boards and build-up boards used in electronic products and electronic devices. Aromatic polyimide resins are also widely used as adhesive compositions for carrier tapes and sheets, which are temporary fixing means for conveying electronic components such as semiconductor devices, and are indispensable for manufacturing electronic products and electronic devices. It is becoming.

However, many of the aromatic polyimide resins are difficult to dissolve in organic solvents, making it difficult to use them as varnishes. Therefore, conventionally, after coating the solution of the precursor (polyamic acid) to a circuit board, the ring-closure reaction was performed under heating, and the film of polyimide resin was formed on the board | substrate. However, in this method, the substrate itself may be heat deteriorated.

Patent Document 1 discloses an aromatic polyimide siloxane obtained by reacting biphenyltetracarboxylic acid, diaminopolysiloxane and diaminobenzoic acid as an aromatic polyimide resin having improved solubility in an organic solvent.

In addition, Patent Document 2 discloses an oxydiphthalic dianhydride (biphenyl tetracarboxylic dianhydride), bisaminopropyl polydimethylsiloxane, and bisaminophenoxy benzene in a predetermined ratio as an aromatic polyimide resin as an adhesive. The aromatic polyimide siloxane whose glass transition temperature which can be obtained is 350 degrees C or less is disclosed.

Further, Patent Document 3 discloses a flexible wiring substrate coated with a composition comprising an aromatic polyimide siloxane having an intended viscosity and an epoxy resin, which is soluble in an organic solvent obtained from various tetracarboxylic acids and diamines.

In addition, Patent Document 4 discloses a carrier tape for tape automated bonding (TAB) obtained by laminating a composition containing an aromatic polyimide siloxane and an epoxy compound obtained by reacting biphenyltetracarboxylic acid, diaminopolysiloxane, and aromatic diamine. Is described.

However, the adhesive composition using the above-mentioned aromatic polyimide siloxane as described above does not have sufficient adhesiveness or adhesiveness (hereinafter, collectively referred to as heat resistance) to an inorganic substrate or an organic substrate at a high temperature.

In addition, when a known aromatic polyimide siloxane is used as an adhesive layer of a carrier tape or a sheet as described above, there is a problem that residues of the adhesive tend to occur. The residue of said adhesive means that a part of adhesive bond layer adheres to the surface of a component, when peeling an electronic component from the adhesive surface of a carrier tape or a sheet, and becomes a factor which reduces the product yield and productivity of a product.

Patent Document 5 discloses that an acrylonitrile butadiene rubber (NBR) is used in place of an aromatic polyimide siloxane as an adhesive of a carrier tape or a sheet. However, the above-mentioned material does not have sufficient heat resistance, tack) is a strong problem.

(Patent Document 1) JP-A 4-36321 (Patent Document 2) Japanese Patent Application Laid-Open No. 5-112760 (Patent Document 3) Japanese Patent Application Laid-Open No. 8-253677 (Patent Document 4) JP-A-7-224259 (Patent Document 5) Japanese Patent Application Laid-Open No. 2006-117899

An object of the present invention can be used as a solution homogeneously dissolved in an organic solvent, it is excellent in heat resistance, hardly any residue of the adhesive, low tack in the hardened state, and a novel polyimide adhesive It is to provide a composition.

In order to achieve the above object, the present invention provides a polyimide adhesive composition obtained by dissolving a predetermined polyimide resin (A) and a thermosetting resin (B) in an organic solvent.

Specifically, in the present invention, at least one polyimide resin (A) selected from the group consisting of the following [1] to [4] and, if necessary, the thermosetting resin (B) and the flame retardant (C) is an organic solvent (D). The polyimide adhesive composition obtained by melt | dissolving in is provided.

[1] polyimide resin obtained by reacting aromatic tetracarboxylic acids (a1) and diamines (a2) containing 30 mol% or more of dimerdiamine;

[2] a polyimide resin obtained by further chain-stretching a polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of dimerdiamine as the component (a2);

[3] polyimide resin obtained by reacting a polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of dimerdiamine and an epoxy group-containing alkoxysilane partial condensate (a3) ; And

[4] A polyimide resin and an epoxy group obtained by further chain-stretching a polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of dimerdiamine in the component (a2). Polyimide resin obtained by making containing alkoxysilane partial condensate (a3) react.

In addition, the present invention is obtained by thermally compressing a sheet substrate on the adhesive sheet obtained by applying the cured product obtained by curing the adhesive composition and the adhesive composition onto a sheet substrate and drying the adhesive sheet. The laminated body which can be obtained, the laminated body obtained by heating the said laminated body again, and the flexible printed circuit board obtained using the said laminated body are provided.

The adhesive composition according to the present invention can be used as a solution homogeneously dissolved in an organic solvent. In addition, it is excellent in the initial adhesiveness and heat resistance adhesion to the inorganic substrate and organic substrate. Furthermore, the hardened | cured material (adhesive layer) obtained with the said adhesive composition is a law tack, it is difficult to foam at the time of heating, and the residue of an adhesive hardly remains.

Furthermore, the adhesive composition according to the present invention is not only an adhesive used for manufacturing printed circuit boards (build-up boards, flexible printed boards, etc.) or copper sheets for flexible printed boards, but also adhesives of carrier tapes or carrier sheets such as TAB tapes or COF tapes. And semiconductor interlayer materials.

<Polyimide adhesive composition>

The polyimide adhesive composition according to the present invention is at least one polyimide resin (A) (hereinafter referred to as component (A)) selected from the group consisting of the following [1] to [4], and thermosetting as necessary. The resin (B) (hereinafter referred to as component (B)) and the flame retardant (C) (hereinafter referred to as component (C)) are dissolved in an organic solvent (D) (hereinafter referred to as component (D)). It is obtained.

[1] Aromatic tetracarboxylic acids (a1) (hereinafter referred to as component (a1)) and diamine (a2) (hereinafter referred to as component (a2)) containing 30 mol% or more of dimerdiamine are reacted to react. Polyimide resin (henceforth (A-1) component) obtained;

[2] a polyimide resin (hereinafter, referred to as (A-2) component) obtained by chain-extending the component (A-1) with the component (a2);

[3] A polyimide resin (hereinafter referred to as (A-3) component) obtained by reacting a component (A-1) with an epoxy group-containing alkoxysilane partial condensate (a3) (hereinafter referred to as component (a3)). ); And

[4] A polyimide resin obtained by reacting the component (A-2) with the component (a3) (hereinafter referred to as component (A-4)).

As (a1) component, a well-known thing can be used as a raw material of a polyimide. Specifically, for example, pyromellitic acid dianhydride or a compound represented by the following formula (1) may be mentioned.

[Formula 1]

(In the formula 1,

X represents a single bond or at least one structure selected from the group represented by the following formula (2).)

(2)

Examples of the compound represented by Formula 1 include 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4, 4'-diphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1, 4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic Acid dianhydrides, 2,3,3 ', 4'-diphenylethertetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfontetracarboxylic dianhydride, 2,2-bis ( 3,3 ', 4,4'-tetracarboxyphenyl) tetrafluoropropane dianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-bis (2,3 -Dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, cyclopentanetetracarboxylic anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic anhydride, 4,4'-propane-2,2'-diylbis (1,4-phenyleneoxy) diphthalic dianhydride, and the like. .

Dimerdiamine which comprises (a2) component is a compound derived from dimer acid which is a dimer of unsaturated fatty acids, such as oleic acid, as described in Unexamined-Japanese-Patent No. 9-12712. In the present invention, a known dimerdiamine can be used without particular limitation, but is preferably represented by the following Chemical Formula 3 or Chemical Formula 4, for example.

(3)

(In the formula (3), m + n = an integer of 6 to 17, p + q = an integer of 8 to 19, the broken line means a carbon-carbon single bond or a carbon-carbon double bond.)

[Formula 4]

(In the formula (4), m + n = an integer of 6 to 17, p + q = an integer of 8 to 19, the broken line means a carbon-carbon single bond or a carbon-carbon double bond).

Dimerdiamine is represented by the above formula (4) in view of organic solvent solubility, initial adhesiveness, heat-resistant adhesiveness, law tack of the adhesive composition according to the present invention, less residue of the adhesive, etc. Preferred are compounds and compounds represented by the following formula (5).

[Formula 8]

As a commercial item of dimerdiamine, Basamin 551 (made by BASF Japan Co., Ltd.), Basamin 552 (made by Cognix Japan Penn; water additive of Basamin 551), PRIAMINE1075, PRIAMINE1074 (Kurodazepan Co., Ltd.) 1) etc. can be mentioned.

The content of dimerdiamine in the component (a2) is generally 30 based on the total 100 mol% of the component (a2) in view of heat resistance, law tack and less residue of the adhesive. It is mol% or more, Preferably it is 45-100 mol%. In addition, the component (a2) may contain other diamines generally in the range of less than 70 mol%, preferably 0 to 55 mol%, as necessary.

As said other diamine, various well-known diamine can be used without a restriction | limiting in particular. Specifically, for example, diamino polysiloxane may be used, and among them, a compound characterized by the following formula (5) is preferable.

[Chemical Formula 5]

(In the above formula (5)

R ₁ represents an alkylene group having 2 to 6 carbon atoms, R ₂ represents an alkyl group having 1 to 4 carbon atoms, and r represents an integer of 1 to 30).

As diamino polysiloxane represented by the said Formula (5), For example, (alpha), (gamma) -bis (2-aminoethyl) polydimethyl siloxane, (alpha), (gamma) -bis (3-aminopropyl) polydimethyl siloxane, (alpha), (gamma)- Bis (4-aminobutyl) polydimethyl siloxane, α, ω-bis (5-aminopentyl) polydimethyl siloxane, α, ω-bis [3- (2-aminophenyl) propyl] polydimethyl siloxane, α, ω- Bis [3- (4-aminophenyl) propyl] polydimethyl siloxane and the like, and two or more kinds thereof may be combined from the group comprising the above.

Moreover, as said other diamine, 2, 2-bis [4- (3-aminophenoxy) phenyl] propane, 2, 2-bis [4- (4-amino phenoxy) phenyl] propane, for example. Bisamino phenoxy phenyl propanes, such as these; Diaminodiphenyl ethers such as 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether and 4,4'-diamino diphenyl ether; phenylenediamines such as p -phenylenediamine and m -phenylenediamine; Diaminodiphenyl sulfides such as 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide and 4,4'-diaminodiphenyl sulfide; Diaminodiphenyl sulfones such as 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone; Diamino benzophenones such as 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone and 3,4'-diaminobenzophenone; Diaminodiphenylmethanes such as 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane and 3,4'-diaminodiphenylmethane; Diaminophenyl propane such as 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane Ryu; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-amino phenyl) -1,1,1,3,3, Diaminophenylhexafluoropropanes such as 3-hexafluoropropane and 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane; 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl Diaminophenyl phenylethanes such as) -1-phenylethane; 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4- Bisaminophenoxy benzenes such as aminophenoxy) benzene; 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) Bisaminobenzoyl benzenes such as benzene; 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, bisaminodimethyl benzenes such as α-dimethylbenzyl) benzene and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene; 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis ( Bisamino ditrifluoromethylbenzylbenzenes such as 3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-trifluoromethylbenzyl) benzene; 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4'-bis (3-aminophenoxy) phenyl, 4,4'-bis Aminophenoxy biphenyls such as (4-aminophenoxy) biphenyl; Aminophenoxy phenyl ketones such as bis [4- (3-amino phenoxy) phenyl] ketone and bis [4- (4-aminophenoxy) phenyl] ketone; Aminophenoxyphenyl sulfides such as bis [4- (3-aminophenoxy) phenyl] sulfide and bis [4- (4-aminophenoxy) phenyl] sulfide; Aminophenoxyphenyl sulfones such as bis [4- (3-aminophenoxy) phenyl] sulfone and bis [4- (4-aminophenoxy) phenyl] sulfone; Aminophenoxy phenyl ethers such as bis [4- (3-aminophenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether; 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Aminophenoxyphenyl propanes such as fluoropropane and 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane; And 1,3-bis 4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-amino Phenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene , 1,3-bis [4- (4-amino phenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene , 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4, 4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] di Phenyl sulfone, 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'- Diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'- Bis (3-aminophenoxy) 3,3,3 ', 3'-te Lamethyl-1,1'-Spirobiindane, 6,6'-bis (4-aminophenoxy) 3,3,3, '3'-tetramethyl-1,1'-Spirobiindane, 1,3 Bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-amino Propyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminopropyl) ethyl] ether, 1,2-bis (Aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2- Aminoethoxy) ethoxy] ethane, ethylene glycol-bis (3-aminopropyl) ether, diethylene glycol-bis (3-aminopropyl) ether, triethylene glycol-bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Tan, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-dia Minocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclo hexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl ) Bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, and the like.

In addition, said (A-1) component can be manufactured by various well-known methods. For example, first, the component (a1) and the component (a2) are generally about 60 to 120 ° C, preferably at a temperature of 80 to 100 ° C, generally about 0.1 to 2 hours, preferably 0.1 to 0.5 hour Addition reaction. The adduct obtained above is about to be obtained by imidization reaction, that is, dehydration ring closure reaction, at a temperature of about 80 to 250 ° C, preferably at 100 to 200 ° C, for about 0.5 to 50 hours, preferably for 1 to 20 hours. (A-1) A component can be obtained.

Moreover, in the said imidation reaction, various well-known reaction catalysts, a dehydrating agent, and the organic solvent mentioned below can be used. As the reaction catalyst, aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as methylaniline, heterocyclic tertiary amines such as pyridine, picoline, isoquinoline and the like can be used. Moreover, as a dehydrating agent, aliphatic acid anhydrides, such as acetic anhydride, aromatic acid anhydrides, such as benzoic anhydride, etc. can be used.

Although the imide ring closure rate of the said (A-1) component is not specifically limited, Generally, it is 70% or more, Preferably it is 85 to 100%. Said "imide cyclization rate" means content of a ring (cyclic) imide bond in (A-1) component, and can be determined by various spectroscopic means, such as NMR and IR analysis. Moreover, initial stage adhesiveness and heat-resistant adhesiveness of the adhesive composition of this invention become further more favorable by making the imide closure rate of (A-1) component 70% or more, and the said imidation reaction to the hardened | cured material of this invention. It is difficult to produce foaming due to the moisture produced by the following.

Although the usage-amount of (a1) component and (a2) component is not specifically limited, From a viewpoint of the solubility of (A-1) component as (D) component, an initial stage adhesiveness, and a heat-resistant adhesiveness, [[a1) component Number of moles to be used / number of moles of the component (a2)] is generally in the range of about 0.6 / 1 to 1.4 / 1, preferably 0.8 / 1 to 1.2 / 1.

The said (A-2) component is a polyimide resin obtained by carrying out chain extension of the (A-1) component obtained by the said method to the said (a2) component further.

Although reaction conditions of (A-1) component and (a2) component are not specifically limited, Generally, reaction temperature is 60 degrees C or less, Preferably it is 50 degrees C or less, Reaction time is about 1 to 6 hours, Preferably React for 1 to 3 hours. Moreover, the organic solvent mentioned below can also be used at the time of reaction.

The amount of the component (a2) used as the chain extender is not particularly limited, but for the purpose of achieving the effect of the present invention, generally, [mole number of the remaining carboxyl groups in the component (A-1)] / [chain extension agent Mole number of component (a2)] is in the range of about 0.6 / 1 to 1.4 / 1.

In addition, in the component (A-2), the imide closure rate is not particularly limited, but is generally 70% or more, preferably 85 to 100%.

(A-3) A component is a polyimide resin containing an alkoxy silyl group in the molecule | numerator obtained by making (A-1) component and (a3) component react, and since it is self-crosslinking resin, it does not use (B) component mentioned below. Moreover, it becomes possible to obtain the adhesive hardened | cured material excellent in heat-resistant adhesiveness.

(a3) A component is a high molecular weight compound which has the silicon atom which the alkyl group and the alkoxy group couple | bonded in the molecular chain using a siloxane bond as a continuous unit, and has an epoxy group at the terminal of a molecule | numerator, and removes various well-known alkoxysilane partial condensates and epoxy alcohols. It can obtain by alcohol reaction (hydrolysis reaction).

The alkoxysilane partial condensate component may be represented by the following formula (6):

[Formula 6]

(6)

R <_3> represents a C1-C3 alkyl group and R <_4> represents a C1-C3 alkyl group or an aryl group. In addition, s is an integer of 2-100, Preferably it is an integer of 2-50, More preferably, the integer of 3-8 is represented).

The epoxy alcohol is characterized in that represented by the following formula (7):

[Formula 7]

(In the said formula (7), t is an integer of 1-10, Preferably the integer of 1-8 is represented.).

The dealcohol reaction can be carried out according to various known methods. Specifically, for example, the alkoxysilane partial condensate and an epoxy alcohol are preferably reacted while removing an alcohol generated by heating under a condition of about 50 to 150 ° C, preferably 70 to 110 ° C.

In addition, the usage-amount of an alkoxysilane partial condensate and an epoxy alcohol is not specifically limited, but in consideration of heat-resistance adhesiveness, the remainder of an adhesive agent, etc., generally, [the number of moles of the alkoxy group in an alkoxysilane partial condensate) / hydroxyl group in an epoxy alcohol Molar number] is generally in the range of about 1 / 0.3 to 1 / 0.01.

Furthermore, in a dealcoholization reaction, (D) component described below and various well-known catalyst can be used as needed. Examples of the catalyst include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, cadmium, and manganese; Oxides, organic acid salts, halides, alkoxides and the like containing such metals may be mentioned.

The reaction between the component (A-1) and the component (a3) is a so-called ring-opening esterification reaction. Although reaction conditions are not specifically limited, Reaction temperature is generally about 40-130 degreeC, Preferably it is 70-110 degreeC, and reaction time is about 1 to 7 hours generally.

In the ring-opening esterification reaction, for example, 1,8-diaza-bicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol as various known catalysts. Tertiary amines such as tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzimidazole Imidazoles; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4 Tetraphenyl boron salts, such as -methylimidazole tetraphenyl borate and N-methylmorpholine tetraphenyl borate, etc. can be used. Although the usage-amount is not specifically limited, Generally, it is about 0.15 weight part with respect to 100 weight part (solid content conversion) of the target (A-3) component.

In addition, in the ring-opening esterification reaction, (D) component described below can be used, Especially aliphatic solvents, such as cyclohexanone, are preferable. Furthermore, the viscosity stability of the solution of (A-3) component and below-mentioned (A-4) component is improved by adding various well-known low molecular alcohols, for example, methanol, ethanol, a propanol, etc.

The component (A-4) is a polyimide resin containing an alkoxysilyl group in a molecule, which is obtained by reacting the component (A-2) with the component (a3), and is self-crosslinking similar to the component (A-3). Since it is resin, it becomes possible to obtain the adhesive hardened | cured material excellent in heat-resistant adhesiveness, without using (B) component mentioned later. The reaction conditions of the component (A-2) and the component (a3) are similar to those of the component (A-3).

The alkoxysilyl group remains in (A-3) component and (A-4) component, and this part becomes a reaction point of the sol-gel reaction described below. The remaining amount of the alkoxysilyl group is not particularly limited, but is preferably 60% or more, preferably 80% or more of each alkoxysilyl group in the component (A-3) and (A-4).

(B) A component is a hardening | curing agent of the polyimide adhesive composition of this invention, A various well-known thing can be used without a special limitation. Specifically, at least 1 sort (s) chosen from the group which consists of an epoxy resin, benzoxazine resin, bismaleimide resin, and a cyanate ester resin is preferable, for example.

As said epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, hydrogenated bisphenol A-type epoxy, for example Resin, hydrogenated bisphenol F type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidyl amine type epoxy resin, triphenol phenol Methane type epoxy resins, alkyl modified triphenol methane type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene skeleton containing epoxy resins, naphthalene skeleton containing epoxy resins, aryl alkylene type epoxy resins and the above epoxy resins as dimer acids Modified epoxy resin obtained by modification, dimeric acid diglycidyl ester, etc. are mentioned. Were, from the viewpoint of transparency and heat resistance of the adhesive composition is preferably at least one member selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resins and alicyclic epoxy resins. Moreover, as a commercial item, for example, "ST-3000" by Mitsubishi Chemical Co., Ltd. "jER828", "jER834", "jER807" Shin-Nitetsu Chemical Co., Ltd., and Daicel Chemical Industries, Ltd. "Ceroxide 2021P""YD-172-X75" by Shin-Nitetsu Chemical Co., Ltd., etc. can be mentioned, Two or more types can also be combined from the group containing this.

In addition, when using an epoxy resin as a thermosetting resin, various well-known hardening | curing agents for epoxy resins can be used together. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydro phthalic anhydride, 3-methyl-hexahydro phthalic anhydride, 4-methyl-hexahydro phthalic anhydride Or a mixture of 4-methyl-hexahydro phthalic anhydride and hexahydro phthalic anhydride, tetrahydro phthalic anhydride, methyl-tetrahydro phthalic anhydride, nadic anhydride, methylnadic anhydride, norbornene-2,3- Dicarboxylic anhydride (norbornene-2,3-dicarboxylic anhydride), methylnorbornene-2,3-dicarboxylic anhydride, methylcyclohexenedicarboxylic acid anhydride, 3 Acid anhydride curing agents such as dodecene anhydride and octenyl succinic anhydride; Amine-based curing agents such as dicyandiamide (cyanoguanidine, DICY), aliphatic diamines (trade names "LonazcureM-DEA", "LonzacureM-DETDA"; Lonzazefen Co., Ltd.) and aliphatic amines; Phenolics such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, triazine modified phenol novolak resin, phenolic hydroxyl group-containing phosphazene (trade name "SPH-100" of Otsuka Chemical Co., Ltd.) A curing agent, a cyclic phosphazene compound, etc. are mentioned. Among these, a phenolic hardening | curing agent, especially a phenolic hydroxyl group containing phosphazene-type hardening | curing agent is preferable since it is easy to provide a flame retardance to the hardened | cured material and laminated body which concern on this invention. Although the usage-amount of said hardening | curing agent is not specifically limited, Generally, when the solid content of the adhesive composition of this invention is 100 weight%, the usage-amount of a hardening | curing agent is about 0.01-5 weight%.

Furthermore, as a catalyst for promoting the reaction of an epoxy resin and the above curing agent, for example, 1,8-diaza-bicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine Tertiary amines such as triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl Imidazoles such as imidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2- Tetraphenylboron salts such as ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate; have.

Furthermore, although the usage-amount of said catalyst is not specifically limited, Generally, the usage-amount of a catalyst is about 0.01-5 weight% with respect to the solid content of the adhesive composition of this invention being 100 weight%.

Examples of the benzoxazine resins include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6 And 6- (1-methylethylidene) bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine). Moreover, even if a phenyl group, a methyl group, a cyclohexyl group, etc. couple | bonded with nitrogen of an oxazine ring, it is preferable. Further, commercially available products include, for example, "benzoxazine Fa type" or "benzoxazine pd type" manufactured by Shikoku Kasei Kogyo Co., Ltd., "RLV-100" manufactured by Air Water Corporation, and the like. It can be used in combination of 2 or more type.

As said bismaleimide resin, 4,4'- diphenylmethane bismaleimide, m -phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'- dimethyl-5, for example. , 5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl ) Hexane, 4,4'- diphenyl ether bismaleimide, 4,4'- diphenyl sulfone bis maleimide, etc. are mentioned. Moreover, as a commercial item, "BAF-BMI" etc. of JFE Chemical Co., Ltd. are mentioned, for example. Furthermore, it can use combining at least 2 type or more from the group which consists of said bismaleimide resin.

As said cyanatoester resin, 2-aryl phenol cyanato ester, 4-methoxy phenol cyanato ester, 2, 2-bis (4-cyanatophenyl) -1,1, for example , 1,3,3,3-hexafluoropropane, bisphenol A cyanatoester, diaryl bisphenol A cyanatoester, 4-phenylphenol cyanatoester, 1,1,1-tris (4-cyanae Tophenyl) ethane, 4-cumylphenolcyanatoester, 1,1-bis (4-cyanatophenyl) ethane, 4,4'-bisphenolcyanatoester, 2,2-bis (4-cyanae) Tophenyl) propane and the like. Moreover, as a commercial item, "PRIMASET BTP-6020S (made by Lonza Pan Co., Ltd.)" etc. are mentioned, for example. These can combine 2 or more types. And at least two kinds of the cyanate ester resins may be used in combination.

The amount of the component (B) to be used is not particularly limited, but it is generally about 1 to 150 parts by weight, preferably about 3 to 100 parts by weight, more preferably about 3 to 100 parts by weight based on 100 parts by weight (in terms of solid content) 3 to 75 parts by weight.

If the component (C) is a flame retardant that can be used in the polyimide adhesive composition, various known ones can be used without particular limitation, but for the effect of flame retardancy, a phosphorus flame retardant and / or an inorganic filler is particularly preferable.

Examples of the phosphorus flame retardant include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives containing no phenolic hydroxyl group. Among the derivatives, cyclic phosphazene derivatives (such as "Ravitol FP300" manufactured by Fushimi Pharmaceutical Co., Ltd.) are preferable in terms of flame retardancy, heat resistance, resistance to plate-out, and the like.

Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, and nitriding. Boron, crystalline silica, amorphous silica, graphite powder, boehmite, and the like. Among these, aluminum hydroxide (boehmite) is particularly preferable because of excellent dispersibility and flame retardancy in the adhesive composition of the present invention.

Although the usage-amount of (C) component is not specifically limited, It is the range which generally becomes about 0-200 weight part with respect to 100 weight part (solid content conversion) of (A) component, Preferably it is about 25-150 weight part.

As (D) component, for example, aprotons such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyltriglyme, and methyl diglyme Polar polar solvents; Alicyclic solvents such as cyclohexanone and methylcyclohexane; Alcohol solvents, such as methanol, ethanol, a propanol, benzyl alcohol, and a cresol, can be mentioned, It can use combining at least 2 or more types from the group containing such a solvent.

Although the usage-amount of (D) component is not specifically limited, Generally, it is preferable to use in the range which the non volatile matter of the adhesive composition of this invention becomes about 20 to 60 weight%.

In addition to the adhesive composition of the present invention, if necessary, the ring-opening esterification reaction catalyst, dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, bleaching agent, colorant, conductive agent, mold release agent, surface treatment agent, viscosity modifier, etc. Additives, such as these, can be used in combination.

<Cured product>

The hardened | cured material of this invention hardened the adhesive composition of this invention. Specifically, first, the adhesive composition is generally heated to about 70 to 200 ° C. and cured for 1 to 10 minutes (step 1); Next, in order to advance hardening reaction with (B) component (thermosetting resin), it heat-processes generally about 150-250 degreeC, and it carries out for reaction for about 10 minutes-3 hours (step 2) obtained, and obtained Since the shrinkage of hardened | cured material can be made gentle, adhesiveness with respect to a base material can be ensured, and foaming due to the water which arises incidentally by the said dehydration ring closure reaction can also be suppressed. Furthermore, the said hardening reaction includes the dehydration ring closure reaction of the polyamic acid derived from (A) component, and the sol-gel reaction of the alkoxy silyl group derived from (a3) component.

In addition, the cured product obtained by including the adhesive composition of the present invention may include silica (SiO ₂ ) particles generated by the sol-gel reaction. Furthermore, although content is generally about 0 to 15 weight%, about the adhesive composition using the (A-3) component and (A-4) component, when carrying out heat-hardening of the said adhesive composition, it can obtain the fluidity appropriately. in order to improve the adhesiveness between the cured material and the base material is preferably silica (SiO ₂₎ content of usually 0.5 to 15%, preferably in the range of 1 to 10% of the particles. The above content is a calculated value calculated from the raw material input amount.

Although the shape of the hardened | cured material of this invention is not specifically limited, When providing for the adhesive use of a base sheet, the film thickness is generally about 1-100 micrometers, Preferably it is about 3-50 micrometers, and can adjust suitably according to a use.

The adhesive sheet of this invention can be obtained by apply | coating the adhesive composition of this invention to a sheet base material, and drying it. Examples of the sheet base material include polyimide, polyimide silica hybrid, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polymethyl methacrylate resin ( PMMA), polystyrene resin (PSt), polycarbonate resin (PC), acrylonitrile butadiene styrene resin (ABS), ethylene terephthalate; And organic base materials such as aromatic polyester resins (so-called liquid crystal polymers; Kurarese, Bexsta, etc.) obtained from parahydroxybenzoic acids such as phenol, phthalic acid and hydroxy naphthoic acid. Also in this, a polyimide film, especially a polyimide silica hybrid film is preferable with respect to heat resistance, dimensional stability, etc. It is preferable to set the thickness of the said sheet base material suitably according to a use. Furthermore, an adhesive sheet can be used as a carrier sheet and a carrier tape.

The laminated body of this invention can be obtained by thermo-compressing another sheet base material on the adhesive surface of the said adhesive sheet. As the sheet substrate, a metal such as glass, iron, aluminum, 42 alloy, copper, or an inorganic substrate such as ITO, silicon or silicon carbide is suitable, and the thickness can be appropriately set depending on the application. Moreover, it is preferable to heat-process the said laminated body further.

The flexible printed circuit board of the present invention can be obtained by bonding the adhesive surface of the adhesive sheet to the inorganic substrate surface of the laminate using the laminate. As said flexible printed circuit board, it is preferable to use a polyimide sheet base material as an organic base material, and metal foil (especially copper foil) as an inorganic base material. In addition, a flexible printed wiring board can be obtained by soft etching the metal surface of the flexible printed board to form a circuit, and attaching the adhesive sheet to the circuit again and thermocompression bonding.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited by the following Examples and Preparation Examples. In addition, the part and% in each case are a basis of weight unless there is particular notice.

<Preparation of the polyimide resin adhesive composition of the silane group modification type>

&Lt; Preparation Example 1 &

3,3 ', 4,4'- benzophenone tetracarboxylic anhydride (brand name "BTDA", the Daicel Chemical Industry Co., Ltd. product) to the reaction container provided with a stirrer, a water fountain, a thermometer, and a nitrogen gas introduction tube; (Briefly referred to as benzophenone tetracarboxylic anhydride) (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were added, and then the solution was heated to 60 ° C. After heating, dimerdiamine (brand name "PRIAMINE1075", manufactured by Kurodazepan Co., Ltd .; hereinafter simply referred to as dimerdiamine) (85.40 g) was added dropwise thereto, and then heated to 140 ° C, followed by imidization reaction for 1 hour. The solution (non-volatile content 38.0%) of polyimide resin (A-1-1) was obtained. The molar ratio of acid component / amine component in the solution is 1.04.

&Lt; Preparation Example 2 &

3,3 ', 4,4'- diphenylsulfontetracarboxylic dianhydride (made by Nippon Kasei Co., Ltd., brand name "Rica sheet DSDA") to the same reaction container as the said Production Example 1; Sulfontetracarboxylic dianhydride) (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were added, and then the solution was heated to 60 ° C. Next, dimerdiamine (76.82 g) was added dropwise thereto, and then heated to 140 ° C and imidized for 1 hour to obtain a solution (non-volatile content 36.0%) of polyimide resin (A-1-2). The molar ratio of acid component / amine component in the solution is 1.04.

&Lt; Preparation Example 3 &

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g), and methylcyclohexane (37.10 g) were put into the same reaction container as the said preparation example 1, and the solution was heated to 60 degreeC. After heating, dimerdiamine (85.40 g) was added dropwise, and then heated to 140 ° C and imidized for 1 hour to obtain a solution of polyimide resin (non-volatile content 37.0%). The molar ratio of acid component / amine component in the solution is 1.04. After cooling the solution of said polyimide resin to room temperature, 2, 2-bis [4- (4-amino phenoxy) phenyl] propane (brand name "BAPP", Wakayama Purification Co., Ltd. product; 1.78) is a chain extender. g) was added slowly in small portions to keep the temperature below 40 ° C. After completion of the addition, chain elongation was continued while stirring at room temperature for 30 minutes, and the solution (non-volatile content 38.0%) of polyimide resin (A-2-1) was obtained.

&Lt; Preparation Example 4 &

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (212.00 g), and methylcyclohexane (42.40 g) were put into the same reaction container as the said preparation example 1, and the solution was heated to 60 degreeC. After heating, dimerdiamine (42.70 g) and α, ω-bis- (3 aminopropyl) polydimethylsiloxane (trade name "KF8010", Shin-Etsu Chemical Co., Ltd .; hereinafter simply referred to as bisaminopropylpolydimethylsiloxane.) (69.59 g) was added dropwise thereto, and then heated to 140 ° C and imidized for 1 hour to obtain a solution of polyimide resin (A-1-3) (non-volatile content 39.0%). In this solution, the dimer diamine in the diamine component is 50 mol%, and the molar ratio of the acid component / amine component is 1.04.

&Lt; Production Example 5 &

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (159.00 g) and methylcyclohexane (31.80 g) were added to the same reaction vessel as in Preparation Example 1, and the solution was heated to 60 ° C. After heating, dimerdiamine (80.74 g) was added dropwise, and then heated to 140 ° C and imidized for 1 hour to obtain a solution of polyimide resin. In the above solution, the molar ratio of acid component / amine component is 1.10. After the polyimide resin solution was cooled to room temperature, dimerdiamine (6.73 g) was gradually added in small portions as a chain extender, followed by elongation reaction with stirring at room temperature for 1 hour to obtain polyimide resin (A-2-2). A solution (42.0% nonvolatile content) was obtained.

&Lt; Production Example 6 &

4,4 '-[propane-2,2'-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride (brand name "BisDA2000", SABIC Innovative Plastic Japan) in the same reaction vessel as in Production Example 1 Co., Ltd .; hereafter simply referred to as diylbisphenyleneoxydiphthalic dianhydride) (70.00 g), cyclohexanone (175.00 g), and methylcyclohexane (35.00 g) were added, and then the solution was heated to 60 ° C. . After heating, dimerdiamine (69.90 g) was added dropwise, and then heated to 140 ° C and imidized for 1 hour to obtain a solution of a polyimide resin (A-1-4) (non-volatile content 40.5%). The molar ratio of acid component / amine component in the solution is 1.04.

&Lt; Production Example 7 >

4,4'- oxydiphthalic anhydride (brand name "ODPA-1000", product made by SABIC Innovative Plastics Japan Co., Ltd .; hereafter referred to simply as oxydiphthalic anhydride) in the same reaction vessel as Preparation Example 1 (50.00 g) ), Cyclohexanone (226.50 g) and methylcyclohexane (25.00 g) were added, and then the solution was heated to 60 ° C. After heating, dimerdiamine (84.56 g) was added dropwise, and then heated to 140 ° C and imidized for 1 hour to obtain a solution of polyimide resin (A-1-5) (non-volatile content 35.0%). The molar ratio of acid component / amine component in the solution is 1.03.

&Lt; Production Example 8 &

Diylbisphenyleneoxydiphthalic dianhydride (65.00 g), cyclohexanone (266.50 g) and methylcyclohexane (44.42 g) were added to the same reaction vessel as in Preparation Example 1, and the solution was heated to 60 ° C. After heating, dimerdiamine (43.71 g) and 1,3-bis (aminomethyl) cyclohexane (trade name "1,3-BAC", manufactured by Mitsubishi Gas Chemical Co., Ltd.) (5.42 g) were gradually added, followed by heating to 140 ° C. And imidation reaction for 1 hour to obtain a solution of a polyimide resin (A-1-6) (non-volatile content 29.5%). The molar ratio of acid component / amine component in the solution is 1.05.

< Comparative Production Example 1>

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g), and methylcyclohexane (37.10 g) were put in the same reaction container as Preparation Example 1, and the solution was heated to 60 ° C. After heating, bisaminopropyl polydimethylsiloxane (139.17 g) was added dropwise in place of the dimerdiamine, and then the solution was heated to 140 ° C and imidized for 1 hour to give a solution of the polyimide resin (a) (non-volatile content). 46.2%). The molar ratio of acid component / amine component in the solution is 1.04.

<Comparative Production Example 2>

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (212.00 g), and methylcyclohexane (42.40 g) were put into the same reaction container as the manufacture example 1, and the solution was heated to 60 degreeC. After heating, dimerdiamine (21.35 g) and bisaminopropyl polydimethylsiloxane (104.38 g) were added dropwise, followed by imidization reaction for 1 hour to obtain a solution of polyimide resin (I) (non-volatile content 41.0%). . The molar ratio of acid component / amine component in the solution is 1.04.

Polyimide resin (a1) (a2) (polyimide component) (a2)
(Chain extension) Dimerdiamine Other diamine Production Example 1 (A-1-1) BTDA PRIAMINE --- --- Production Example 2 (A-1-2) DSDA PRIAMINE --- --- Production Example 3 (A-2-1) BTDA PRIAMINE --- BAPP Production Example 4 (A-1-3) BTDA PRIAMINE
(50 mol%) KF8010
(50 mol%) --- Production Example 5 (A-2-2) BTDA PRIAMINE --- PRIAMINE Production Example 6 (A-1-4) BISDA PRIAMINE --- --- Production Example 7 (A-1-5) ODPA PRIAMINE --- --- Production Example 8 (A-1-6) BISDA PRIAMINE
(68 mol%) 1,3-BAC
(32 mol%) --- Comparative Preparation Example 1 (end) BTDA --- KF8010 --- Comparative Production Example 2 (I) BTDA PRIAMINE
(25 mol%) KF8010
(75 mol%) ---

BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride

DSDA ： 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride

BISDA: 4,4 '-[propane-2,2'-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride

PRIAMINE ： Dimerdiamine

KF8010: α, ω-bis (3-aminopropyl) polydimethylsiloxane

BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane

1,3-BAC: 1,3-bis (aminomethyl) cyclohexane

&Lt; Example 1 >

As a component (A), the solution (100.0 g) of the polyimide resin (A-1-1) of the said manufacture example 1, bisphenol-A epoxy resin (brand name "jER828", epoxy equivalent 190 g / eq, as a component), Japan Epoxy Resin Co., Ltd. product; 4.23 g), phenol novolak resin (trade name "Tamanole T759", hydroxyl equivalent 106 g / eq, Arakawa Chemical Industries; 2.18 g) and 2-ethyl-4-methyl Midazole (brand name "2E4MZ", Shikoku Kagaku Kogyo Co., Ltd .; 0.06 g) is mixed. Next, boehmite (brand name "Cerasul BMT-3LV", Kawaii Lime Industry Co., Ltd .; 25.66 g), a cyclic cyanophenoxy phosphazene derivative (brand name "Ravitol FP-300"), Fushi as (C) component Unrefined Co., Ltd .: 12.00 g), cyclohexanone (49.33 g) and methanol (8.55 g) were added and stirred as an organic solvent, and the adhesive composition (non-volatile content 40.7%) was obtained.

<Examples 2 to 13>

As the component (A), the component (B), the component (C) and the organic solvent, those used in the amounts shown in Table 2 below were used in the same manner as in Example 1 to obtain respective adhesive compositions.

&Lt; Comparative Examples 1 and 2 &

In place of the solution of the component (A-1-1) used in Example 1, the solution of the component (A) or the solution of the component (B) was used in an amount shown in Table 2 below, and the component (B) , (C) component and the organic solvent were performed similarly to the method of Example 1 except having used the thing of the kind shown in following Table 2 respectively, and obtained each adhesive composition.

&Lt; Comparative Example 3 &

In place of the solution of the component (A-1-1) used in Example 1, NBR (trade name "XER 32C", manufactured by JSR Corporation) containing a carboxyl group was used in an amount shown in Table 2 below, ( Each adhesive composition was obtained in the same manner as in Example 1, except that the components B), (C) and the organic solvent were each used in the amounts shown in Table 2 below.

jER828 (brand name): Bisphenol A type epoxy resin (product made in Japan epoxy resin Co., Ltd., epoxy equivalent 190 g / eq)

Tamanol T759 (brand name): Phenolic novolak resin (Arakawa Chemical Co., Ltd. product, hydroxyl equivalent 106 g / eq)

2E4MZ (brand name): 2-ethyl-4-methylimidazole (made by Shikoku Kagaku Kogyo Co., Ltd.)

BMI-TMH (brand name): 1,6'-bismaleimide (2,2,4-trimethyl) hexane (made by Daiwa Kasei Kogyo Co., Ltd.)

Park mill D (brand name): Dicumyl peroxide (made in Japan)

PRIMASET BTP-6020S (brand name): cyanatoester resin (product made in Lauder Japan)

Cerasul BMT-3LV (brand name): Boehmite (product made in Kawai lime industry)

Labitol FP-300: phenoxyphosphazene derivative (made by Fushimi Pharmaceutical Co., Ltd.)

<Preparation of the polyimide resin adhesive composition of the silane modification type>

<Synthesis of (a3) Component>

In a reaction vessel equipped with a stirrer, a water fountain, a thermometer, and a nitrogen gas introduction tube, glycidol (trade name "Epiol OH", Nippon Oil Industries, Ltd .; 1400 g) and tetramethoxysilane partial condensate (brand name "methyl silicate") 51 ”, Tama Chemical Co., Ltd., the average number of Si, 4957.9 g) were added, and it heated up to 90 degreeC, stirring under nitrogen stream, and added dibutyltin laurate (2.0 g), and hydrolyzed reaction. I was. The methanol additionally generated during the reaction was removed by a water fountain, and cooled to room temperature for 5 hours when the amount of methanol reached about 630 g. Next, methanol remaining in the reaction system was removed under reduced pressure at 13 kPa for about 10 minutes to obtain a methoxysilane partial condensate (a3-1) containing an epoxy group.

&Lt; Example 14 >

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g), and methylcyclohexane (37.10 g) were put into the same reaction container as the preparation example 1, and the solution was heated to 60 degreeC. . After heating, dimerdiamine (85.40 g) was added dropwise, followed by imidization reaction at 140 ° C. for 1 hour to obtain a solution of polyimide resin. The molar ratio of acid component / amine component in the solution is 1.04.

After the polyimide resin solution was cooled to room temperature, the (a3-1) component (47.0 g) was added thereto, followed by deethanol reaction at 90 ° C. for 3 hours to form a methoxysilyl group-containing silane-modified polyimide resin (A-3- The solution of 1) was obtained. Next, after cooling the said solution to room temperature, methanol (93.9g) was added and the resin solution (non-volatile content 38.0%) was obtained. Furthermore, the said resin solution was further diluted with cyclohexanone, and the resin varnish (35.0% of non volatile matter) was obtained. The said resin varnish was used as an adhesive composition as it was.

< Example 15>

Diphenylsulfontetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were put in the same reaction vessel as Preparation Example 1 above, and the solution was heated to 60 ° C. . After heating, dimerdiamine (768.2 g) was added dropwise, followed by imidization reaction at 140 ° C. for 1 hour to obtain a solution of polyimide resin. The molar ratio of acid component / amine component in the solution is 1.04.

Next, after cooling the resin solution to room temperature in another reaction vessel, the (a3-1) component (44.1 g) was added thereto, followed by deethanol reaction at 90 ° C. for 3 hours to form a methoxysilyl group-containing silane-modified polyimide resin ( A-3-2) was obtained. After the solution was cooled to room temperature, methanol (88.3 g) was added to obtain a solution of resin (36.5% nonvolatile content). The resin solution was further diluted with cyclohexanone to obtain a resin varnish (35.0% of nonvolatile matter). The said resin varnish was used as an adhesive composition.

&Lt; Example 16 >

After putting the solution (3610.0 g) and the component (a3-1) (228.0 g) of the (A-1-1) component obtained by the same method as the said Preparation Example 1 in the same reaction container as the said Preparation Example 1, at 90 degreeC The reaction was carried out for 3 hours to obtain a solution of the methoxysilyl group-containing silane-modified polyimide resin. The solution was cooled to room temperature, and methanol (456.0 g) was added to obtain a solution (non-volatile content 36.0%) of the methoxysilyl group-containing silane-modified polyimide resin (A-3-3). Furthermore, the said solution was further diluted with cyclohexanone and the resin varnish (35.0% of non volatile matter) was obtained. The said resin varnish was used as an adhesive composition as it was.

&Lt; Example 17 >

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (1484.0 g), and methylcyclohexane (296.8 g) were put into the same reaction container as the said preparation example 1, and the solution was heated to 60 degreeC. After heating, dimerdiamine (807.4 g) was added dropwise, followed by imidization reaction at 140 ° C. for 3 hours to obtain a solution of polyimide resin (42.0% of nonvolatile matter). The molar ratio of acid component / amine component in the solution was 1.10. Next, after cooling a polyimide resin solution to room temperature, 2, 2-bis [4- (4-amino phenoxy) phenyl] propane (brand name "BAPP", Wakayama Purification Co., Ltd. product; 40.9 g) is heated. Was slowly added in small portions to keep it below 40 ° C. After completion of the addition, the solution was subjected to a stretching reaction with stirring at room temperature for 30 minutes to obtain a solution of the polyimide resin. Next, the (a3-1) component (46.8 g) was added to the reaction vessel and reacted at 90 ° C. for 3 hours to prepare a solution of methoxysilyl group-containing silane-modified polyimide resin (A-4-1). Got it. After cooling the said solution to room temperature, methanol (93.5g) was added, and also diluted with cyclohexanone, and the resin varnish (35.0% of non volatile matter) was obtained. The said resin varnish was used as an adhesive composition as it was.

&Lt; Example 18 >

The solution (3610.0 g) of the component (A-1-1) obtained in the same manner as in Preparation Example 1 was placed in the same reaction vessel as in Preparation Example 1, followed by 4, 4'-diaminodiphenyl ether as a chain extender. (Trade name "DPE / ODA", Wakayama Purification Co., Ltd .; 9.2 g) was added little by little so that temperature may be maintained below 40 degreeC. After the addition was completed, the reaction was elongated with stirring at room temperature for 30 minutes to obtain a solution of polyimide resin. Next, the (a3-1) component (46.8 g) was added to the reaction vessel and reacted at 90 ° C. for 3 hours to prepare a solution of methoxysilyl group-containing silane-modified polyimide resin (A-4-2). Got it. Next, after cooling the said solution to room temperature, methanol (93.5g) was added, and also diluted with cyclohexanone, and the resin varnish (35.0% of non volatile matter) was obtained. The said resin varnish was used as an adhesive composition as it was.

&Lt; Example 19 >

In the same reaction vessel as Preparation Example 1, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (2120.0 g) and methylcyclohexane (424.0 g) were added thereto. The solution was then heated to 60 ° C. After heating, dimerdiamine (427.0 g) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd .; 695.9 g) were added dropwise thereto, and then 140 The imidation reaction was carried out at 1 ° C. for 1 hour to obtain a solution of polyimide resin. In the above solution, the dimerdiamine in the diamine component is 50 mol%, and the molar ratio of the acid component / amine component is 1.04. Next, after cooling the said polyimide resin solution to room temperature, the said (a3-1) component (47.0g) is put, and the solution of a methoxy silyl group containing silane modified polyimide resin (A-3-4) is added at 90 degreeC. Got it. After cooling the said solution to room temperature, methanol (113.0g) was added, and also diluted with cyclohexanone, and the resin varnish (35.0% of non volatile matter) was obtained. The said resin varnish was used as an adhesive composition as it was.

&Lt; Example 20 >

JER828 (1.8 g) and cyclohexanone (12.0 g) were added to the resin varnish ((A-3-1) component containing) obtained in the said Example 13, and the resin varnish (35.0% of non volatile matter) was obtained. The said resin varnish was used as an adhesive composition as it was.

&Lt; Comparative Example 4 &

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were put in the same reaction container as Preparation Example 1, and the solution was heated to 60 ° C. After heating, dropwise addition of α, ω-bis- (3 aminopropyl) polydimethylsiloxane (1391.7 g) in place of dimerdiamine, the solution was heated to 140 ℃ and imidized for 1 hour to a solution of polyimide resin Got. In addition, the molar ratio of the acid component / amine component in the solution of the said resin is 1.04. Next, after cooling the polyimide resin solution to room temperature, the (a3-1) component (66.1 g) was added and reacted at 90 ° C. for 3 hours, followed by cooling to room temperature to add methanol (132.1 g). The solution (45.0% of non volatile matter) of the methoxy silyl group containing silane modified polyimide resin (c) was obtained. The above solution was further diluted with cyclohexanone to obtain a resin varnish (35.0% of nonvolatile matter). The said resin varnish was used as an adhesive composition as it was.

&Lt; Comparative Example 5 &

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (2120.0 g) and methylcyclohexane (424.0 g) were added to the same reaction container as Preparation Example 1, and the solution was heated to 60 ° C. After heating, dimerdiamine (213.5 g) and α, ω-bis- (3 aminopropyl) polydimethylsiloxane (1043.8 g) were added dropwise thereto, and the solution was imidized at 140 ° C. for 1 hour to obtain polyimide resin. A solution was obtained. In the above solution, the dimer diamine in the diamine component is 25 mol%, and the molar ratio of the acid component / amine component is 1.04. Next, after the polyimide resin solution was cooled to room temperature, the (a3-1) component (56.5 g) was added thereto, reacted at 90 ° C. for 3 hours, and then cooled to room temperature to add methanol (113.0 g). And the solution (non-volatile content 40.0%) of the methoxy silyl group containing polyimide resin (d) were obtained. The above solution was further diluted with cyclohexanone to obtain a resin varnish (35.0% of nonvolatile matter). The said resin varnish was used as an adhesive composition as it was.

Poly
Imide
Suzy (a1)
(a2) polyimide component (a2)
Chain extension (a3) SiO ₂
wt%
Dimerdiamine Other dimerdiamine Example 14 (A-3-1) BTDA PRIAMINE --- --- (a3-1) 2 Example 15 (A-3-2) DSDA PRIAMINE --- --- (a3-1) 2 Example 16 (A-3-3) BTDA PRIAMINE --- --- (a3-1) 9 Example 17 (A-4-1) BTDA PRIAMINE --- BAPP (a3-1) 2 Example 18 (A-4-2) BTDA PRIAMINE --- DPE / ODA (a3-1) 2 Example 19 (A-3-4) BTDA PRIAMINE
(50 mol%) KF8010
(50 mol%) --- (a3-1) 2 Example 20 (A-3-1) BTDA PRIAMINE --- --- (a3-1) 2 Comparative Example 4 (All) BTDA --- KF8010 --- (a3-1) 2 Comparative Example 5 (la) BTDA PRIAMINE
(25 mol%) KF8010
(75mol%) --- (a3-1) 2

(※) Example 19 uses (B) component.

BTDA, PRIAMINE, DSDA, KF8010 and BAPP are shown in Table 1 above.

DPE / ODA (brand name): 4,4'-diaminophenyl ether (made by Wakayama purification)

SiO ₂ (%): Silica particle content rate (calculated from input weight)

<Production of adhesive sheet>

The adhesive composition of Example 1 was dried on a block copolymerized polyimide silica hybrid film (trade name "Pomiran N25", manufactured by Arakawa Chemical Industry Co., Ltd .; thermal expansion coefficient = 18 ppm, tensile modulus = 5.9 GPa, and film thickness of 25 µm). After apply | coating with a gap coater so that the thickness may be set to 30 micrometers, it dried at 180 degreeC for 3 minutes, and obtained the adhesive sheet. The adhesive sheet was obtained by the same method also about the adhesive composition of the said other Example and a comparative example. Next, the process surface of electrolytic copper foil (brand name "F2-WS", Furukawa Saku foil Co., Ltd .; 18 micrometers thickness) was superimposed on the adhesive surface of each adhesive sheet, and this was moved to the horizontal direction. At that time, the case where the electrolytic copper foil could not be moved due to adhesiveness was judged as "tack free" and the case where it could be moved in the horizontal direction was "tack free" and the above results are shown in Table 4 below. Indicated.

<Production of laminated body 1>

On the adhesive surface of the adhesive sheet produced in Example 1, the treated surface of the electrolytic copper foil (brand name "F2-WS", manufactured by Furukawa Sakku Co., Ltd .; 18 μm thickness) was piled up under pressure of 10 MPa, 180 ° C. and 1 minute. After heat-pressing on conditions, it heated again at 200 degreeC for 1 hour, and produced the laminated body (1). Each laminated body 1 was obtained by the same method also about the adhesive composition of the said other Example and a comparative example. In addition, the laminated body 1 assumes use as an FPC board | substrate.

<Production of laminated body 2>

The adhesive composition according to Example 1 was applied to a gap coater so as to have a thickness of 30 μm after drying on pomiran N25, and then heated at 200 ° C. for 30 minutes to obtain an adhesive sheet. Next, after laminating | stacking the process surface of the said electrolytic copper foil (F2-WS) on the adhesive surface of the said adhesive sheet, it heat-pressed for 1 minute on the conditions of 10 MPa and 200 degreeC, and produced the laminated body 2. Each laminated body 2 was obtained by the same method also about the adhesive composition of the said other Example and a comparative example. In addition, the laminated body 2 assumes use as a carrier sheet and a carrier tape.

<Adhesive test>

About each laminated body of the said Example and a comparative example, peeling strength was measured based on JISC-6481 standard. The measurement results are shown in Tables 4 and 5 below.

<Soldering heat resistance test: high temperature area>

After heating at 120 ° C. for 5 minutes for each of the laminates 1 of the above-described examples and comparative examples, the surface of the plastic substrate was raised upward, floated in a solder bath at 340 ° C. for 1 minute, and then the foaming of the adhesive layer and the peeling of the metal substrate were removed. It confirmed and the peeling strength of copper foil was measured based on JISC-6481 standard. The measurement results are shown in Tables 4 and 5. Further, since the layered product 1 is assumed to be used as an FPC board, the larger the value of the peel strength is, the better the adhesion is.

<Flammability>

About each of the laminated bodies 1 of the said Example and the comparative example, flame retardance was evaluated based on UL94 standard. The case where the laminated body 1 corresponded to the V94 class of UL94 standard was "flame retardant oil", and the case where it burned was "flame-free flameless".

<Soldering heat resistance: low temperature range>

After heating at 120 ° C. for 5 minutes for each of the laminates 2 of the Examples and Comparative Examples, the plastic substrate surface was lowered and floated in a solder bath at 260 ° C. for 5 minutes, followed by foaming of the adhesive layer or peeling off of the metal substrate. Was confirmed and the peeling strength of the electrolytic copper foil was measured based on JISC-6481 standard. At the time of a measurement, the surface state of the reflecting surface of an electrolytic copper foil was observed, and the presence or absence of the residue of the adhesive agent of the base material to measure was confirmed. The results are shown in Tables 4 and 5 below. In addition, since the laminated body 2 is assumed to be used as a carrier sheet or a carrier tape, it is necessary to peel electronic components, such as a temporarily fixed semiconductor element, and it is considered that the smaller the peel strength is, the better.

Silane
Undenatured
condition
Adhesive sheet
   Laminate (1)     Laminate (2) Early
Exfoliation
burglar
(N / cm) Solder heat resistance
After the test
(340 ℃ × 1min)
Flammability
Early
Exfoliation
burglar
(N / cm) Solder heat resistance
After the test
(260 ℃ × 5min) Tack Peel Strength (N / cm) Exterior Peel Strength (N / cm) Exterior Attach
Cured goods Example 1 radish 9 8 No change U 2 3 No change radish Example 2 radish 8 7 No change U 2 3 No change radish Example 3 radish 8 7 No change U 2 3 No change radish Example 4 radish 7 6 No change U 2 2 No change radish Example 5 radish 9 7 No change U 3 4 No change radish Example 6 radish 9 8 No change U 2 3 No change radish Example 7 radish 8 7 No change U 2 3 No change radish Example 8 radish 8 7 No change U 2 3 No change radish Example 9 radish 8 7 No change U 2 3 No change radish Example 10 radish 8 7 No change U 2 3 No change radish Example 11 radish 8 7 No change U 2 3 No change radish Example 12 radish 8 7 No change U 2 3 No change radish Example 13 radish 8 7 No change U 2 3 No change radish Comparative Example 1 U 7 6 No change U 4 6 No change U Comparative Example 2 U 8 6 No change U 4 6 No change U Comparative Example 3 U 9 3 firing U 4 6 No change U

Silane
Denaturation Adhesive sheet
   Laminate (1)     Laminate (2) Early
Exfoliation
burglar
(N / cm) Solder heat resistance
After the test
(340 ℃ × 1min)
Flammability
Early
Exfoliation
burglar
(N / cm) Solder heat resistance
After the test
(260 ℃ × 5min) Tack Peel Strength (N / cm) Exterior Peel Strength (N / cm) Exterior Attach
Cured goods Example 14 radish 9 6 No change radish 3 4 No change radish Example 15 radish 9 6 No change radish 3 4 No change radish Example 16 radish 8 7 No change radish 3 4 No change radish Example 17 radish 9 7 No change radish 3 4 No change radish Example 18 radish 9 7 No change radish 3 4 No change radish Example 19 radish 9 7 No change radish 3 4 No change radish Example 20 radish 9 7 No change radish 3 4 No change radish Comparative Example 4 U 8 7 No change radish 5 6 No change U Comparative Example 5 U 8 7 No change radish 5 6 No change U

<Production of flexible printed wiring board>

The adhesive composition which concerns on the said Example 1 was apply | coated to pomiran N25 so that the thickness after drying might be set to 30 micrometers, and it dried at 180 degreeC for 3 minutes, and obtained the adhesive sheet. The treated surface of the electrolytic copper foil (F2-WS) was superimposed on the adhesive face of the adhesive sheet and pressed with a laminate roll at 180 ° C., and then treated at 200 ° C. for 2 hours to obtain a flexible copper clad laminate. The copper surface of this copper clad laminated board was soft-etched and the copper circuit was formed, and the laminated body 1 using the adhesive composition of this invention concerning Example 1 obtained by the said method was piled up on it, and the pressure was 10 MPa, 180 degreeC, and After heat-pressing on the conditions of 1 minute, it heated again at 200 degreeC for 1 hour, and was able to manufacture the flexible printed wiring board. Moreover, the flexible printed wiring board was produced by the same method also about the adhesive composition of another Example.

Claims (22)

Polyimide obtained by dissolving at least one polyimide resin (A) selected from the group consisting of the following [1] to [4] and, if necessary, the thermosetting resin (B) and the flame retardant (C) in an organic solvent (D). Adhesive composition:
[1] polyimide resin obtained by reacting aromatic tetracarboxylic acids (a1) and diamines (a2) containing 30 mol% or more of dimerdiamine;
[2] a polyimide resin obtained by further chain-stretching a polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of dimerdiamine as the component (a2);
[3] polyimide resin obtained by reacting a polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of dimerdiamine and an epoxy group-containing alkoxysilane partial condensate (a3) ; And
[4] A polyimide resin and an epoxy group obtained by further chain-stretching a polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of dimerdiamine as the component (a2). Polyimide resin obtained by making containing alkoxysilane partial condensate (a3) react.
The method of claim 1,
The (a1) component is a polyimide adhesive composition, characterized in that represented by the following formula (1):
[Chemical Formula 1]

(In the formula 1,
X represents a single bond or at least one structure selected from the group represented by the following formula (2).)
(2)

.
3. The method according to claim 1 or 2,
The dimerdiamine is a polyimide adhesive composition, characterized in that represented by the following formula (3) or (4):
(3)

(In the formula (3), m + n = an integer of 6 to 17, p + q = an integer of 8 to 19, the broken line means a carbon-carbon single bond or a carbon-carbon double bond.)
[Chemical Formula 4]

(In the formula (4), m + n = an integer of 6 to 17, p + q = an integer of 8 to 19, the broken line means a carbon-carbon single bond or a carbon-carbon double bond).
4. The method according to any one of claims 1 to 3,
[The number of moles of use of (a1) component / the number of moles of use of (a2) component] are 0.6 / 1-1.4 / 1 with respect to the polyimide resin obtained by making the said (a1) component and (a2) component react. Polyimide adhesive composition.
5. The method according to any one of claims 1 to 4,
(A2) A component as said polyimide resin raw material contains diamino polysiloxane further, The polyimide adhesive composition characterized by the above-mentioned.
The method of claim 5,
The diamino polysiloxanes are polyimide adhesive composition, characterized in that represented by the following formula (5):
[Chemical Formula 5]

(In the above formula (5)
R ₁ represents an alkylene group having 2 to 6 carbon atoms, R ₂ represents an alkyl group having 1 to 4 carbon atoms, and r represents an integer of 1 to 30).
7. The method according to any one of claims 1 to 6,
(A2) A component as a chain extender is 1 or more types chosen from the group which consists of bisaminophenoxy phenyl propanes and dimer diamine, The polyimide adhesive composition characterized by the above-mentioned.
8. The method according to any one of claims 1 to 7,
[A mole number of the remaining carboxyl groups in the polyimide resin obtained by reacting the (a1) component and the (a2) component] / [the number of moles of the component (a2) as the chain extender] is 0.6. It is a range which becomes / 1-1.4 / 1, The polyimide adhesive composition characterized by the above-mentioned.
The method according to any one of claims 1 to 8,
The said (a3) component can obtain the alkoxysilane partial condensate and the de-alcohol reaction of the epoxy alcohol, The polyimide adhesive composition characterized by the above-mentioned.
10. The method of claim 9,
The alkoxysilane partial condensate is a polyimide adhesive composition of claim 9, characterized in that represented by the following formula (6):
[Chemical Formula 6]

(6)
R ₃ represents an alkyl group having 1 to 3 carbon atoms, R ₄ represents an alkyl group or an aryl group having 1 to 3 carbon atoms, and s represents an integer of 2 to 100).
The method according to claim 9, wherein
The epoxy alcohol is a polyimide adhesive composition, characterized in that represented by the following formula (7):
(7)

(In the formula (7), t represents an integer of 1 to 10).
12. The method according to any one of claims 9 to 11,
Polyis characterized in that the amount of the alkoxysilane partial condensate and the epoxy alcohol is in a range such that [the number of moles of alkoxy groups in the alkoxysilane partial condensate / the number of moles of hydroxyl groups in the epoxy alcohol] becomes 1 / 0.3 to 1 / 0.01. Mid type adhesive composition.
13. The method according to any one of claims 1 to 12,
Said (B) component is polyimide adhesive composition which is at least 1 sort (s) chosen from the group which consists of an epoxy resin, benzoxazine resin, bismaleimide resin, and a cyanatoester resin.
The method according to any one of claims 1 to 13,
The polyimide adhesive composition whose usage-amount of (B) component is 1-150 weight part with respect to 100 weight part (solid content conversion) of (A) component.
15. The method according to any one of claims 1 to 14,
Said (C) component is 1 or more types chosen from the group which consists of a phosphorus flame retardant and an inorganic filler, The polyimide adhesive composition characterized by the above-mentioned.
16. The method of claim 15,
The polyimide adhesive composition whose usage-amount of (C) component is 0.1-200 weight part with respect to 100 weight part (solid content conversion) of (A) component.
Hardened | cured material obtained by hardening | curing the polyimide adhesive composition of any one of Claims 1-16.
18. The method of claim 17,
And the content of the silica component is 0 to 15% by weight.
An adhesive sheet obtained by applying the polyimide adhesive composition of any one of claims 1 to 18 to a sheet base material and drying the same.
A laminate obtained by thermally compressing a sheet substrate in addition to the adhesive face of the adhesive sheet of claim 19.
A laminate obtained by further heating the laminate of claim 20.
The flexible printed circuit board obtained using the laminated body of Claim 21.