KR101472920B1 - Polyimide-based adhesive composition, cured product, adhesive sheet, laminate, and flexible printed circuit board - Google Patents

Abstract

[assignment]
The present invention provides a novel polyimide-based adhesive composition which can be used as a solution homogeneously dissolved in an organic solvent, excellent in heat-resistant adhesiveness, hard to leave residues of an adhesive, and low in tack in a cured state.
[Solution]
At least one polyimide resin (A) selected from the group consisting of the following [1] to [4] and a polyimide obtained by dissolving the thermosetting resin (B) and the flame retardant (C) Based adhesive composition:
[1] A polyimide resin obtained by reacting aromatic tetracarboxylic acids (a1) and diamines (a2) containing 30 mol% or more of dimer diamine;
[2] A polyimide resin obtained by further elongating a polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of a diamine diamine with the component (a2)
(3) a 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 a diamine diamine with an epoxy group-containing alkoxysilane partial condensate (a3) ; And
[4] A polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of a diamine diamine, with a polyimide resin obtained by further chain- Containing alkoxysilane partial condensate (a3).

Description

[0001] The present invention relates to a polyimide-based adhesive composition, a cured product, an adhesive sheet, a laminate, a flexible printed circuit board,

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

BACKGROUND ART Conventionally, aromatic polyimide resins excellent in heat resistance, flexibility, adhesion to circuit boards, and the like have been commonly used as adhesives for use in the production of printed circuit boards and build-up substrates used in electronic products and electronic devices. The aromatic polyimide resin is also commonly used as an adhesive composition for a carrier tape or sheet, which is a temporary fixing means for carrying an electronic component such as a semiconductor element, and thus a material that is indispensable for manufacturing electronic products and electronic devices .

However, a large number of aromatic polyimide resins are difficult to dissolve in an organic solvent, making it difficult to use them as varnish. Therefore, conventionally, a solution of the precursor (polyamic acid) was coated on a circuit substrate, and then a ring-closing reaction was carried out under heating to form a film of polyimide resin on the substrate. However, in this method, the substrate itself may be subjected to heat deterioration.

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

In Patent Document 2, oxydiphthalic acid anhydride (biphenyltetracarboxylic dianhydride), bisaminopropylpolydimethylsiloxane and bisaminophenoxybenzene are reacted at a predetermined ratio as an aromatic polyimide resin as an adhesive An aromatic polyimide siloxane having a glass transition temperature of 350 DEG C or less is obtained.

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.

Patent Document 4 discloses a carrier tape for TAB (Tape Automated Bonding) obtained by laminating a composition comprising an aromatic polyimide siloxane obtained by reacting biphenyltetracarboxylic acid, diaminopolysiloxane and aromatic diamine with an epoxy compound .

However, the adhesive composition using the known aromatic polyimide siloxane as described above is insufficient in adhesion to an inorganic substrate or an organic substrate at high temperatures (hereinafter, referred to as heat-resistant adhesiveness).

In addition, when the known aromatic polyimide siloxane is used as an adhesive layer of a carrier tape or sheet, there is a problem that residues of the adhesive tend to be generated. The residue of the above adhesive means that a part of the adhesive layer adheres to the surface of the component when the electronic component is peeled off from the adhesion surface of the carrier tape or sheet, and this leads to a deterioration in the product yield and productivity of the product.

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

(Patent Document 1) JP-A-4-36321 (Patent Document 2) JP-A-5-112760 (Patent Document 3) JP-A-8-253677 (Patent Document 4) JP-A-7-224259 (Patent Document 5) JP-A-2006-117899

It is an object of the present invention to provide a polyimide-based adhesive which can be used as a solution homogeneously dissolved in an organic solvent, has excellent heat-resistant adhesiveness and is difficult to leave residues of the adhesive, has a low tack in a cured state, To provide a composition.

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

Specifically, the present invention relates to a polyimide resin composition comprising at least one polyimide resin (A) selected from the group consisting of the following [1] to [4], and optionally a thermosetting resin (B) and a flame retardant (C) To provide a polyimide-based adhesive composition.

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

[2] A polyimide resin obtained by further elongating a polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of a diamine diamine with the component (a2)

(3) a 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 a diamine diamine with an epoxy group-containing alkoxysilane partial condensate (a3) ; And

[4] A polyimide resin obtained by reacting an aromatic tetracarboxylic acid (a1) and a diamine (a2) containing 30 mol% or more of a diamine diamine, with a polyimide resin obtained by further chain- Containing alkoxysilane partial condensate (a3).

The present invention also relates to a cured product obtainable by curing the adhesive composition and an adhesive sheet obtainable by applying the adhesive composition to a sheet substrate and drying the adhesive sheet, A laminate which can be obtained by heating the laminate again, and a flexible printed substrate obtained by using the laminate.

The adhesive composition according to the present invention can be used as a solution homogeneously dissolved in an organic solvent. In addition, it has excellent initial adhesion and heat-resistant adhesiveness to an inorganic substrate and an organic substrate. Furthermore, the cured product (adhesive layer) obtained with the above adhesive composition is a law tack, hard to foam when heated, and hard to leave a residue of the adhesive.

Furthermore, the adhesive composition according to the present invention can be used not only as an adhesive for use in the production of a printed circuit board (build-up substrate, flexible printed board, etc.) or a copper plate for a flexible printed board, but also as an adhesive for a carrier tape such as a TAB tape or a COF tape, , Semiconductor interlayer materials, and the like.

≪ Polyimide-based adhesive composition >

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

(A2) containing 30 mol% or more of an aromatic tetracarboxylic acid (a1) (hereinafter referred to as a component (a1)) and a dimer diamine (hereinafter referred to as a component (a2) (Hereinafter referred to as component (A-1));

[2] A polyimide resin (hereinafter referred to as component (A-2)) obtained by chain extruding component (A-1) with component (a2) again;

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

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

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

[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)

Examples of the compound represented by the formula (1) include 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3' Diphenyl ether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid anhydride, 1, Naphthalene tetracarboxylic acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic acid Acid dianhydride, 2,3,3 ', 4'-diphenylether tetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2-bis ( 3,3 ', 4,4'-tetracarboxyphenyl) tetrafluoropropane dianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-bis -Dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, cyclopentanetetracarboxylic acid anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,4-tricarboxycyclopentyl acetic anhydride, 4,4'-propane-2,2'-diyl bis (1,4-phenyleneoxy) diphthalic acid dianhydride and the like, .

The dimer diamine constituting the component (a2) is a compound derived from dimer acid, which is an aliphatic unsaturated fatty acid such as oleic acid, as described in JP-A-9-12712. In the present invention, a known diamine diamine can be used without particular limitation, but it is preferably represented by the following formula (3) or (4) as shown below.

(3)

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

[Chemical Formula 4]

Wherein m + n = an integer of 6 to 17 and p + q = an integer of 8 to 19, and the broken line represents a carbon-carbon single bond or a carbon-carbon double bond.

The dimer diamine is preferably a dimer diamine represented by the general formula (4) in view of solubility of an organic solvent, initial adhesive property, heat-resistant adhesive property, law tack property, Compounds and compounds represented by the following formula (5) are preferred.

[Chemical Formula 8]

Examples of commercial products of dimer diamine include BASAMAIN 551 (manufactured by BASF Japan), BASAMAIN 552 (water additive of Vasamin 551, manufactured by Cognix Zaphen Co.), PRIAMINE 1075, PRIAMINE 1074 (manufactured by Kuroda Japan Co., And the like.

The content of dimer diamine in the component (a2) is generally 30 (mol%) based on 100 mol% of the total of the component (a2) from the viewpoints of heat resistant adhesiveness, law tack resistance, Mol% or more, preferably 45 to 100 mol%. The component (a2) may contain other diamines, if necessary, generally in an amount of less than 70 mol%, preferably 0 to 55 mol%.

As the other diamines, various known diamines can be used without any particular limitation. Specifically, for example, diaminopolysiloxane can be used, and among them, a compound represented 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).

Examples of the diaminopolysiloxane represented by the formula (5) include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω- Bis [3- (2-aminophenyl) propyl] polydimethylsiloxane, [alpha], [omega] -trimethoxysilane, Bis [3- (4-aminophenyl) propyl] polydimethylsiloxane, and the like, and they may be used in combination of two or more species from the above-mentioned groups.

Examples of other diamines include 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- And the like; Diaminodiphenyl ethers such as 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether; phenylenediamines such as p -phenylenediamine and m -phenylenediamine; Diaminodiphenyl sulfides such as 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide and 4,4'-diaminodiphenylsulfide; Diaminodiphenylsulfones such as 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone and 4,4'-diaminodiphenylsulfone; Diaminobenzophenones 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; Diaminophenylpropane such as 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane and 2- (3-aminophenyl) -2- Ryu; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) Diaminophenylhexafluoropropanes such as 3-hexafluoropropane and 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane; Di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- ) -1-phenylethane; Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, Bisaminophenoxybenzenes such as benzophenone and aminophenoxy) benzene; Benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, Bisaminobenzoylbenzenes such as benzene; Benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, bis (4-amino-α, α-dimethylbenzyl) benzene, and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene; Benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3- Bisaminoditrifluoromethylbenzylbenzenes such as 3-amino-?,? - ditrifluoromethylbenzyl) benzene, and 1,4-bis (4-amino-?,? - trifluoromethylbenzyl) benzene; Bis (3-aminophenoxy) benzene, 2,6-bis (3-aminophenoxy) pyridine, 4,4'- (4-aminophenoxy) biphenyl; Aminophenoxyphenyl ketones such as bis [4- (3-aminophenoxy) 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; Aminophenoxyphenyl ethers such as bis [4- (3-aminophenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether; 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; Benzoyl] benzene, 1,4-bis [4- (3-amino-benzoyl) Benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) , 1,3-bis [4- (4-aminophenoxy) -?,? - dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) , 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-aminophenoxy) Bis [4- (4-amino- alpha, alpha -dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- Phenylsulfone, 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3'-diamino-4,4'-diphenoxybenzophenone, Diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'- Bis (3-aminophenoxy) 3,3,3 ', 3'-te 3,3,3 ', 3'-tetramethyl-1,1'-spirobIndane, 1,3,6-bis (4-aminophenoxy) Bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) tetramethyldisiloxane, Bis (2-aminomethoxy) ethyl] ether, bis [2- (3-aminopropyl) ethyl] ether, (Aminomethoxy) ethane, 1,2-bis [2- (2-aminoethoxy) ethane, Ethoxy) ethane, ethylene glycol-bis (3-aminopropyl) ether, diethylene glycol-bis (3-aminopropyl) ether, triethylene glycol- 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diamine (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,3-diaminocyclohexane, Bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) aminocarbonyl group, ) Bicyclo [2.2.1] heptane, and 1,3-bis (aminomethyl) cyclohexane.

Further, the component (A-1) can be produced by various known methods. For example, the component (a1) and the component (a2) are first heated at a temperature of generally 60 to 120 ° C, preferably 80 to 100 ° C, for about 0.1 to 2 hours, preferably 0.1 to 0.5 hours Addition reaction is carried out. The adduct thus obtained is subjected to imidization reaction, that is, dehydration cyclization reaction at a temperature of about 80 to 250 ° C, preferably 100 to 200 ° C, for about 0.5 to 50 hours, preferably for 1 to 20 hours (A-1) can be obtained.

In the imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents described below can be used. As the reaction catalyst, aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as methyl aniline, and heterocyclic tertiary amines such as pyridine, picoline, isoquinoline and the like can be used. As the dehydrating agent, an aliphatic acid anhydride such as acetic anhydride or an aromatic acid anhydride such as an anhydrous benzoic acid can be used.

The imide termination rate of the component (A-1) is not particularly limited, but is generally 70% or more, preferably 85 to 100%. Refers to the content of the ring (cyclic) imide bond in the component (A-1), and can be determined by various spectroscopic means such as NMR or IR analysis. Further, by setting the imide waste rate of the component (A-1) to 70% or more, the initial adhesive property and the heat-resistant adhesive property of the adhesive composition of the present invention are further improved, and the imidation reaction The foaming due to the moisture generated becomes difficult to occur.

The use amount of the component (a1) and the component (a2) is not particularly limited, but from the viewpoints of solubility in the component (D) of the component (A-1), initial adhesion property, The number of moles used / the number of moles of the component (a2)] is generally about 0.6 / 1 to 1.4 / 1, preferably 0.8 / 1 to 1.2 / 1.

The component (A-2) is a polyimide resin obtained by chain extending the component (A-1) obtained by the above method to the component (a2).

The reaction conditions of the component (A-1) and the component (a2) are not particularly limited. In general, the reaction temperature is 60 ° C or less, preferably 50 ° C or less, the reaction time is 1 to 6 hours, Is subjected to addition reaction for 1 to 3 hours. In the reaction, an organic solvent described below may be used.

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

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

The component (A-3) is a polyimide resin containing an alkoxysilyl group in the molecule obtained by reacting the component (A-1) and the component (a3) and is a self-crosslinkable resin, It is possible to obtain an adhesive cured product excellent in heat-resistant adhesiveness.

The component (a3) is a high molecular weight compound having a siloxane bond as a continuous unit and having a silicon atom bonded to an alkyl group and an alkoxy group in a molecular chain and having an epoxy group at the molecular end, and is obtained by removing various known alkoxysilane partial condensates and an epoxy alcohol Alcohol reaction (hydrolysis reaction).

The alkoxysilane partial condensate component is characterized by being represented by the following formula (6)

[Chemical Formula 6]

(6)

R ₃ represents an alkyl group having 1 to 3 carbon atoms, and R ₄ represents an alkyl group or an aryl group having 1 to 3 carbon atoms. S is an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 8).

The epoxy alcohol is characterized by being represented by the following formula (7)

(7)

(In the formula (7), t is an integer of 1 to 10, preferably an integer of 1 to 8).

The above alcohol elimination reaction can be carried out according to various known methods. Concretely, for example, it is preferable to react the partial condensate of alkoxysilane and the epoxy alcohol while removing the alcohol generated by heating under the condition of about 50 to 150 ° C, preferably 70 to 110 ° C.

The amount of the alkoxysilane partial condensate and the epoxy alcohol to be used is not particularly limited, but is generally in the range of [number of moles of the alkoxy group in the alkoxysilane partial condensate] / hydroxyl group in the epoxy alcohol Is generally in the range of about 1 / 0.3 to 1 / 0.01.

Further, in the dealcoholization reaction, the component (D) described below or various known catalysts may 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; An oxide, an organic acid salt, a halide, an alkoxide, and the like containing the above-mentioned metals.

The reaction between the component (A-1) and the component (a3) is a so-called ring-opening esterification reaction. The reaction conditions are not particularly limited, but the reaction temperature is generally about 40 to 130 DEG C, preferably 70 to 110 DEG C, and the reaction time is generally about 1 to 7 hours.

In the ring-opening esterification reaction, various known catalysts such as 1,8-diazabicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol , Tris (dimethylaminomethyl) phenol and the like; amines such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4 -Methylimidazole-tetraphenylborate, and tetramhenylboron salts such as N-methylmorpholine-tetraphenylborate. The amount to be used is not particularly limited, but is generally about 0.15 parts by weight based on 100 parts by weight (in terms of solid content) of the target component (A-3).

In the ring-opening esterification reaction, the component (D) described below can be used, and an aliphatic solvent such as cyclohexanone is particularly preferable. Further, by adding various known low-molecular alcohols such as methanol, ethanol, propanol and the like, the viscosity stability of the solution of the component (A-3) and the solution of the component (A-4) described later is improved.

The component (A-4) is a polyimide resin containing an alkoxysilyl group in the molecule obtained by reacting the component (A-2) and the component (a3) It is possible to obtain an adhesive cured product excellent in heat-resistant adhesiveness without using the component (B) described 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 the component (A-3) and the component (A-4), and this portion serves as a reaction point of the sol-gel reaction described below. The residual amount of the alkoxysilyl group is not particularly limited, but it is generally 60% or more, preferably 80% or more, of the respective alkoxysilyl groups in the component (A-3) and the component (A-4).

Component (B) is a curing agent of the polyimide-based adhesive composition of the present invention, and various known ones can be used without any particular limitation. Specifically, for example, at least one kind selected from the group consisting of epoxy resin, benzoxazine resin, bismaleimide resin and cyanate ester resin is preferable.

Examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy A hydrogenated bisphenol F type epoxy resin, a stilbene type epoxy resin, a triazine skeleton containing epoxy resin, a fluorene skeleton containing epoxy resin, a linear aliphatic epoxy resin, an alicyclic epoxy resin, a glycidylamine type epoxy resin, a triphenol phenol Methane type epoxy resin, alkyl modified triphenolmethane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene skeleton containing epoxy resin, naphthalene skeleton containing epoxy resin, aryl alkylene type epoxy resin, A modified epoxy resin obtained by modification, dimer acid diglycidyl ester, and the like 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. Examples of commercially available products include "jER828" and "jER834" manufactured by Mitsubishi Chemical Corporation, "ST-3000" manufactured by Shin-Tetsu Chemical Co., Ltd., "jER807" YD-172-X75 " of Shin-Nittsu Chemical Co., Ltd., and the like, and combinations of two or more of them may be combined.

When an epoxy resin is used as the thermosetting resin, various known curing agents for epoxy resins can be used in combination. Specifically, there may be mentioned, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride , Or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornene- Norbornene-2,3-dicarboxylic anhydride, methylnorbornene-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-norbornene-2,3-dicarboxylic anhydride, - acid anhydride-based curing agents such as dodecenyl chrysin acid and octenylsuccinic acid anhydride; Amine curing agents such as dicyandiamide, cyanoguanidine (DICY), aliphatic diamines (trade names: LonazcureM-DEA, Lonzacure M-DETDA and the like; (Phenol novolak resin, cresol novolac resin, bisphenol A type novolac resin, triazine-modified phenol novolac resin, phenol hydroxyl group-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Curing agents, and cyclic phosphazene-based compounds. Among them, a phenol-based curing agent, particularly a phenazine-based hydroxyl group-containing curing agent, is preferable because it gives flame retardancy to the cured product and the laminate according to the present invention. The amount of the curing agent to be used is not particularly limited, but when the solid content of the adhesive composition of the present invention is 100 wt%, the amount of the curing agent used is about 0.01 to 5 wt%.

Further, as a catalyst for promoting the reaction between the epoxy resin and the curing agent as described above, for example, 1,8-diazabicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine , Tertiary amines such as triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; aliphatic amines such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as imidazoles, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine, tetraphenylphosphonium tetraphenylborate, 2- Ethyl-4-methylimidazole, tetraphenylborate, N-methylmorpholine, tetraphenylborate and the like, and combinations of at least two of these groups have.

Further, although the amount of the catalyst is not particularly limited, the amount of the catalyst used is generally about 0.01 to 5% by weight based on 100% by weight of the solid content of the adhesive composition of the present invention.

Examples of the benzoxazine resin include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6 , 6- (1-methylethylidene) bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine). It is also preferable that a phenyl group, a methyl group, a cyclohexyl group and the like are bonded to the nitrogen of the oxazine ring. Further, commercially available products include, for example, " benzooxazine type Fa type " or " benzoxazine type Pd type " manufactured by Shikoku Chemical Industry Co., Ltd., and " RLV- Two or more species can be used in combination.

Examples of the bismaleimide resin include 4,4'-diphenylmethane bismaleimide, m -phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5 , 5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4- ) Hexane, 4,4'-diphenyl ether bismaleimide, and 4,4'-diphenyl sulfone bismaleimide. Examples of commercially available products include "BAF-BMI" manufactured by JFE Chemical Co., Ltd. and the like. Further, at least two kinds or more of the above-mentioned bismaleimide resins may be used in combination.

Examples of the cyanate ester resin include 2-arylphenol cyanatoester, 4-methoxyphenol cyanate ester, 2,2-bis (4-cyanatophenyl) -1,1 , 1,3,3,3-hexafluoropropane, bisphenol A cyanate ester, diaryl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanate Bis (4-cyanatophenyl) ethane, 4,4'-bisphenol cyanate ester, 2,2-bis (4-cyanate Tolyl) propane and the like. Commercially available products include, for example, " PRIMASET BTP-6020S " (manufactured by Lonza Japan K.K.). These may be used in combination of two or more. 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.

The component (C) may be any known flame retardant that can be used in the polyimide-based adhesive composition without any particular limitation, but a phosphorus-based flame retardant and / or an inorganic filler is particularly preferable for the flame retardant effect.

Examples of the phosphorus-based flame retardant include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives that do not contain a phenolic hydroxyl group. Particularly, the phosphorus- Of the derivatives, cyclic phosphazene derivatives ("Rabitol FP300" manufactured by Fushimi Chemical Co., Ltd.) are preferred because of their flame retardancy, heat resistance and plate-out resistance.

The inorganic filler includes, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum borate whisker, Boron, crystalline silica, amorphous silica, graphite powder, boehmite, and the like. Of these, aluminum hydroxide (boehmite) is particularly preferred because of its excellent dispersibility and flame retardancy in the adhesive composition of the present invention.

The amount of the component (C) to be used is not particularly limited, but is generally about 0 to 200 parts by weight, preferably about 25 to 150 parts by weight, per 100 parts by weight (in terms of solid content) of the component (A).

Examples of the component (D) include non-proton such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyltriglyme, A polar solvent; Alicyclic solvents such as cyclohexanone and methylcyclohexane; Alcohols such as methanol, ethanol, propanol, benzyl alcohol, and cresol may be used. At least two kinds of solvents may be used in combination.

The amount of the component (D) to be used is not particularly limited, but it is generally preferable to use the adhesive composition in a range where the nonvolatile content of the adhesive composition of the present invention is about 20 to 60% by weight.

In addition to the adhesive composition of the present invention, if necessary, the above-mentioned ring-opening esterification catalyst, dehydrating agent, plasticizer, lubricant, antistatic agent, bleaching agent, colorant, And the like can be used in combination.

<Hard goods>

The cured product of the present invention is obtained by curing the adhesive composition of the present invention. Specifically, first, the adhesive composition is heated to about 70 to 200 ° C and cured for 1 to 10 minutes (Step 1); Next, in order to advance the curing reaction with the component (B) (the thermosetting resin), heating is again carried out generally at about 150 to 250 ° C for about 10 minutes to 3 hours (step 2) The shrinkage of the cured product can be made gentle so that the adhesion to the substrate can be ensured and foaming due to the water produced incidentally due to the dehydration ring-closing reaction can be suppressed. Furthermore, the curing reaction includes a dehydration ring closure reaction of a polyamic acid derived from the component (A) and a sol-gel reaction of an alkoxysilyl group derived from the component (a3).

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. The adhesive composition using the component (A-3) and the component (A-4) can be obtained by suitably adjusting the fluidity when the adhesive composition is heated and cured In order to improve the adhesion between the cured product and the substrate, the content of the silica (SiO ₂ ) particles is generally in the range of about 0.5 to 15%, preferably 1 to 10%. The above content is a calculated value calculated from the input amount of raw material.

The shape of the cured product of the present invention is not particularly limited, but when it is provided for the application of a substrate sheet, the thickness of the film is generally about 1 to 100 μm, preferably about 3 to 50 μm, and can be appropriately adjusted according to the application.

The adhesive sheet of the present invention can be obtained by applying the adhesive composition of the present invention to a sheet substrate and drying. Examples of the sheet base material include polyimide, polyimide silica hybrid, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethylmethacrylate resin PMMA), polystyrene resin (PSt), polycarbonate resin (PC), acrylonitrile butadiene styrene resin (ABS), ethylene terephthalate; And organic substrates such as aromatic polyester resins (so-called liquid crystal polymers; available from Kuraray Co., Ltd., &quot; Beckstar &quot;, etc.) obtained from parahydroxybenzoic acid such as phenol, phthalic acid and hydroxynaphthoic acid. Among them, a polyimide film, particularly a polyimide silica hybrid film, is preferable in terms of heat resistance and dimensional stability. The thickness of the sheet base material is preferably set appropriately in accordance with the use. Furthermore, the adhesive sheet can be used as a carrier sheet or a carrier tape.

The laminate of the present invention can be obtained by thermocompression bonding another sheet base material to the adhesive surface of the adhesive sheet. As the sheet substrate, an inorganic substrate such as glass, iron, aluminum, 42 alloy or copper, or ITO, silicon and silicon carbide is suitable, and the thickness can be suitably set according to the use. Further, it is preferable that the laminate is further subjected to heat treatment.

The flexible printed 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 the flexible printed board, it is preferable to use a polyimide sheet base as an organic base and a metal foil (in particular, a copper foil) as an inorganic base. In addition, a flexible printed wiring board can be obtained by soft etching the metal surface of the flexible printed circuit board to form a circuit, pasting the adhesive sheet on the circuit again, and thermocompression bonding.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the scope of the present invention is not limited by the following examples and production examples. In the examples, parts and percentages are by weight unless otherwise specified.

&Lt; Preparation of polyimide resin-based adhesive composition of silane-modified type &

&Lt; Preparation Example 1 &

3,3 ', 4,4'-benzophenonetetracarboxylic acid anhydride (trade name: "BTDA", manufactured by Daicel Chemical Industries, Ltd., hereinafter referred to as "a") was charged in a reaction vessel equipped with a stirrer, a separator, a thermometer and a nitrogen gas- (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were added to the solution, and the solution was heated to 60 占 폚. After heating, 85.04 g of dimer diamine (trade name: PRIAMINE 1075, manufactured by Kuroda Denko KK; hereinafter, simply referred to as dimer diamine) was added dropwise, and the mixture was heated to 140 ° C and imidized for 1 hour To obtain a solution (non-volatile matter content of 38.0%) of the polyimide resin (A-1-1). The molar ratio of the acid component / amine component in the solution is 1.04.

&Lt; Preparation Example 2 &

In the same reaction vessel as in Production Example 1, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "Recasit DSDA" (53.50 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were placed in a flask, and the solution was heated to 60 占 폚. Next, dimer diamine (76.82 g) was added dropwise, and the mixture was heated to 140 占 폚 and imidized for 1 hour to obtain a solution (nonvolatile matter content: 36.0%) of the polyimide resin (A-1-2). The molar ratio of the acid component / amine component in the solution is 1.04.

&Lt; Preparation Example 3 &

Benzophenonetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 占 폚. After heating, dimer diamine (85.40 g) was added dropwise, and the mixture was heated to 140 占 폚 and imidized for 1 hour to obtain a polyimide resin solution (nonvolatile content: 37.0%). The molar ratio of the acid component / amine component in the solution is 1.04. After the solution of the polyimide resin was cooled to room temperature, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (trade name "BAPP", manufactured by Wakayama Chemical Industry Co., g) was slowly added in small amounts so that the temperature was maintained at 40 占 폚 or lower. After completion of the addition, the solution was subjected to a chain extension reaction with stirring at room temperature for 30 minutes to obtain a solution (non-volatile matter content of 38.0%) of the polyimide resin (A-2-1).

&Lt; Preparation Example 4 &

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (212.00 g) and methylcyclohexane (42.40 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 占 폚. After heating, dimer diamine (42.70 g) and?,? - bis- (3 aminopropyl) polydimethylsiloxane (trade name "KF8010", Shin-Etsu Chemical Co., hereinafter simply referred to as bisaminopropylpolydimethylsiloxane) (69.59 g) was added dropwise, and the mixture was heated to 140 占 폚 and imidized for 1 hour to obtain a polyimide resin (A-1-3) solution (nonvolatile matter content 39.0%). In this solution, the diamine component of the diamine component is 50 mol%, and the molar ratio of the acid component / amine component is 1.04.

&Lt; Production Example 5 &

Benzophenonetracarboxylic dianhydride (53.00 g), cyclohexanone (159.00 g) and methylcyclohexane (31.80 g) were placed in the same reaction vessel as that of Production Example 1, and the solution was heated to 60 占 폚. After heating, dimer diamine (80.74 g) was added dropwise, and the mixture was heated to 140 占 폚 and imidized for 1 hour to obtain a solution of polyimide resin. In this solution, the molar ratio of acid component / amine component is 1.10. After the polyimide resin solution was cooled to room temperature, dimer diamine (6.73 g) was slowly added as a chain extender in small portions and elongation reaction was performed at room temperature for 1 hour with stirring to obtain a polyimide resin (A-2-2) To obtain a solution (nonvolatile matter content 42.0%).

&Lt; Production Example 6 &

(Propylene-2,2'-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydride (trade name: "BisDA2000", manufactured by SABIC Innovative Plastics Japan Co., (70.00 g), cyclohexanone (175.00 g) and methylcyclohexane (35.00 g) were placed in a flask, and the solution was heated to 60 ° C . After heating, dimer diamine (69.90 g) was added dropwise, and the mixture was heated to 140 占 폚 and imidized for 1 hour to obtain a solution (nonvolatile matter content: 40.5%) of polyimide resin (A-1-4). The molar ratio of the acid component / amine component in the solution is 1.04.

&Lt; Production Example 7 >

Oxydiphthalic anhydride (trade name: ODPA-1000, manufactured by SABIC Innovative Plastics Japan Ltd.) (hereinafter, simply referred to as oxydiphthalic anhydride) (50.00 g ), Cyclohexanone (226.50 g) and methylcyclohexane (25.00 g), and the solution was heated to 60 &lt; 0 &gt; C. After heating, dimer diamine (84.56 g) was added dropwise, and the mixture was heated to 140 占 폚 and imidized for 1 hour to obtain a solution (nonvolatile matter content: 35.0%) of the polyimide resin (A-1-5). The molar ratio of the acid component / amine component in the solution is 1.03.

&Lt; Production Example 8 &

Dihebisphenylenoxydiphthalic dianhydride (65.00 g), cyclohexanone (266.50 g) and methylcyclohexane (44.42 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 ° C. After heating, dimer diamine (43.71 g), 1,3-bis (aminomethyl) cyclohexane (trade name: 1,3-BAC, manufactured by Mitsubishi Gas Chemical Company) (5.42 g) was slowly added, And imidization reaction was carried out for 1 hour to obtain a solution (non-volatile matter content of 29.5%) of the polyimide resin (A-1-6). The molar ratio of the acid component / amine component in the solution is 1.05.

< Comparative Production Example 1>

Benzophenonetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 占 폚. After heating, bisaminopropyl polydimethylsiloxane (139.17 g) was added dropwise in place of dimer diamine, the solution was heated to 140 占 폚 and imidized for 1 hour to obtain a solution of polyimide resin (a) 46.2%). The molar ratio of the acid component / amine component in the solution is 1.04.

<Comparative Production Example 2>

Benzophenonetracarboxylic dianhydride (53.00 g), cyclohexanone (212.00 g) and methylcyclohexane (42.40 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 占 폚. After heating, dimer diamine (21.35 g) and bisaminopropylpolydimethylsiloxane (104.38 g) were added dropwise and then imidized for 1 hour to obtain a solution (nonvolatile matter content of 41.0%) of the polyimide resin . The molar ratio of the acid component / amine component in the solution is 1.04.

Polyimide resin (a1) (a2) (polyimide component) (a2)
(Chain elongation agent) Dimer diamine Other diamines 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 acid dianhydride

DSDA: 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride

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

PRIAMINE: Dimer Diamine

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 >

(100.0 g) of the polyimide resin (A-1-1) of Production Example 1 as the component (A), a bisphenol A type epoxy resin (trade name &quot; jER828 &quot;, epoxy equivalent 190 g / (Trade name: Tamanol T759, hydroxyl group equivalent: 106 g / eq; Arakawa Chemical Industries, Ltd.: 2.18 g) and 2-ethyl-4-methyl (Trade name &quot; 2E4MZ &quot;, manufactured by Shikoku Chemical Industry Co., Ltd., 0.06 g) were mixed. Next, as a component (C), boehmite (trade name "Seraculse BMT-3LV", Kawai Lime Industry Co., Ltd., 25.66 g), cyclic cyanophenoxyphosphazene derivative (trade name " 12.00 g), cyclohexanone (49.33 g) and methanol (8.55 g) as an organic solvent were added and stirred to obtain an adhesive composition (nonvolatile matter content: 40.7%).

&Lt; Examples 2 to 13 >

Each of the adhesive compositions was obtained in the same manner as in Example 1 except that the component (A), the component (B), the component (C) and the organic solvent were used in the respective amounts shown in Table 2 below.

&Lt; Comparative Examples 1 and 2 &

The solution of the component (A) or the solution of the component (B) was used in the amount shown in the following Table 2 instead of the solution of the component (A-1-1) used in Example 1, , The component (C), and the organic solvent were used in the same manner as in Example 1, except that each of the components shown in Table 2 was used in the amounts shown below.

&Lt; Comparative Example 3 &

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

jER828 (trade name): Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 190 g / eq)

Tamanol T759 (trade name): phenol novolak resin (manufactured by Arakawa Chemical Industries, Ltd., hydroxyl equivalent weight: 106 g / eq)

2E4MZ (trade name): 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)

BMI-TMH (trade name): 1,6'-bismaleimide (2,2,4-trimethyl) hexane (manufactured by Daika Chemical Industry Co., Ltd.)

Park Mill D (trade name): Dicumyl peroxide (manufactured by Iyu Corporation)

PRIMASET BTP-6020S (trade name): cyanate ester resin (manufactured by RONDER Japan)

Cerasule BMT-3LV (trade name): boehmite (manufactured by Kawai Lime Industry Co., Ltd.)

Rabitol FP-300: Phenoxyphosphazene derivative (manufactured by Fushimi Pharmaceutical Co., Ltd.)

<Preparation of silane-modified polyimide resin-based adhesive composition>

&Lt; Synthesis of component (a3) &gt;

(Trade name &quot; Epiol OH &quot;, manufactured by Nippon Oil & Fats Co., Ltd.) (1400 g) and a tetramethoxysilane partial condensate (trade name: &quot; methyl silicate (Dibutyltin dilaurate, 2.0 g) was added to the solution, and the solution was subjected to a hydrolysis reaction . The methanol additionally generated during the reaction was removed with a fractionizer and cooled to room temperature for 5 hours when the amount of methanol reached about 630 g. Next, the methanol remaining in the reaction system was removed under reduced pressure at 13 kPa for about 10 minutes to obtain a partial condensation product of a methoxysilane (a3-1) containing an epoxy group.

&Lt; Example 14 >

Benzophenonetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g), and methylcyclohexane (37.10 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 ° C . After heating, dimer diamine (85.40 g) was added dropwise, and imidization reaction was conducted at 140 캜 for 1 hour to obtain a solution of polyimide resin. The molar ratio of the acid component / amine component in the solution is 1.04.

After the polyimide resin solution was cooled to room temperature, the above-mentioned (a3-1) component (47.0 g) was added and the mixture was reacted at 90 ° C for 3 hours to give a methoxysilyl group-containing silane-modified polyimide resin (A- 1) was obtained. Next, after the solution was cooled to room temperature, methanol (93.9 g) was added to obtain a resin solution (nonvolatile matter content: 38.0%). Further, the above resin solution was further diluted with cyclohexanone to obtain a resin varnish (nonvolatile matter content 35.0%). The resin varnish was used as it was as an adhesive composition.

&Lt; Example 15 >

Diphenylsulfonetetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 ° C . After heating, dimer diamine (768.2 g) was added dropwise and then imidized at 140 ° C for 1 hour to obtain a solution of polyimide resin. The molar ratio of the acid component / amine component in the solution is 1.04.

Next, after the resin solution was cooled to room temperature in another reaction vessel, the above-mentioned (a3-1) component (44.1 g) was added, and the resulting solution was reacted at 90 DEG C for 3 hours to give a methoxysilyl group-containing silane modified polyimide resin A-3-2). After the solution was cooled to room temperature, methanol (88.3 g) was added to obtain a resin solution (nonvolatile matter content 36.5%). The resin solution was further diluted with cyclohexanone to obtain a resin varnish (nonvolatile content 35.0%). The resin varnish was used as an adhesive composition.

&Lt; Example 16 >

A solution (3610.0 g) of the component (A-1-1) and the component (a3-1) (228.0 g) obtained in the same manner as in Preparation Example 1 were charged in the same reaction vessel as in the above-mentioned Production Example 1, And reacted for 3 hours to obtain a solution of a siloxane-modified polyimide resin having a methoxysilyl group. The solution was cooled to room temperature, and methanol (456.0 g) was added to obtain a solution (nonvolatile content: 36.0%) of the methoxysilyl group-containing silane-modified polyimide resin (A-3-3). Further, the solution was further diluted with cyclohexanone to obtain a resin varnish (nonvolatile content 35.0%). The resin varnish was used as it was as an adhesive composition.

&Lt; Example 17 >

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (1484.0 g) and methylcyclohexane (296.8 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 占 폚. After heating, dimer diamine (807.4 g) was added dropwise and then subjected to imidization reaction at 140 占 폚 for 3 hours to obtain a polyimide resin solution (nonvolatile matter content: 42.0%). The molar ratio of the acid component / amine component in the solution was 1.10. Next, after the polyimide resin solution was cooled to room temperature, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (trade name "BAPP", 40.9 g, manufactured by Wakayama Chemical Industry Co., Lt; RTI ID = 0.0 &gt; 40 C &lt; / RTI &gt; 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 above-mentioned (a3-1) component (46.8 g) was added to the above reaction vessel and the reaction was conducted at 90 占 폚 for 3 hours to obtain a solution of the methoxysilyl group-containing silane modified polyimide resin (A- . After the solution was cooled to room temperature, methanol (93.5 g) was added and further diluted with cyclohexanone to obtain a resin varnish (nonvolatile content 35.0%). The resin varnish was used as it was as an adhesive composition.

&Lt; Example 18 >

A 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 that of Production Example 1, and then 4,4'-diaminodiphenyl ether (Trade name &quot; DPE / ODA &quot;, Wakayama Chemical Industry Co., Ltd., 9.2 g) was added in small amounts so that the temperature was maintained at 40 캜 or lower. After completion of the addition, the mixture was subjected to a stretching reaction with stirring at room temperature for 30 minutes to obtain a solution of the polyimide resin. Next, the above-mentioned (a3-1) component (46.8 g) was added to the above reaction vessel and the reaction was conducted at 90 占 폚 for 3 hours to obtain a solution of the methoxysilyl group-containing silane modified polyimide resin (A- . Next, after the solution was cooled to room temperature, methanol (93.5 g) was added and further diluted with cyclohexanone to obtain a resin varnish (nonvolatile content 35.0%). The resin varnish was used as it was as an adhesive composition.

&Lt; Example 19 >

3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (2120.0 g) and methylcyclohexane (424.0 g) were placed in the same reaction vessel as in Production Example 1 The solution was then heated to 60 &lt; 0 &gt; C. Dimer diamine (427.0 g) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (trade name "KF-8010", manufactured by Shinetsu Kagaku Kogyo Co., Ltd., 695.9 g) Deg.] C for 1 hour to obtain a polyimide resin solution. In this solution, the diamine component of the diamine component is 50 mol%, and the molar ratio of the acid component / amine component is 1.04. Next, the polyimide resin solution was cooled to room temperature, then the component (a3-1) (47.0 g) was added, and a solution of the methoxysilyl group-containing silane modified polyimide resin (A-3-4) . After the solution was cooled to room temperature, methanol (113.0 g) was added and further diluted with cyclohexanone to obtain a resin varnish (nonvolatile content 35.0%). The resin varnish was used as it was as an adhesive composition.

&Lt; Example 20 >

JER 828 (1.8 g) and cyclohexanone (12.0 g) were added to the resin varnish (containing component (A-3-1)) obtained in Example 13 to obtain a resin varnish (nonvolatile content 35.0%). The resin varnish was used as it was as an adhesive composition.

&Lt; Comparative Example 4 &

Benzophenonetracarboxylic dianhydride (53.00 g), cyclohexanone (185.50 g) and methylcyclohexane (37.10 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 占 폚. After heating, α, ω-bis- (3 aminopropyl) polydimethylsiloxane (1391.7 g) was added dropwise in place of dimer diamine, and the solution was heated to 140 ° C. and imidized for 1 hour to obtain a solution of polyimide resin &Lt; / RTI &gt; Further, the molar ratio of the acid component / amine component in the solution of the resin is 1.04. Next, after the polyimide resin solution was cooled to room temperature, the component (a3-1) (66.1 g) was added thereto, and the mixture was reacted at 90 ° C for 3 hours. After cooling to room temperature, methanol (132.1 g) To obtain a solution (nonvolatile content of 45.0%) of the methoxysilyl group-containing silane-modified polyimide resin (c). The above solution was further diluted with cyclohexanone to obtain a resin varnish (nonvolatile content 35.0%). The resin varnish was used as it was as an adhesive composition.

&Lt; Comparative Example 5 &

Benzophenonetetracarboxylic dianhydride (53.00 g), cyclohexanone (2120.0 g) and methylcyclohexane (424.0 g) were placed in the same reaction vessel as in Production Example 1, and the solution was heated to 60 ° C. After heating, dimer diamine (213.5 g) and α, ω-bis- (3 aminopropyl) polydimethylsiloxane (1043.8 g) were added dropwise and the solution was imidized at 140 ° C. for 1 hour to obtain a polyimide resin Solution. In this solution, the diamine component of 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 component (a3-1) (56.5 g) was added thereto and reacted at 90 ° C for 3 hours. After cooling to room temperature, methanol (113.0 g) , And a solution (non-volatile matter content of 40.0%) of the methoxysilyl group-containing polyimide resin (D) was obtained. The above solution was further diluted with cyclohexanone to obtain a resin varnish (nonvolatile content 35.0%). The resin varnish was used as it was as an adhesive composition.

Poly
Imide
Suzy (a1)
(a2) polyimide component (a2)
Chain growth factor (a3) SiO ₂
wt%
Dimer diamine Other dimer diamines 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
(75 mol%) --- (a3-1) 2

(*) In Example 19, component (B) was used.

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

DPE / ODA (trade name): 4,4'-diaminophenyl ether (manufactured by Wakayama Chemical Industries Co., Ltd.)

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

&Lt; Preparation of adhesive sheet &gt;

The adhesive composition of Example 1 was dried (dried) on a block copolymerized polyimide silica hybrid film (trade name "Formyl N25", Arakawa Chemical Industries, Ltd., thermal expansion coefficient = 18 ppm, tensile elastic modulus = 5.9 GPa, And then dried at 180 캜 for 3 minutes to obtain an adhesive sheet. Adhesive sheets were also obtained for the adhesive compositions of the other examples and comparative examples by the same method. Next, the treated surface of an electrolytic copper foil (trade name "F2-WS", made by Furukawa Sakifoil Co., Ltd., thickness: 18 μm) was superimposed on the adhesive surface of each adhesive sheet and moved in the horizontal direction. In this case, it was judged that the case where the electrolytic copper foil could not move due to tackiness and the case where it was possible to move it in the horizontal direction was referred to as "tacking property" Respectively.

&Lt; Production of layered product (1)

The treated surface of the electrolytic copper foil (trade name "F2-WS", made by Furukawa Sakitayu K.K., 18 μm thick) was superimposed on the adhesive surface of the adhesive sheet prepared in Example 1, and a pressure of 10 MPa, 180 ° C. and 1 minute , And then heated again at 200 DEG C for 1 hour to prepare a layered product (1). For each of the adhesive compositions of the other examples and the comparative examples, each layered product (1) was also obtained in this manner. It is also assumed that the layered product 1 is used as an FPC board.

&Lt; Production of layered product (2)

The adhesive composition according to Example 1 was dried in Pomilan N25, coated on a gap coater to a thickness of 30 mu m, and then heated at 200 DEG C for 30 minutes to obtain an adhesive sheet. Next, the treated surface of the electrolytic copper foil (F2-WS) was superimposed on the adhesive surface of the adhesive sheet, followed by hot pressing for 1 minute under the conditions of a pressure of 10 MPa and a temperature of 200 DEG C to produce a layered product (2). For each of the adhesive compositions of the other examples and the comparative examples, each layered product 2 was obtained in the same manner. It is also assumed that the layered product 2 is used as a carrier sheet or a carrier tape.

&Lt; Adhesion test &gt;

The peel strengths of the respective laminates in the examples and comparative examples were measured according to JISC-6481 standard. The measurement results are shown in Tables 4 and 5 below.

<Soldering heat resistance test: high temperature station>

After heating the laminate (1) of each of the examples and the comparative examples at 120 DEG C for 5 minutes, the plastic substrate surface was moved upward in a solder bath of 340 DEG C for 1 minute, and then the foaming of the adhesive layer and the peeling of the metal substrate And peeling strength of the copper foil was measured in accordance with 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>

Each of the layered product (1) of the example and the comparative example was evaluated for flame retardancy in accordance with the UL94 standard. The case where the laminate 1 corresponds to the V-0 class of the UL94 standard is referred to as "flammable oil"

<Soldering heat resistance: low temperature>

After heating the laminate (2) of the above example and the comparative example at 120 캜 for 5 minutes, the plastic substrate side was lowered and allowed to stand in a solder bath at 260 캜 for 5 minutes. Then, the foams of the adhesive layer and the peeling And the peeling strength of the electrolytic copper foil was measured according to JISC-6481 standard. At the time of measurement, the surface state of the reflecting surface of the electrolytic copper foil was observed, and the presence or absence of the residue of the adhesive of the substrate to be measured was confirmed. The results are shown in Tables 4 and 5 below. Since the layered product 2 is assumed to be used as a carrier sheet or a carrier tape, it is necessary to peel off an electronic component such as a hardened semiconductor element, so that the smaller the value of the peel strength is, the better.

Silane
Unmodified
condition
Adhesive sheet
   The laminate (1)     The laminate (2) Early
Exfoliation
burglar
(N / cm) Solder heat resistance
After the test
(340 DEG C x 1 min)
Flammability
Early
Exfoliation
burglar
(N / cm) Solder heat resistance
After the test
(260 DEG C x 5 min) 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 group
Denaturation state Adhesive sheet
   The laminate (1)     The laminate (2) Early
Exfoliation
burglar
(N / cm) Solder heat resistance
After the test
(340 DEG C x 1 min)
Flammability
Early
Exfoliation
burglar
(N / cm) Solder heat resistance
After the test
(260 DEG C x 5 min) 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

<Fabrication of Flexible Printed Circuit Board>

The adhesive composition according to Example 1 was applied to a Pomilan N25 by a gap coater so as to have a thickness of 30 mu m after drying and then dried at 180 DEG C for 3 minutes to obtain an adhesive sheet. The treated surface of the electroconductive copper foil (F2-WS) was overlaid on the adhesive surface of the above-mentioned adhesive sheet, pressed with a laminate roll of 180 DEG C, and then treated at 200 DEG C for 2 hours to obtain a flexible copper clad laminate. The copper layer of the copper-clad laminate was soft-etched to form a circuit, and the layered product (1) using the adhesive composition of the invention of Example 1 obtained in the above-described manner was laminated thereon. And then heated at 200 ° C for one hour to obtain a flexible printed wiring board. Also, a flexible printed wiring board was produced by the same method for the adhesive composition of another embodiment.

Claims (22)

At least one polyimide resin (A) selected from the group consisting of the following [1] to [4] and a polyimide obtained by dissolving the thermosetting resin (B) and the flame retardant (C) Based adhesive composition:
[1] A polyimide obtained by reacting a diamine (a2) containing at least 30 mol% of at least one dimer diamine selected from the group consisting of aromatic tetracarboxylic acids (a1) and the following formula (3) Suzy;
[2] A polyimide obtained by reacting a diamine (a2) containing at least 30 mol% of at least one dimer diamine selected from the group consisting of aromatic tetracarboxylic acids (a1) and the following formula (3) A resin obtained by chain elongation of a resin as chain elongation agent with at least one diamine selected from the group consisting of dimer diamine, bisaminophenoxyphenyl propane and 4,4'-diaminodiphenyl ether;
[3] Polyimide obtained by reacting diamines (a2) containing at least 30 mol% of at least one dimer diamine selected from the group consisting of aromatic tetracarboxylic acids (a1) and the following formula (3) A polyimide resin obtained by reacting a resin and an epoxy group-containing alkoxysilane partial condensate (a3); And
[4] A polyimide obtained by reacting a diamine (a2) containing at least 30 mol% of at least one dimer diamine selected from the group consisting of aromatic tetracarboxylic acids (a1) and the following formula (3) The resin is further subjected to chain extension with one or more diamines selected from the group consisting of dimer diamines, bisaminophenoxyphenyl propanes and 4,4'-diaminodiphenyl ether as a chain extender, and a polyimide resin obtained by chain- Containing alkoxysilane partial condensate (a3).
(3)

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

(Wherein m + n = an integer of 6 to 17 and p + q = an integer of 8 to 19). The method according to claim 1,
The polyimide-based adhesive composition according to claim 1, wherein the component (a1)
[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)

delete The method according to claim 1,
(Number of moles of the component (a1) / number of moles of the component (a2)) is 0.6 / 1 to 1.4 / 1 with respect to the polyimide resin obtained by reacting the component (a1) Based adhesive composition.
The method according to claim 1,
Wherein the component (a2) as the polyimide resin raw material further comprises a diaminopolysiloxane.
6. The method of claim 5,
Wherein the diaminopolysiloxanes are 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).
The method according to claim 1,
Wherein the component as a chain extender is at least one member selected from the group consisting of bisaminophenoxyphenyl propane and dimer diamine.
The method according to claim 1,
The amount of the component used as the chain extender is preferably from 0.6 / 1 to 1.4 / 1 [number of moles of the residual carboxyl group in the polyimide resin obtained by reacting the component (a1) and the component (a2)] / By weight based on the total weight of the polyimide-based adhesive composition.
The method according to claim 1,
Wherein the component (a3) is obtained by subjecting an alkoxysilane partial condensate and an epoxy alcohol to a deblocking reaction.
10. The method of claim 9,
Wherein the partial condensate of alkoxysilane is represented by the following formula (6): &lt; EMI ID =
[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).
10. The method of claim 9,
Wherein the epoxy alcohol is represented by the following general formula (7): &lt; EMI ID =
(7)

(In the above formula (7), t represents an integer of 1 to 10).
10. The method of claim 9,
Wherein the amount of the alkoxysilane partial condensate and the amount of the epoxy alcohol is in the range of [the number of moles of alkoxy groups in the alkoxysilane partial condensate / the number of moles of hydroxyl groups in the epoxy alcohol] ranges from 1 / 0.3 to 1 / 0.01. Based adhesive composition.
The method according to claim 1,
Wherein the component (B) is at least one member selected from the group consisting of an epoxy resin, a benzoxazine resin, a bismaleimide resin and a cyanate ester resin.
The method according to claim 1,
Wherein the amount of the component (B) used is from 1 to 150 parts by weight based on 100 parts by weight of the component (A) (in terms of solid content).
The method according to claim 1,
Wherein the component (C) is at least one member selected from the group consisting of a phosphorus-based flame retardant and an inorganic filler.
16. The method of claim 15,
Wherein the amount of the component (C) used is 0.1 to 200 parts by weight based on 100 parts by weight of the component (A) (in terms of solid content).
A cured product obtained by curing the polyimide-based adhesive composition of any one of claims 1, 2, and 4 to 16.
18. The method of claim 17,
And the content of the silica component is 0 to 15% by weight.
An adhesive sheet obtainable by applying the polyimide-based adhesive composition according to any one of claims 1, 2, and 4 to a sheet substrate and drying the same.
A laminate obtainable by thermocompression bonding a sheet substrate to the adhesive surface of the adhesive sheet of claim 19.
A laminate obtained by further heating the laminate of claim 20.
A flexible printed board obtained by using the laminate of claim 21.