WO2008032669A1

WO2008032669A1 - Polyimide resin composition, process for production thereof, and metal laminate

Info

Publication number: WO2008032669A1
Application number: PCT/JP2007/067577
Authority: WO
Inventors: Masahiro Toriida; Yoshihiro Sakata; Masaki Okazaki; Hitoshi Onishi; Wataru Yamashita
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2006-09-11
Filing date: 2007-09-10
Publication date: 2008-03-20
Also published as: JP5139986B2; TW200819501A; JPWO2008032669A1

Abstract

Disclosed is a polyimide resin composition which can be processed by thermocompression bonding under relative low temperature conditions while having excellent heat resistance, which has a high desmear property (a high desmear rate), and which is excellent in processability including reduced contamination of a processing environment. Specifically, disclosed is a polyimide resin composition comprising a polyimide having a repeating unit represented by the general formula (1-1) and a repeating unit represented by the general formula (1-2) and an imide oligomer represented by the general formula (2).

Description

Specification

Polyimide resin composition and method for producing the same, and metal laminate

[0001] The present invention relates to a polyimide resin composition, a method for producing the same, and a metal laminate having a resin layer made of the resin composition.

Background art

[0002] Polyimides are excellent in heat resistance, chemical resistance, mechanical strength, electrical properties, etc.! /, So they are used for aircraft structural materials and cable coating materials, and also for flexible printing. It is also widely applied as a heat-resistant adhesive used in the electronic field represented by substrates and semiconductor packages.

[0003] In some cases, an electric circuit is produced from a metal laminate using a polyimide adhesive as a resin layer. In some cases, a chip or electronic component is mounted on the polyimide metal laminate using solder, or a chip or electronic component called a repair is removed. In recent years, lead-free solder has come to be used for mounting chips and electronic components from the viewpoint of environmental protection. Therefore, more excellent “solder heat resistance” is required!

In applications called rigid flex and flexible multilayer substrates, it has been pointed out that reliability is insufficient at solder heat resistance temperatures that have been conventionally required, and higher heat resistance is desired.

[0004] When a metal laminate including a polyimide-based adhesive as a resin layer is used as a chip-on-film (hereinafter sometimes abbreviated as "COF"), the bonding between the chip and the metal wiring is performed in an inner layer. Bonder is done by Au-Au bonding or Au-Sn bonding using flip chip bonder. Since Au-Au bonding or Au-Sn bonding requires high temperature conditions of 300 ° C or higher, a substrate with excellent solder heat resistance is desired even when used for COF.

Furthermore, recent polyimide-based heat-resistant adhesives are required to have low-temperature adhesiveness in addition to heat-resistant properties from the viewpoint of processing characteristics. Bonding with a conventional resin composition containing a specific polyamic acid may require a bonding temperature of 300 ° C or higher, and many of them are still insufficient from the viewpoint of low-temperature adhesiveness. ,. [0006] Thus, polyimide adhesives are required to have both improved heat resistance and improved low-temperature adhesion. As a polyimide heat-resistant adhesive having sufficient adhesive strength and heat resistance, a resin composition composed of a specific polyamic acid and bismaleimide has been developed! /, E.g. See).

[0007] On the other hand, when an electric circuit is manufactured from a metal laminate having a polyimide adhesive as a resin layer, through-hole formation (via processing) may be performed by laser processing. In through-hole formation, generally, a resin layer (also called “smear”) that could not be removed by laser processing is removed with an alkaline solution (also called “desmear treatment”! /). ) Is performed. From the viewpoint of productivity, it is preferable that smear be removed quickly (desmear rate is high), that is, high solubility in an alkaline solution / polyimide adhesive is desired. However, polyimide adhesives with improved low-temperature adhesion tend to have a low desmear rate.

[0008] Further, as a polyimide heat-resistant adhesive having sufficient low-temperature adhesiveness, a resin composition comprising a bismaleimide compound and a polyamic acid power has been reported! (See Patent Document 5) . However, when a resin composition containing bismaleimide is used for the resin layer of the metal laminate, a volatile substance (bismaleimide) may be generated depending on the production conditions, which may cause production problems. In addition, when applying or laminating resin compositions, volatile substances sometimes affected production facilities.

Patent Document 1: JP-A-1 289862

Patent Document 2: JP-A-6-145638

Patent Document 3: Japanese Patent Laid-Open No. 6-192639

Patent Document 4: JP-A-2-274762

Patent Document 5: JP 2004 209962 Koyuki

Disclosure of the invention

Problems to be solved by the invention

[0009] An object of the present invention is to improve desmearability (increase desmear speed) while maintaining low-temperature adhesiveness of the polyimide-based resin composition (capable of thermocompression bonding under relatively low temperature conditions). That is. In addition, the object of the present invention is to maintain the low temperature adhesiveness while processing. An object of the present invention is to provide a polyimide resin composition excellent in processability by suppressing generation of volatile substances.

Furthermore, the metal laminated body preferably applied as a flexible printed circuit board etc. is provided using the resin composition of this invention.

Means for solving the problem

[0010] The first of the present invention relates to the following polyimide resin composition.

[1] Contains a repeating unit represented by the following general formula (11), a polyimide resin containing a repeating unit represented by the general formula (12), and an imide oligomer represented by the following general formula (2) A polyimide resin composition.

[0011] [Chemical 1]

[In the formulas (1 1) and (1 2), A and A are the following formulas (a 1) or 2

1 2

B and B may be the same or different from each other.

1 2

bl) or (b2), which may be the same or different from each other! /, may! /,]

[Chemical 2]

[0013] [Chemical 3]

[In the formula (2), A is any one of the following formulas (cl) to (c4), and B is the following formula (dl)

3 3

To (d4), Z is the following formula (el) or (e2), and 1 is an integer from;! To 5]

[Chemical 4]

[In the formulas (cl) to (c4), X is a direct connection,-O S CO COO

7 12

Selected from the group consisting of C (CH) C (CF) SO --NHCO

3 2 3 2 2

Even if they are the same, they are different! /

[0015] [Chemical 5]

[In formulas (dl) to (d4), Y is a direct connection, _o S CO COO

7 12

Selected from the group consisting of C (CH) C (CF) SO --NHCO

3 2 3 2 2

Even if they are the same, they are different! /

[0016] [Chemical 6

[In the formula (el) or (e2), R 1 represents a hydrogen atom, a halogen atom, and a carbon number;

1!

Selected from the group consisting of 3 alkyl groups, which may be the same or different from each other, R is O S—, —CH 2 C (CH 2) CO, or 1 COO.

5 2 3 2

]

[2] Any one of A in the general formula (1 1) and A in the general formula (1 2)

1 2

One is (al) and the other is (a2), The polyimide resin composition as described in [1]. [3] The polyimide resin composition according to [1] or [2], wherein 1 in the general formula (2) is 1. [4] 5 parts by weight or more and 100 parts by weight or less of the imide oligomer represented by the general formula (2) with respect to 100 parts by weight of the polyimide resin, [1] to [3] A polyimide resin composition according to claim 1. [5] The polyimide resin composition according to claim 1, wherein the glass transition temperature is in the range of 100 ° C to 300 ° C. [6] In the general formula (2), A is

3 is the following formula (c5) or (c6), and B is a group consisting of the following formulas (dl) and (d5) to (dl0)

Three

The polyimide resin composition according to any one of [1] to [5], wherein Z is (e3) or (e4), and 1 is an integer of !!-5.

[0018] [Chemical 7]

[0019] [Chemical 8]

[0020] [Chemical 9]

[R and R are defined as in the above formula (e2)]

3 4

[7] A polyamic acid comprising a repeating unit represented by the following general formula (3-1) and a repeating unit represented by the following general formula (3-2), represented by the general formula (2) Imide oligomers, and mixtures containing solvents as required.

[0022] [Chemical 10]

[In the formulas (3-1) and (3-2), Α and A represent the formulas (a 1) and (a2

1 2

B and B may be the same or different from each other.

1 2

bl) or (b2), which may be the same or different from each other! /, may! /,]

[Chemical 11]

[In the formula (2), A is any one of the formulas (cl) to (c4), and B is the formula (dl)

3 3

To (d4), Z is the formula (el) or (e2), and 1 is an integer of 1 to 5]

[8] A method for producing a cured polyimide resin comprising heating the mixture according to [7] to include an imidization reaction-Γ. [0025] In addition, the present invention relates to members shown below. [9] A film comprising a cured product of the polyimide resin composition according to any one of [1] to [6]. [10] A metal laminate comprising a metal layer and a resin layer, wherein at least one of the resin layers is a metal laminate comprising a cured product of the polyimide resin composition according to any one of [1] to [6] body. [11] A polyimide film, a polyimide layer formed on one or both sides of the polyimide film, a metal layer laminated on one or both of the polyimide layers,

A metal layered product, which is a resin layer made of a cured product of the polyimide resin composition according to any one of [1] to [6], in which the polyimide layer force [1] to [6] is in contact with the metal layer. [12] A resin film and a resin layer made of a cured product of the polyimide resin composition according to any one of [1] to [6], laminated on one or both surfaces of the resin film, Having an adhesive sheet.

The invention's effect

[0026] The polyimide resin composition of the present invention is excellent in low-temperature adhesiveness! /, But has high desmearability (high desmear speed) and suppresses generation of volatile substances during processing.

[0027] Further, the polyimide resin composition of the present invention can produce a metal laminate by bonding the metal layer and the resin layer, and it is not necessary to use a high processing temperature for the bonding. Voids hardly remain at the interface between the layer and the polyimide. Therefore, a metal laminate having a high adhesive strength between the metal layer and the resin layer can be obtained. The resulting metal laminate can be suitably used as a flexible printed circuit board.

The resulting metal laminate and the adhesive sheet that is the precursor of the metal laminate (sheet without the metal layer) have excellent soldering heat resistance. Even during these repair processes! /, Swelling is unlikely to occur.

BEST MODE FOR CARRYING OUT THE INVENTION

[0028] 1. Polyimide resin composition

The polyimide resin composition of the present invention contains a polyimide resin and an imide oligomer.

[0029] Polyimide resin

The polyimide resin contained in the polyimide resin composition contains a repeating unit represented by the following general formula (11) and a repeating unit represented by the following general formula (12); By doing so, it may be a precursor (that is, a polyamic acid) that generates a repeating unit represented by the following general formula (11) and a repeating unit represented by the general formula (12).

[0030] [Chemical 12]

[0031] A in the formula (1 1) and A in the formula (1 2) are triethylene ether structures.

1 2

And is represented by the following formula (al) or (a2).

[0032] [Chemical 13]

[0033] A and A may be the same or different from each other, but preferably one of A and A

1 2 1 2 is (al) and the other is (a2). If both A and A are (al),

1 2

Desmear speed may be slow. On the other hand, if both A and A are (a2),

1 2

The roll strength and low-temperature adhesiveness may decrease. A and A, a combination of (al) and (a2)

1 2

In order to balance the desmear speed and the low temperature adhesion (glass transition temperature), the number ratio of (al) and (a2) contained in the polyimide should be 8: 2 to 5: 5. Is more preferable, and 7: 3 is more preferable.

[0034] B and B in the formula (1) are represented by the following formula (bl) or (b2). B and

1 2 1

It is preferable that either one or both of B is (bl). B and B are expressions (

The combination of (2 1 2 bl) and (b2) improves the desmearing speed of the resin composition, but if the ratio of (b2) is too high, the solder heat resistance in a humidified environment deteriorates. There is.

[0035] [Chemical 14]

[0036] The polyimide resin contained in the polyimide resin composition of the present invention may contain a force containing repeating units represented by the above formulas (11) and (12) or other repeating units. Good.

[0037] The molecular weight of the polyimide resin contained in the polyimide-based resin composition is not particularly limited, and is adjusted according to the molecular weight of the monomer components (diamin and tetracarboxylic dianhydride) and the mole ratio thereof as described later.

[0038] Manufacture of polyimide resin

The polyimide resin contained in the polyimide resin composition is preferably manufactured from a raw material containing tetracarboxylic dianhydride and diamine.

[0039] The raw material for the polyimide resin includes 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) or bis (3,4-dicarboxyl), which are tetracarboxylic dianhydrides. Enil) Sulphone dianhydride (DSDA) is preferred!

[0040] Further, the raw material of the polyimide resin may contain one or more other tetracarboxylic dianhydrides. By copolymerizing them, the performance of the polyimide resin can be improved or modified without impairing the effects of the present invention.

[0041] Examples of other tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyl Phenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3- Bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyloxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dica Norepoxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, and the like.

[0042] Further examples of other tetracarboxylic dianhydrides include ethylenetetracarboxylic dianhydride , Butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane anhydride, 1,1-bis (3,4-dicarboxy Phenyl) ethane anhydride, 1,2-bis (2,3-dicarboxyphenyl) ethane anhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane anhydride, 1,2, 5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7 , 8-phenanthrenetetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

[0043] In addition, other tetracarboxylic dianhydrides are substituted with a fluoro group or a trifluoromethyl group for some or all of the hydrogen atoms on the aromatic ring of the tetracarboxylic dianhydride exemplified above. Tetracarboxylic dianhydride may be used.

[0044] The raw material of the polyimide resin may contain 1,3-bis (3-aminophenoxy) benzene (APB) or 1,3-bis (4-aminophenoxy) benzene (APB-R) which is diamine. It is more preferable to include V and slippage!

[0045] The raw material of the polyimide resin contains other diamines! The other diamine may be an aromatic diamine or an S amizuki triamine.

[0046] Examples of aromatic diamines include m-phenylenediamine, 0-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyletherole, 3,4'-diaminodiphenyl ether, 4 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diamino Diphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4 ' -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (3-aminophenol) propane, 2,2-bis (4-aminophenol) propane, 2,2-bis (3-Aminophenyl) -1,1,1,3,3,3-hexafluoro Lopan, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diamino Diphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenol) Ninore) benzene, 1,4-bis (4-aminophenyl) Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenylsulfide) benzene, 1,3-bis ( 4-Aminophenyl norephido) benzene, 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenyl) Sulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3-bis (3-aminobenzyl) benzene, 1,

3-bis (4-aminobenzyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 3,3'-bis (3-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [ 3- (3-Aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] etherole, bis [4- (4-aminophenoxy) Phenenole] etherole, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenenole] ketone, bis [4- (3-aminophenoxy) phenenole] ketone, bis [4- (4-Aminophenoxy ) Phenyl] ketone, bis [3- (3-aminophenoxy) phenyl] sulfide, bis [3- (4-aminophenoxy) phenole] sulfide, bis [4- (3-aminophenoxy) phenole] sulfide, Bis [4- (4-aminophenoxy) phenyl] sulfide, Bis [3- (3-aminophenoxy) phenyl] sulfone, Bis [3- (4-aminophenoxy) phenenole] sulfone, Bis [4- (3-aminophenoxy) ) Phenolene] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, bis [

4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3 -(4-Aminophenoxy) phenol] propane, 2,2-bis [4- (3-Aminophenoxy) phenol] propane, 2,2-bis [4- (4-Aminophenoxy) phenol] propane 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3, Examples include 3-hexafluoropropane and 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane. These aromatic diamines may be used alone or in combination. [0047] The raw material of the polyimide resin contains an aliphatic diamine! /, May! /. Aliphatic diamines are used to improve or modify performance. Examples of aliphatic diamines include 1,3-bisdisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) Ether, 1,2-bis (aminomethoxy) ethane, bis [(2-aminomethoxy) ethyl] ether, 1,2-bis [(2-aminomethoxy) ethoxy] ethane, bis (2-aminoethynole) ether, 1 , 2-bis (2-aminoethoxy) ethane, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethoxy] ethane, bis (3-aminopropyl) ether, 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-Diaminoheptane, 1,8-Diaminooctane, 1,9-Diaminononane, 1,10-Diaminodecane 1,1;! _ Diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3_di (2-aminoethynole) cyclohexane, 1,4-di (2-aminoethynole) cyclohexane, bis (4-aminocyclohexyl) methane, 2 , 6-bis (aminomethyleno) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, and the like. These diamines can be used alone or in combination of two or more.

[0048] The molecular weight (degree of polymerization) of the polyimide resin contained in the polyimide resin composition of the present invention can be controlled by adjusting the molar ratio of the monomer components in the same manner as the molecular weight of a normal polycondensation polymer. In other words, it is preferable that the raw material of the polyimide resin contains 0 · 900 mol to 0.999 mol of tetracarboxylic dianhydride per mol of diamine. It is more preferable to include acid dianhydride, and it is more preferable to include 0.995 to 0.995 monotetracarboxylic dianhydride. Even more preferably.

[0049] It is preferable that the raw material of the polyimide resin (monomer raw material containing diamine and tetracarboxylic dianhydride) is once converted to polyamic acid (polyimide precursor) and then polyimide. That's right. In order to use the monomer raw material as the polyamic acid, the monomer raw material may be added to a solvent and heated.

[0050] The solvent to which the monomer raw material for the polyimide resin is added is not particularly limited, but is preferably an aprotic polar solvent, and more preferably an aprotic amide solvent. Specifically, N N-dimethylformamide, N N-dimethylacetamide, N N-jetylacetamide, N N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3- Dimethyl-2-imi

[0051] Further, the solvent to which the monomer raw material of the polyimide resin is added may further coexist with the following solvent. Examples of organic solvents that can coexist include benzene, toluene, 0-xylene, m-xylene, p-xylene, 0-chlorotolenene, m-chlorotonolene, p-chlorotonolene, 0-bromotonolene, m-bromotonolene, p-bromotolenene, This includes black mouth benzene and bromobenzene. These organic solvents may be used alone or in combination of two or more.

[0052] Polyamic acid produced as a polyimide precursor is used as a varnish. 7] inh is preferably 0.2 dl / g 2. Odl / g, more preferably 0.3 to 1; more preferably Od 1 / g. More preferably, it is 0.4 0. 9 dl / g. The logarithmic viscosity of the polyimide precursor is the viscosity at 35 ° C. of a solution obtained by dissolving the solid content of the polyimide precursor in NN-dimethylacetamide at a concentration of 0.5 g / dl.

[0053] When the logarithmic viscosity of the polyimide precursor is in the above range, the cured resin obtained by the precursor strength becomes strong, and it becomes easy to form a film or a metal laminate. Also, in the coating process when manufacturing a film or metal laminate, the film thickness tends to be uniform, which is preferable.

[0054] Imide oligomer

The imide oligomer contained in the polyimide resin composition has a structure represented by the formula (2). 1 in the formula (2) is 15; When 1 in Formula (2) is 1, the effect of the imide oligomer as a plasticizer is further increased, and as a result, the low-temperature adhesiveness of the polyimide resin composition is further increased.

[0055] [Chemical 15] … (2)

[0056] A in the formula (2) has a structure represented by any of the following formulas (cl) to (c4). The

Three

Furthermore, A in the formula (2) preferably has a structure represented by the following formula (c5) or (c6)

Three

The In the formulas (cl) to (c4), X is a direct connection, 101, 1S, 1C001, -COO-

7-12

, -C (CH 1), -C (CF) 1, -SO 1, NHC 0 1

3 2 3 2 2

They may be the same or different. X is any of the benzene rings

7-12

It is bonded to some carbon. Similarly, the oxygen atom in the formula (c5) or (c6) is bonded to any carbon constituting the benzene ring. For example, A in equation (2) is

Three

C7) or a structure represented by formula (C8).

[0057] [Chemical 16]

Β in formula (2) has a structure represented by any of the following formulas (dl) to (d4). The

Three

In addition, B in formula (2) represents the structure represented by formula (dl) or any of (d5) to (dl0). It is preferable to have. If the structure of B is selected from the viewpoint of solvent solubility and cost, etc.

Three

Good. In formulas (dl) to (d4), Y is a direct connection, 〇 S C〇1, C〇〇

7 12

C (CH) ― C (CF) ― -SO ― NHC

3 2 3 2 2

These may be the same or different. Y is the carbon constituting the benzene ring

7 12

It is bonded to one of the atoms. Y force C001 or NHC001

7 12

In that case, the direction of the bond may be any.

[0059] [Chemical 17]

[0060] Z in the formula (2) is more preferably a force represented by the following formula (el) or (e2), and further represented by the following formula (e3) or (e4). In Formula (el), Formula (e2), or Formula (e4), R is selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 13 carbon atoms.

Four

These may be the same as or different from each other. In formula (e4), R and R are preferably

3 4 Preferably it is a hydrogen atom. R is 〇 S- -CH -C (CH)

5 2 3 2

C001 or C001. If R is 1 C001, the direction of the bond is

Five

Either is acceptable. [0061] [Chemical 18]

[0062] The imide oligomer contained in the polyimide resin composition of the present invention preferably has a weight average molecular weight of 1000 or more and 5000 or less (both Mw! /). The weight average molecular weight of the imide oligomer is measured by gel permeation chromatography (measurement conditions, detector; RI, developing solvent; tetrahydrofuran, flow rate; lml / min, column temperature; 40 ° C).

When the weight average molecular weight of the imide oligomer is within this range, it is preferable that the amount of evaporation when the resin composition is heated is reduced and the plasticizing effect is not lowered. Furthermore, from the viewpoint of balance between evaporation amount suppression and plasticity improvement, the weight average molecular weight Mw should be not less than 1000 and not more than 400 S. Preferably, it should be not less than 1000 and not more than 3500, more preferably not less than 1500 and not more than 3500. Is even more preferable.

[0063] Method for producing imide oligomer

The imide oligomer contained in the polyimide-based resin composition of the present invention can be produced by any method. For example, tetracarboxylic dianhydride, diamine and dicarboxylic anhydride, and a raw material containing a solvent as necessary. , Produced by imidization reaction. A preferable imide oligomer can be obtained by controlling the molar ratio of each component (tetracarboxylic dianhydride, diamine and dicarboxylic anhydride) contained in the raw material (described later).

[0064] Examples of the tetracarboxylic dianhydride contained in the raw material of the imide oligomer include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-Benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis ( 3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxy) Siphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2, 2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride and the like are included. One or more tetracarboxylic dianhydrides are included in the raw material of the imide oligomer.

Examples of diamines contained in imide oligomer raw materials include m-phenylene diamine, 0-phen diendiamine, p-phenylene diamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl. Ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulphoide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3 '-Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-di Aminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2_bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) ) -1,1,1, 3,3, 3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4 ' -Diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis (3-aminophenol) benzene, 1,3-bis (4-aminophenol) benzene, 1,4- Bis (3-aminophenol) benzene, 1,4-bis (4-aminophenol) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1 , 4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenylsulfide) benzene, 1,3-bis (4-a Minophenylsulfide) benzene, 1,4-bis (4-aminophenylsulfide) benzene, 1,3-biphenyl (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3-bis (3- Aminobenzyl) benzene, 1,3-bis (4-aminobenzyl) benzene, 1,4-bis (4-aminobenzyleno) benzene, 1,3-bis (3-amino-4-phenoxybenzoy) Nole) benzene, 3,3'-bis (3-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4 -(4-Aminophenoxy) fu Phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4_ (4- Aminophenoxy) phenyl] ketone, bis [3- (3-aminophenoxy) phenyl] sulfide, bis [3- (4-aminophenoxy) phenenole] snoreido, bis [4- (3-aminophenoxy) phenenole] sulfide, bis [4- (4-aminophenoxy) phenole] sulfide, bis [3- (3-aminophenoxy) phenenole] sulfone, bis [3- (4-aminophenoxy) phenenole] sulfone, bis [4-( 3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-Aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [3- (3- Aminophenoxy) phenol] propane, 2,2-bis [3- (4-aminophenoxy) phenol] propane, 2,2-bis [4- (3-aminophenoxy) phenol] propane, 2,2- Bis [4- (4-aminophenoxy) phenole] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoroprop Bread, and the like. One or more diamines are contained in the raw material of the polyimide oligomer.

[0066] Examples of the dicarboxylic acid anhydride contained in the raw material of the imide oligomer include maleic anhydride, nadic anhydride and the like. Alternatively, a compound that forms a benzene ring by trimerization, such as 4- (2-phenyl) phthalic anhydride and 4- (2-ethyl) phthalic anhydride, may be used.

[0067] It is preferable that the solvent contained in the raw material of the imide oligomer is an organic solvent. In the column of the organic solvent, there are the following: -Cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6_xylenol, 3,4_xylenol, 3,5_xylenol, N, N -Dimethylformamide, N, N-dimethylacetamide, N, N-jetylacetamide, Ν, Ν-dimethylmethoxyacetamide, 、 -methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidino , Ν-methylcaprolatatam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ethanol, tetrahydrofuran, 1,3-di-xane, 1,4-di-xanthane, pyridine, picoline Dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, anisole and the like. These organic solvents may be used alone or in admixture of two or more.

[0068] The following solvent may coexist in the raw material of the imide oligomer. Examples of organic solvents that can coexist are benzene, toluene, 0-xylene, m-xylene, p-xylene, 0-dichlorotolenene, _m- chlorotolenene, p-chlorotolenene, 0-p, motomotolene, _m -p Examples include motonoren, p-bromotoluene, black benzene, and bromobenzene.

[0069] The raw material of the imide oligomer may contain a catalyst for increasing the rate of the imidization reaction (described later), for example, an organic base catalyst. Examples of organic base catalysts include triethylamine, tributylamine, tripentinoreamine, N, N-dimethylaniline, N, N-jetylaniline, pyridine, α_picoline, / 3_picoline, γ-picoline, 2,4 -Noretidine, 2,6-norethidine, quinoline, isoquinoline and the like are included, and pyridine and γ-picoline are preferred.

The content of the catalyst in the raw material of the imide oligomer is not particularly limited as long as the polymerization reaction rate is substantially improved, but for example, 0.001 to 0.5 monolayer per 1 mol of tetracarboxylic dianhydride. is there.

[0070] The procedure for producing an imide oligomer is as follows: (1) the reaction of diamine and tetracarboxylic dianhydride, followed by addition of dicarboxylic anhydride, and (2) diamine and dicarbon After adding acid anhydride and reacting, add tetracarboxylic dianhydride component to continue reaction, (3) Add diamine compound, tetracarboxylic dianhydride and dicarboxylic anhydride simultaneously There are procedures such as reacting, but any procedure is acceptable.

[0071] Examples of the imidization reaction include thermal imidization, chemical imidization, and direct thermal imidization.

Thermal imidation is the reaction of the aforementioned raw materials at a low temperature of 100 ° C or lower, specifically 20 to 70 ° C, preferably 0 to 60 ° C, to synthesize an imide oligomer precursor, and then 100 This is a method of obtaining an imide oligomer by raising the temperature to ˜200 ° C. and imidizing. Chemical imidation refers to chemical immobilization of the imide oligomer precursor using an imidizing agent such as acetic anhydride. This is a method for performing a middation.

Direct thermal imidation, on the other hand, is a mixture of diamine, tetracarboxylic dianhydride, and dicarboxylic anhydride, followed by rapid heating in the presence or absence of an organic base and / or azeotropic dehydration solvent. In this way, the imide oligomer precursor produced in the reaction system is imidized as it is.

[0072] The reaction time for imidation varies depending on the type of monomer used, the type of solvent, the type of organic base catalyst, the type and amount of the azeotropic dehydration solvent, and the reaction temperature. Usually several hours.

In the case of direct thermal imidation, as a guideline, the reaction is carried out until the distilled water reaches almost the theoretical amount (usually not all is recovered, so the recovery rate is 50 to 90%). Approximately several hours of reaction time are required. In this case, a method of removing water generated by imidization with an azeotropic agent such as toluene is general and effective.

[0073] The reaction pressure for imidization is not particularly limited, but may usually be atmospheric pressure. The imidation reaction is usually performed in an atmosphere of air, nitrogen, helium, neon, or argon, and is preferably a force that is preferably performed in an inert gas such as nitrogen or argon.

[0074] The concentration (polymerization concentration) of the monomer component contained in the raw material of the imide oligomer is not particularly limited, but is generally about 10 to 60 wt%. If it is less than 10 wt%, an extremely long reaction time may be required, and if it exceeds 60 wt%, the raw material will be dissolved and the reaction efficiency may be deteriorated. The polymerization concentration is preferably 20 to 50 wt%, more preferably 30 to 40 wt%.

[0075] The molecular weight of the imide oligomer can be controlled by adjusting the molar ratio of the monomer components contained in the raw material, as in the case of the molecular weight of a normal polycondensation polymer. It is important that the raw material of imidoligomer contains 0.50-0.80 moles of tetracarboxylic dianhydride, more preferably 0.50-0.70 moles per mole of diamine. More preferably, 0.50 to 0.65 monole, and even more preferably 0.50 to 0.60 monole tetra-force norevonic dianhydride is included. An imide oligomer having a preferable molecular weight can be produced as described above by appropriately controlling the ratio of the monomer components.

If the amount of tetracarboxylic dianhydride per mole of diamine is less than 0.5 mole, A large amount of bisimide consisting of styrene and dicarboxylic acid anhydride is formed, and the amount of evaporation during heating increases, which is not preferable. On the other hand, if it exceeds 0.80 mol, the molecular weight increase causes a reduction in the plasticizing effect when used as a plasticizer, for example.

[0076] Further, the number of moles of dicarboxylic anhydride M5 contained in the raw material of the imide oligomer satisfies the relationship of the following formula with the number of moles M3 of tetracarboxylic dianhydride and the number of moles M4 of diamine. is important.

(M4-M3) X2X1.0 ≤ M5 ≤ (M4— M3) X 2 X 2. 2

[0077] Preferably, (Μ4— Μ3) Χ2Χ1 · 0≤Μ5≤ (Μ4-Μ3) Χ2Χ2.0, more preferably (好ましく 4— Μ3) X2X1.0≤1.05≤ (Μ4-Μ3 ) X2X1.5 is satisfied, and more preferably (Μ4—Μ3) X2X1.0≤Μ5≤ (Μ4—Μ3) X2X1.2 is satisfied.

[0078] (Μ4-Μ3) If X2X1.0> Μ5, an amino group remains in the imide oligomer to be formed, and it is colored upon heating, which is not preferable in appearance. On the other hand, if (Μ4-—3) Χ2Χ2.2 <Μ5, a large amount of bisimide consisting of diamine and dicarboxylic acid anhydride is formed and the amount of evaporation during heating increases, which is not preferable.

[0079] Polyimide resin composition

The polyimide resin composition of the present invention is represented by the polyimide resin containing the repeating unit represented by the general formula (11) and the repeating unit represented by the general formula (12), and the general formula (2). It contains an imide oligomer. Further, even if the polyimide resin is a cured resin, it is a resin (polyamide acid) that generates a repeating unit represented by the general formula (11) and a repeating unit represented by the general formula (12) when cured. May be! /

[0080] In the polyimide resin composition, the general formula is used with respect to 100 parts by weight of the polyimide resin.

The imide oligomer represented by (2) is preferably contained in an amount of 5 parts by weight or more and 100 parts by weight or less, more preferably 10 parts by weight or more and 90 parts by weight or less, and more preferably 20 parts by weight or more and 80 parts by weight or less. More preferably it is.

When the ratio between the polyimide resin and the imide oligomer is within the above range, the glass transition temperature of the polyimide resin composition is sufficiently low, which is particularly useful when used for a metal laminate requiring low-temperature adhesion. . Furthermore, the polyimide resin composition is cured to form a film or layer In this case, the brittleness is reduced, which is preferable.

[0081] When the polyimide resin composition of the present invention is cured and used as a laminate for a flexible circuit board or a resin layer of an adhesive sheet, the glass transition temperature of the polyimide resin composition is 100 ° C or higher. A range of 300 ° C. or lower is preferable. Furthermore, from the viewpoint of realizing adhesion under low temperature conditions, the temperature is preferably 100 to 240 ° C, more preferably 100 to 200 ° C.

[0082] The polyimide resin composition of the present invention may contain any other thermoplastic resin, thermosetting resin, and the like as long as the object of the present invention is not impaired.

Examples of optional thermoplastics include polyethylene, polypropylene, poly (vinyl chloride), poly (vinylidene chloride), polybutadiene, polystyrene, poly (acetate), ABS resin, poly (butylene terephthalate), polyethylene terephthalate, poly (phenylene dioxide), polycarbonate, P FE, senoreroid ', polyrelate, polyutenorenitrinole, polyamide', polysenolephone, polyethersulfone, polyetherketone, polyphenylenesulfide, polyamidoimide, polyetherimide, modified polyphenyleneoxide, polyimide, etc. . Examples of optional thermosetting resins include thermosetting polybutadiene, formaldehyde resin, amino resin, polyurethane, silicone resin, SBR, NBR, unsaturated polyester, epoxy resin, polycyanate, phenolic resin and polybismaleimide .

Depending on the purpose, one or two or more thermoplastic resins or thermosetting resins can be blended or alloyed in an appropriate amount and contained in the polyimide resin composition. These methods are not particularly limited, and known methods can be applied.

[0083] The polyimide resin composition may be mixed with various fillers or additives within a range not impairing the object of the present invention. Examples of fillers or additives include wear resistance improvers such as graphite, carborundum, keystone powder, molybdenum disulfide, and fluorine resins; improved flame retardancy such as antimony trioxide, magnesium carbonate, and calcium carbonate Agents: Electrical property improvers such as clay and my strength; Tracking resistance improvers such as asbestos, silica, and graphite; Acid resistance improvers such as barium sulfate, silica, and calcium metasilicate; Iron powder, zinc powder, aluminum powder , Copper powder and other thermal conductivity improvers; other glass beads, glass spheres, talc, kieselguhr, alumina, shirasu balun, hydrated alumina, metal oxides, colorants and pigments Etc. are included. A mixing method is not particularly limited, and a known method can be applied.

[0084] The polyimide resin composition of the present invention comprises a polyamic acid (polyimide precursor) containing the repeating unit represented by the general formula (3-1) and the repeating unit represented by the general formula (3-2). And an imide oligomer represented by the general formula (2) can be obtained by imidizing polyamic acid and reacting the imide oligomer. Imide oligomers are irreversibly polymerized by polymerization of terminal double bonds. The polymer of an imide oligomer can be detected by confirming the presence of a double bond by IR.

[0085] In particular, a coating film of a solution containing a polyamic acid (polyimide precursor) and an imide oligomer is heated and dried to remove the solvent and cure by imidization to form a film or a layered film. A polyimide resin cured product can be obtained.

[0086] The solvent of the solution containing the polyamic acid and the imide oligomer is not particularly limited, but is preferably an aprotic polar solvent. More preferred are aprotic amide solvents, such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-jetylacetamide, N, N-dimethylmethoxy. Examples include acetonitrile, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone.

[0087] The viscosity of the solution containing the polyamic acid and the imide oligomer is not particularly limited! /. For example, when the viscosity measured at 25 ° C using an E-type viscometer is in the range of 100 to 20000 mPa'S, the coating thickness can be easily controlled when trying to apply the solution.

[0088] When a solution containing the polyamic acid and the imide oligomer is heat-treated, imidization of the polyamic acid or a reaction between the imide oligomers occurs to obtain a cured polyimide resin. As the pressure in the heat treatment, atmospheric pressure is usually sufficient, but it can be performed under pressure. The atmosphere for the heat treatment is not particularly limited, but is usually air, nitrogen, helium, neon or anoregon, preferably nitrogen or argon which is an inert gas.

[0089] The solution containing the polyamic acid and the imide oligomer is added with an additive such as a catalyst for the purpose of accelerating or suppressing the crosslinking reaction that proceeds by heat treatment, or controlling the reaction rate. May be. Examples of catalysts include metal catalysts containing gallium, germanium, indium or lead; transition metal catalysts containing molybdenum, manganese, nickel, cadmium, cobalt, chromium, iron, copper, tin or platinum; and phosphorus compounds, silicon Compounds, nitrogen compounds Or a sulfur compound etc. are contained.

Also in the solution containing polyamic acid and imide oligomer, for the same purpose, infrared, ultraviolet and alpha, radiation such as β and _Ί line, irradiation of electron beams and X-rays, and further, a plasma treatment or doping process It can also be applied.

[0090] The polyimide resin composition of the present invention may be a film. In order to form a film, a solution containing polyamic acid and an imide oligomer is applied to a substrate, and the resulting coating film is cured by desolvation and imidization reaction, and then peeled off from the substrate. Good. Examples of the substrate include inorganic substrates such as metal foil and glass, or polymer films. The coating on the substrate may be performed using a coater or the like. The coating thickness is affected by the solid content concentration of the solution containing polyamic acid and imide oligomer, but the film thickness of the cured polyimide resin after desolvation and imidization reaction (that is, “after curing”) It is preferable that the force be less than mm.

The method of desolvation and imidization (that is, “curing”) is not particularly limited! /, But may be performed under reduced pressure or in an inert atmosphere such as nitrogen, helium, or argon. Also, it should be higher than the boiling point of the solvent used and higher than the temperature at which the imidization reaction proceeds. For example, when a non-proton amide solvent is used, it should be 200 ° C or higher! /. The time required for solvent removal and imidization is not particularly limited, but usually 2 hours or more is sufficient.

[0091] 2. Metal laminate

The metal laminate of the present invention includes a metal layer and a resin layer. The metal laminate includes a force S including one or more resin layers, and one or more of the resin layers are cured products of the polyimide resin composition of the present invention (also referred to as “resin cured products”). ). Preferably, the metal laminate includes a polyimide film, a polyimide layer formed on one or both sides of the polyimide film, and a metal layer laminated on any one or both of the polyimide layers. The polyimide layer in contact with the layer is made of a cured product of the polyimide resin composition of the present invention described above.

[0092] Resin layer

As described above, the metal laminate of the present invention has a force S including one or two or more polyimide resin layers, and one or more of the resin layers are made of a cured product of the polyimide resin composition of the present invention. The When two or more polyimide resin layers are included, adjacent layers are preferably made of polyimides having different components. Different polyimide components mean different types and / or contents of monomer units. Further, at least one of the layers constituting the single-layer polyimide layer or the multilayer polyimide layer is formed from a composition (mixture) made of two or more different polyimides.

That is, when the polyimide layer constituting the metal laminate is a single layer, the layer is made of a cured product of the polyimide resin composition of the present invention. On the other hand, when the polyimide layer constituting the metal laminate is a multilayer, among the polyimide layers formed on one or both sides of the polyimide film, the polyimide layer in contact with the metal layer is the polyimide resin composition of the present invention. It is preferable that the layer has a cured product strength. This is to improve the adhesion with the metal layer. The thickness of the polyimide layer in contact with the metal layer is 0.1 m to 20 m, preferably 0.1

m or less, more preferably 0.1 m or more and 5 m or less.

[0094] If the total thickness of the polyimide layer (single layer or multilayer) constituting the metal laminate is too thick, the rigidity becomes so strong that it cannot be used for applications that require bending, and if it is too thin, it is insulated. There is a restriction that it cannot be used in terms of performance and handling.

Accordingly, the total thickness of the polyimide layers contained in the metal laminate is preferably from 3,1 m to 75 μm, and more preferably from 10 m to 45 m. When the thickness of the polyimide layer is within the above range, the metal laminate tends to be excellent in insulation, flexibility and workability and at low cost.

[0096] Polyimide Finolem

As described above, the metal laminate may have a polyimide film, a polyimide layer formed on one or both sides of the polyimide film, a force of the polyimide layer, or a metal layer laminated on both. The polyimide film contained in the metal laminate may be a film obtained by applying and drying a precursor varnish of non-thermoplastic polyimide or a commercially available non-thermoplastic polyimide film. Examples of commercially available non-thermoplastic polyimide films include: Upilex S, Upilex SGA, Upilex SN (Ube Industries, registered trademark / trade name), Kapton Kapton ¥, Kapton EN (Toray Dupont, Registered trademark / trade name), Abiki Nore AH, Abical NPI, Abical HP (manufactured by Kaneiki Co., Ltd. Registered trademark / product name).

[0097] When the polyimide film contained in the metal laminate is a commercially available non-thermoplastic polyimide film, the thickness is usually 3 m or more and 75 m or less, preferably 7.5 5 111 or more and 40 111 or less. Range. Further, when the polyimide film is formed by applying and drying a precursor varnish of non-thermoplastic polyimide, the thickness is preferably 0.1 to 40 am, preferably (0.5 to 01 to 25). 〃01 or less, more preferably (between 0.5〃01 and 16〃01).

[0098] Metal layer

The metal layer included in the metal laminate is not particularly limited, but is a metal layer selected from copper and copper alloys, stainless steel and alloys thereof, nickel and nickel alloys (including 42 alloys), aluminum and aluminum alloys, and the like. Yes, preferably a copper or copper alloy layer or a stainless steel layer. The metal layer may be formed by laminating a metal foil to the resin layer, or may be formed by a known means that may be formed on the resin by a sputtering method or the like. The metal layer is preferably in contact with the resin layer made of the polyimide resin composition of the present invention.

[0099] The thickness of the metal layer included in the metal laminate is not particularly limited as long as the metal laminate can be used as a tape, and is usually 0.1 111 to 150 111, and preferably 2 to 150 am, more preferably 3 to 50 μm, more preferably 3 to 35 Hm, and most preferably 3 to 12 m. .

[0100] Method for producing metal laminate

The metal laminate of the present invention is not particularly limited and can be produced by appropriately referring to a known method for producing a metal laminate as long as the effects of the present invention are not impaired. For example, it is possible to manufacture with the following method. (1) A method in which a single-layer or multilayer polyimide film and a metal foil are heat-pressed. (2) A method in which a varnish of a polyimide resin composition is applied to a metal foil and then dried. (3) Laminate the following laminated body ω or laminated body (ϋ) and the following laminated body ω or laminated body (ϋ) so that the metal layer is the outermost layer. ) Method. Laminate (i): A laminate having a metal layer only on one surface obtained by thermocompression bonding a single layer or multilayer polyimide film and a metal foil.

Laminate (ii): A laminate having a metal layer only on one surface obtained by applying a varnish of a polyimide resin composition to a metal foil and then drying.

[0101] The metal foil used for the production of the metal laminate is not particularly limited, and known ones can be used. Examples of metal foil materials include copper and copper alloys, stainless steel and its alloys, nickel and nickel alloys (including 42 alloys), aluminum and aluminum alloys, preferably copper or copper alloys, or stainless steel. is there. The thickness of the metal foil is not particularly limited as long as it can be used in the form of a tape, but is usually 0.1 m or more and 150 mm or less, preferably 2 πι or more and 150 m or less, and further 3 m or more and 50 m. The range is more preferably 3 m or more and 35 m or less, and most preferably 3 m or more and 12 m or less. When manufacturing a metal laminate, the surface of the polyimide layer to which the metal foil is pressed is subjected to plasma treatment or corona discharge treatment!

[0102] The thermocompression bonding at the time of producing the metal laminate of the present invention is performed between a metal roll heated by oil or the like as a heat medium or a dielectric roll, or a roll whose surface is lined with rubber or the like. What is necessary is just to perform by the method of laminating, the method by a heat press. The former is suitable for the production of continuous roll products, and the latter is suitable for the production of cut sheet-like single-sheet products.

The thermocompression bonding may be performed in a gas atmosphere such as air, nitrogen, or argon. The heating temperature is required to be higher than the glass transition temperature of the thermoplastic polyimide, preferably about 20 ° C. higher than the glass transition temperature, and is usually 100 to 400 ° C., preferably 150 to 300 ° C. It may be performed between ° C. In addition, the heating time is preferably 0.01 seconds or more and 15 hours or less, and the heating pressure is preferably in the range of 0.5;! To 30 MPa, usually 0.5 to OMPa.

[0103] Further, after thermocompression bonding, post-treatment may be performed using an autoclave or the like for the purpose of further improving the adhesion of the metal laminate. Post-processing is performed under the following conditions. The post-treatment temperature is usually from 150 to 400 ° C, preferably from 200 to 350 ° C, the treatment time is from 1 minute to 50 hours, and the pressure is from normal pressure to 3 MPa. It is preferable to prevent oxidation of the metal foil by replacing the inside of the autoclave apparatus with an inert gas such as vacuum, nitrogen or argon. Good.

[0104] In the method for producing a metal laminate of the present invention, when a polyimide resin composition varnish (a solution containing a polyamic acid and an imide oligomer) is applied to a metal foil, a roll coater, a die coater, a gravure It can be applied using a general coating apparatus such as a coater, dip coater, spray coater, comma coater, curtain coater, bar coater, etc., and can be appropriately selected according to the viscosity and coating thickness of the varnish.

[0105] The applied varnish of the polyimide resin composition can be appropriately dried using a roll support using an electric heating, oil calorie, hot air or infrared ray as a heat source, an air float type drying furnace, or the like. it can. If necessary, the dry atmosphere may be replaced with a gas such as nitrogen, argon or hydrogen in addition to air to prevent resin alteration or discoloration due to metal foil oxidation! /.

It is preferable to dry the varnish of the applied polyimide resin composition in a temperature range of 60 to 600 ° C., preferably by increasing the temperature stepwise. It is possible to prevent foaming from the coating film during drying and unevenness on the film surface after drying, and to obtain a resin film with a uniform film thickness and excellent dimensional stability. Preferred for formation. The drying time may be appropriately selected from about 0.05 to 500 minutes.

[0106] Adhesive sheet

The adhesive sheet of the present invention has a resin film and a resin layer made of a cured product of the resin composition of the present invention formed on one or both surfaces of the film. The resin film can be a known resin film, and the type is not particularly limited, but the above-mentioned polyimide film can be preferably exemplified. The method for forming the resin layer on one or both sides of the resin film is not particularly limited, but preferably, as shown in the method for producing a metal laminate, a varnish of a polyimide resin composition is applied and dried. Can be formed. Example

[0107] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The scope of the present invention is not construed as being limited in any way by this! /.

[0108] In the examples and comparative examples, each physical property was measured by the following method.

[0109] Evaluation of polyamic acid 1) Logarithmic viscosity (7] inh): Add polyamic acid varnish into N, N-dimethylacetamide solvent and adjust the solids concentration to 0.5g / dl, then set to 35 ° C Measured in a constant temperature bath

Yes

Using a 2 ^ -type viscometer (! ^-1058, Toki Sangyo Co., Ltd.), it was measured with a 3 ° cone rotor at 25 ° C-constant conditions.

[0110] Evaluation of imide oligomers

1) Logarithmic viscosity (7] inh): The imide oligomer was added into N, N-dimethylacetamide solvent to adjust the imide oligomer solid content concentration to 0.5 g / dl. The solution was adjusted to 35 ° C and the logarithmic viscosity was measured.

2) Molecular weight (weight average molecular weight Mw, number average molecular weight Mn): GPCsystem — 21H series (detector; RI, developing solvent; tetrahydrofuran, flow rate; lml / min, column temperature; 40 ° C) manufactured by Shodex It was measured.

3) Glass transition temperature (Tg): Measured in a nitrogen atmosphere using a DSC60 series thermal analyzer manufactured by Shimadzu Corporation.

[0111] Evaluation of polyimide resin composition

1) Glass transition temperature (Tg): Measured in a nitrogen atmosphere using a thermal analyzer DSC60 series manufactured by Shimadzu Corporation.

2) Desmear speed: A polyamic acid solution was coated on a glass plate and heated at 300 ° C for 4 hours in a nitrogen atmosphere to prepare a polyimide film. A sample with a size of 6 X 2 cm ² was cut out and used as a measurement sample. The etching solution was prepared by mixing 50 g of MAYUUTIZER 9275 (manufactured by Nihon Mcdermid), 50 ml of MAKIUTAZER 9276 (manufactured by Nihon Mcdermid) and ion-exchanged water so that the total amount was 1 L. The sample was immersed in an etching solution for 15 minutes, washed with water, dried, and calculated from the weight change before and after immersion.

3) Volatility: A solution was prepared by adding 33 parts by weight of an imide oligomer to a polyamic acid varnish to 100 parts by weight of a polyamic acid solid, and cast on a glass substrate. The film obtained by heating at 240 ° C for 15 minutes in a nitrogen atmosphere was peeled off and cut into 5 cm squares. This film was placed in a petri dish, heated at 280 ° C for 30 minutes in a nitrogen atmosphere, and cooled to room temperature. Observe the amount of deposits on the petri dish top, ○ (no deposits), △ Crab precipitates) and X (precipitates almost entirely) were evaluated.

[0112] Evaluation of metal laminates

1) Peel strength: Measured according to JIS C-6471. Prepare a sample with a length of 50 mm and a width of 1 mm parallel to the flow direction of the metal foil, and insulate the metal foil at a 90-degree angle in an environment of 23 ° C and relative humidity of 50%. The layer was peeled off at a peeling speed of 50 mm / min, and the stress was measured.

2) Solder heat resistance temperature: Measured according to IPC-TM-650 (The institute for Interconnecting and Packaging Electronic Circuits) No. 2. 4. 13 240. C force, et al. 340. The maximum temperature at which no blistering or discoloration of the metal / polyimide interface occurs at 10 ° C intervals between C was defined as the solder heat resistance temperature. Samples were stored for 48 hours in an environment of 85 ° C and 85% relative humidity.

[0113] The chemical structure was confirmed using a nuclear magnetic resonance (NMR) apparatus EX400 manufactured by JEOL Ltd.

[0114] Abbreviations of solvents, diamines, tetracarboxylic dianhydrides, and dicarboxylic anhydrides used in Examples and Comparative Examples are as follows.

1) Solvent:

DMAc: N, N-dimethylacetamide

2) Jimin:

APB: 1,3-bis (3-aminophenoxy) benzene,

APB-R: 1,3-bis (4-aminophenoxy) benzene,

m-BP: 4,4'-bis (3-aminophenoxy) biphenol,

3) Tetracarboxylic dianhydride

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

DSDA: bis (3,4-dicarboxyphenol) sulfone dianhydride,

ODPA: bis (3,4-dicarboxyphenyl) ether dianhydride,

BPDA: 3,3 ', 4,4, -biphenyltetracarboxylic dianhydride,

PMDA: pyromellitic dianhydride,

4) Dicarboxylic anhydride: MA: Maleic anhydride

NDA: Nadic anhydride

[0115] [Synthesis Example 1 1]

Synthesis of polyamic acid varnish

After charging DMAc (991g) as a solvent into a vessel equipped with a stirrer and nitrogen introduction tube, APB (146.25g) and APB-R (61.39g) are charged into this container and dissolved. Stir at room temperature. Next, BTDA (219.92 g) was charged and stirred at 50 ° C. for 6 hours to obtain a polyamic acid varnish.

The obtained polyamic acid varnish had a polyamic acid solid content of 30 wt%, a logarithmic viscosity of 0 · 61 dl / g, and an E-type viscosity at 25 ° C. of 13000 mPa ′S.

[0116] [Synthesis Example 1 2 ~ ;!

A polyamic acid varnish was synthesized in the same manner as in Synthesis Example 1, except that the types of tetracarboxylic dianhydride, diamine, and molar ratio were changed to those shown in Table 1. The results are shown in Table 1 together with Synthesis Example 1.

[0117] [Table 1]

Tetracarboxylic acid 亍 tracarponic acid A / B C / D A + B / C + D 1) inh E-type viscosity Synthesis example Diamine C Diamine D

Dianhydride A Dianhydride B [mol / mol] [mol / mol] [mol / mol] [D Ac, dl / g] [mPa-S]

1-1 BTDA ― 10/0 APB APB- 7/3 0.975 / 1.000 0.61 13,000

1-2 BTDA 1 10/0 APB ― 10/0 0.975 / 1.000 0.60 12,500

1-3 BTDA 1 10/0 APB APB-R 9/1 0.975 / 1.000 0.62 13,500

1-4 BTDA 1 10/0 APB APB-R 5/5 0.975 / 1.000 0.62 13,400

1-5 BTDA One 10/0 One APB-R 0/10 0.975 / 1.000 0.61 13,000

1-6 BTDA 1 10/0 APB APB-R 7/3 0.995 / 1.000 0.83 42,000

1-7 BTDA ― 10/0 APB APB-R 7/3 0.995 / 1.000 0.50 3,400

1-8 BTDA ― 10/0 APB APB-R 7/3 1.000 / 1.000 2.30 ≥ 100,000

1-9 BTDA 1/0 APB APB-R 7/3 0.945 / 1.000 0.38 2,100

1-10 BTDA 1/0 APB APB-R 7/3 0.890 / 1.000 0.11 400

1-11 BTDA DSDA 8/2 APB APB-R 7/3 0.975 / 1.000 0.59 10,000

1-12 BTDA DSDA 6/4 APB APB-R 7/3 0.975 / 1.000 0.58 8,100

1-13 BTDA DSDA 3/7 APB APB-R 7/3 0.975 / 1 flat 0.60 9,500

1-14 One DSDA 0/10 APB APB-R 7/3 0.975 / 1.000 0.49 3,200

1-15 ― DSDA 0/10 One APB-R 0/10 0.975 / 1.000 0.52 4,000

Synthesis of imide oligomers

A PB (29. 23 g, 0. lOmol), ODPA (15. 51 g, 0.05 mol), maleic anhydride (hereinafter MA) in a flask equipped with a stirrer, nitrogen inlet tube, Dean Stark, condenser and thermometer (11. 77 g, 0.12 mol), DMAc (132 g) as a solvent, and toluene (42 g) as a dehydrated azeotropic solvent. The solution was then stirred and heated to 130-; 135 ° C while passing nitrogen gas. As the internal temperature reached around 130 ° C, evaporation of toluene and water occurred. A part of them is condensed in a cooler, water and toluene are separated by Dean Stark, and then only toluene is refluxed into the system, and a part of the nitrogen gas is circulated from the upper part of the cooling pipe to the outside of the system. Left.

[0119] After the reaction for 7 hours, the reaction vessel was cooled to terminate the polymerization reaction. The reaction mixture was charged into methanol to precipitate an imide oligomer, and then washed with methanol. Thereafter, it was dried at 90 ° C. for 12 hours under a nitrogen flow to obtain 39.59 g of an imide oligomer (yield 78%). The resulting imide oligomer has a logarithmic viscosity of 7] inh of 0 · 07 dl / g, GPC measurement number average molecular weight (Mn) of 2100, weight average molecular weight (Mw) of 3100, and polydispersity as an indicator of molecular weight distribution. Degree Mw / Mn was 1.5.

[0120] In order to confirm the structure of the obtained imide oligomer, the formation of an imide oligomer having the target structure was confirmed by NMR and FD-MS measurements. The imide oligomer had a Tg of 118 ° C as measured by DSC. When this imide oligomer was mixed with DMAc at a concentration of 40 wt% at room temperature, it quickly dissolved.

[0121] [Synthesis Example 2-2 to 2-7]

An imide oligomer was synthesized and evaluated in the same manner as in Synthesis Example 16 except that the types of tetracarboxylic dianhydride and diamine were changed to those shown in Table 2. The results are shown in Table 2 together with Synthesis Example 2-1.

[0122] [Synthesis Example 2-8]

A PB (29.23 g, 0.10 mol), ODPA (15.51 g, 0.05 mol), NDA (9.85 g, 0) were added to a flask equipped with a stirrer, nitrogen inlet tube, Dean Stark, condenser and thermometer. 06 mol) and DMAc (163 g) as solvent.

The resulting solution was stirred and heated to 160 ° C. while passing nitrogen gas. Internal temperature is 160 ° C A small amount of DMAc and water evaporation occurred as it reached the vicinity. A part of them was condensed in a cooler and extracted from the Dean Stark, and a part was distilled out of the system from the upper part of the cooling pipe together with the flowing nitrogen gas. After 2 hours, NDA (9.85 g, 0.06 mol) was charged into the reactor and further heated for 4 hours. Thereafter, the reaction vessel was cooled to stop the polymerization reaction.

[0123] The reaction mixture was charged into methanol to precipitate an imide oligomer, which was washed with methanol. The washed product was dried at 90 ° C. for 12 hours under a nitrogen stream to obtain 41.81 g of an imide oligomer (yield 73%). Logarithmic viscosity η inh of the obtained imide oligomer is 0.007 dl / g, number average molecular weight Mn by GPC measurement is 1500, weight average molecular weight Mw is 2100, polydispersity index of molecular weight distribution Mw / Mn is 1.4 Met.

[0124] In order to confirm the structure of the imide oligomer, the formation of an imide oligomer having the target structure was confirmed by NMR and FD-MS measurements. The Tg of the imide oligomer measured by DSC was 120 ° C. When this imide oligomer was mixed with DMAc at a concentration of 40 wt% at room temperature, it quickly dissolved.

[0125] [Synthesis Example 2—9 to 2-14]

Imide oligomers were synthesized and evaluated in the same manner as Synthesis Example 2-6, except that the types of tetracarboxylic dianhydride and diamine were changed to those shown in Table 2. The results are summarized in Table 2.

[0126] [Synthesis Examples 2-15 and 2-16]

Synthesis of bisimide

They were synthesized and evaluated by the method described in JP-A-4-99764. The results are summarized in Table 2.

[0127] [Table 2]

[Example 1]

In a polyamide acid tank, add the polyamic acid varnish obtained in Synthesis Example 11 and the imide oligomer obtained in Synthesis Example 2-1 to a flask equipped with a stirrer, a nitrogen inlet tube and a thermometer. The polyimide acid solid content was 100 parts by weight, and the imide oligomer was 33 parts by weight.

Heated to 40 ° C and mixed, and DMAc was charged to obtain a light brown transparent solution having a viscosity of 100 1 000 in an E-type viscometer. The Tg of the film obtained by casting the resulting solution was 177 ° C. In addition, the desmear rate measured according to the above procedure was ² ug / cm ² / min, and the evaluation of the volatility test was “good”.

[0129] Next, a commercially available polyimide resin film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 100E) Apply the above solution to both sides of N) with a roll coater and dry at 70 ° C for 5 minutes, 100 ° C for 2 minutes, 140 ° C for 2 minutes, 180 ° C for 2 minutes, and 220 ° C for 10 minutes. The thickness after drying was 4 m. In this manner, a polyimide insulating film having a polyimide resin cured material layer laminated on both surfaces of the resin film was obtained.

[0130] Copper foil (made by Furukawa Circuit Oil Co., Ltd., product name: F1-WS, thickness 9 m) is directly stacked on the polyimide resin cured layer of the resulting polyimide insulation film and covered with silicon rubber. The roll laminator was used for bonding at 240 ° C under a pressure of 1.4 MPa. Thereafter, annealing was performed for 4 hours in a batch autoclave at a temperature of 320 ° C. in a nitrogen atmosphere to obtain a polyimide metal laminate. The peel strength of the polyimide metal laminate was 1. OkN / m, and the solder heat resistance temperature was 340 ° C.

[0131] [Examples 2 to 29]

A polyimide resin composition was synthesized and evaluated in the same manner as in Example 1 except that the types of polyamide acid varnish and imide oligomer were changed as shown in Table 3A or Table 3B, and a polyimide metal laminate was prepared and evaluated. The results are shown in Table 3A or Table 3B.

[0132] [Comparative Example 1]

A polyimide resin composition was synthesized and evaluated in the same manner as in Example 1 except that no imide oligomer was used, and a polyimide metal laminate was further prepared and evaluated. The results are shown in Table 3A.

[0133] [Comparative Examples 2 and 3]

A polyimide resin composition was synthesized and evaluated in the same manner as in Example 1 except that the type of polyamic acid varnish and the crosslinkable group-containing additive bisimide was changed to those shown in Table 3B. The body was made and evaluated. The results are shown in Table 3B.

[Table 3A] ^ l imide General formula (2) Polyamic acid solids / τ «Desmear speed Volatility Peel strength Solder heat resistance) ¾

[] ¾3B / ^ So

1 Imidoligomer in oligomers [arrangement ratio] [. c] and g / cm2 / min] Test [kN / m] Temperature [° c] Example 1 Synthesis Example 1-1 Synthesis Example 2-1 1 100/33 177 2 ○ 1.0 340 Example 2 Synthesis Example 1-2 Synthesis Example 2-1 1 100/33 168 <1 O 1.0 340 Example 3 Synthesis Example 1-3 Synthesis Example 2-1 1 100/33 172 <1 0 1.0 340 Example 4 Synthesis Example 1-4 Synthesis Example 2- 1 1 100/33 1 6 3 ○ 1.0 340 Example 5 Synthesis example 1-5 Synthesis example 2-1 1 100/33 205 5 ○ 0.8 300 Example 6 Synthesis example 1-6 Synthesis example 2-1 1 100/33 182 2 ○ 1.0 340 Example 7 Synthesis Example 1-7 Synthesis Example 2-1 1 100/33 172 2 0 1.0 340 Example a Synthesis Example 1-8 Synthesis Example 2-1 1 100/33 185 2 ○ 1.0 300 Implementation Example 9 Synthesis Example 1-9 Synthesis Example 2-1 1 100/33 165 3 0 1.0 320 Example 10 Synthesis Example 1-10 Synthesis Example 2-1 1 100/33 155 3 ○ 0.6 300 Example 11 Synthesis Example 1- 11 Synthesis example 2-1 1 100/33 180 3 ○ 1.0 330 Example 12 Synthesis example 1-12 Synthesis example 2-1 1 100/33 182 3 ○ 1.0 320 Example 13 Synthesis example 1-13 Synthesis example 2-1 1 100/33 186 4 ○ 1.0 300 Example 14 Synthesis example 1-14 Synthesis example 2-1 1 100/33 190 4 ○ 1.0 290 Ratio Example 1 Synthesis example 1-15 ― ― 100/0 265 4 ○ 0.2 290 Example 15 Synthesis example 1-Τ Synthesis example 2-1 1 100/11 190 3 ○ 0.8 300 Example 16 Synthesis example 1-1 Synthesis example 2 -1 1 100/150 156 <1 厶 1.0 320

o o o O o O o o O o O O o

E

\ o o o o o o o o o o o o o o Pide quick strength volatility Doic acid generalized type Li-form (Rumimi /) Sua 2 ——

Podoacid Limia

Degree [°] Temperature c O O O ○ ○ O O o ○ ○ O ○ o

\ E

E o O o

卜卜 m

M w TO ∞

1 t \ t ヽ t

o o o o o o o o o o O o o o o

* π o o o o o o o o o o o o o o o

V o ε

+ O o u

o

1 to

h 'w

V

An

Aa <

cn o ∞

Tsutsumi 蜀 m m &

m As shown in Table 3, the metal laminate produced using the resin composition containing no imide oligomer (Comparative Example 1) is inferior in peel strength. Therefore, the performance as an adhesive may not be sufficient.

Resin compositions containing bisimide instead of imide oligomer (Comparative Examples 2 and 3) are inferior to the evaluation results of the volatility test, and part of the composition (bisimide) is exposed to high temperature environments. Is considered to sublimate.

[0135] On the other hand, as shown in Examples 1 to 14; the resin composition containing the polyamide acid varnish obtained in Synthesis Examples 1-1 to 14-14 and the imide oligomer is volatile. The peel strength of the metal laminate produced by using it, which is highly evaluated by the property test, is sufficient. In addition, as shown in Examples 15 and 16, regardless of the amount ratio of the polyamic acid solid content and the imide oligomer, the resin composition of the present invention has an excellent participatory strength. If it is too high (too little imide oligomer), the peel strength may be inferior, and if the amount ratio of imide oligomer is too high, the evaluation of the volatility test may be lowered.

[0136] Also, as shown in Examples 17 to 29, the resin composition containing polyamic acid and the imide oligomer obtained in Synthesis Example 2-2 to 2-14 is also volatile. The peel strength of the metal laminate produced using the high test evaluation is sufficient.

Industrial applicability

[0137] The polyimide resin composition of the present invention can be used for heat-resistant films, flexible printed boards, semiconductor packages, and the like.

[0138] This application claims priority based on application number JP2006-244946 filed on September 11, 2006 (Japanese Patent Application No. 2006-244946). All the contents described in the application specification and drawings are incorporated herein by reference.

Claims

Claims A polyimide resin containing a repeating unit represented by the following general formula (11) and a repeating unit represented by the general formula (12), and an imide oligomer represented by the following general formula (2): A polyimide-based resin composition to contain.

[Chemical 1]

[In the formulas (1 1) and (1 2)

A and A are respectively the following formulas (al) or (a2), which may be the same as or different from each other:

1 2

You may

B and B are the following formulas (bl) or (b2), respectively,

1 2

You may go on]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[In Formula (2),

A is any one of the following formulas (cl) to (c4),

Three

B is any of the following formulas (dl) to (d4),

Three

Z is the following formula (el) or (e2),

1 is an integer between! And 5]

[Chemical 5]

[In the formulas (cl) to (c4), X is a direct connection,-O S CO COO

7 12

Selected from the group consisting of C (CH) C (CF) SO --NHCO

3 2 3 2 2

Even if they are the same, they can be different.]

[Chemical 6]

[In formulas (dl) to (d4), Y is a direct connection, _ o S CO COO

7 12

Selected from the group consisting of C (CH) C (CF) SO --NHCO

3 2 3 2 2

Even if they are the same, they can be different.]

[Chemical 7]

[In formula (e 1) or (e2)! / R 1 ~! Are selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other! /

R is O S—, —CH 2 C (CH 2) CO, or one COO

5 2 3 2

]

One of A in the general formula (1 1) and A in the general formula (1 2)

1 2

2. The polyimide resin composition according to claim 1, wherein one is (al) and the other is (a2). 2. The polyimide resin composition according to claim 1, wherein 1 in the general formula (2) is 1. 2. The polyimide resin composition according to claim 1, comprising 5 parts by weight or more and 100 parts by weight or less of the imide oligomer represented by the general formula (2) with respect to 100 parts by weight of the polyimide resin.

2. The polyimide resin composition according to claim 1, wherein the glass transition temperature is in the range of 100 ° C. or more and 300 ° C. or less.

In the general formula (2),

A is the following formula (c5) or (c6),

Three

B is also selected from the following formula (dl), and group force consisting of (d5) to (dl0),

Three

Z is (e3) or (e4),

1 is an integer from;! To 5;

The polyimide resin composition according to claim 1.

[Chemical 8]

[Chemical 9]

[Chemical 10]

[R and R are defined as in the above formula (e2)]

[7] A polyamic acid comprising a repeating unit represented by the following general formula (3-1) and a repeating unit represented by the following general formula (3-2),

An imide oligomer represented by the general formula (2), and

A mixture, optionally containing a solvent.

[Chemical 11]

.. Ο Ο

(3-1)

^ΗΟ τί ίΓ ^ΟΗ

ο ο u ο ο _u

(3-2)

ΗΟ frOH

ο ο

[In the formulas (3-1) and (3-2),

Α and A are respectively the following formulas (al) or (a2), which may be the same or different from each other.

B and B are the following formulas (bl) or (b2), respectively, You may go on]

[Chemical 12]

[Chemical 13]

[Chemical 14]

• ·, (2)

[In Formula (2),

A is any one of the following formulas (cl) to (c4),

Three

B is any of the following formulas (dl) to (d4),

Three

Z is the following formula (el) or (e2),

1 is an integer from:! To 5]

[Chemical 15]

[In the formulas (cl) to (; c4), X is a direct connection, 101, 1S—, 1CO—, 1C001,

7-12

— A group force consisting of C (CH) ―, -C (CF) ―,-SO ―, and one NHCO ―

3 2 3 2 2

Even if they are the same, they can be different.]

[Chemical 16]

[In formulas (d :!) to (d4), Y is a direct connection, —Ο— —S— —CO— —COO

7-12

— C (CH) ― C (CF) ―-SO― NHCO

3 2 3 2 2

Even if they are the same, they are different! /

[Chemical 17]

[In formula (e 1) or (e2)! /

R is selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 13 carbon atoms

1

May be the same or different from each other,

R is O—S——CH C (CH 2) CO—, or one COO—.

5 2 3 2

]

[8] A method for producing a cured polyimide resin, comprising the step of heating the mixture according to claim 7 to cause an imidization reaction.

[9] A film comprising a cured product of the polyimide resin composition according to claim 1.

[10] A metal laminate comprising a metal layer and a resin layer, wherein at least one of the resin layers is a cured product of the polyimide resin composition according to claim 1.

[11] A polyimide film, a polyimide layer formed on one or both sides of the polyimide film, a metal layer laminated on one or both of the polyimide layers,

2. A metal laminate in which the polyimide layer in contact with the metal layer is a resin layer made of a cured product of the polyimide resin composition according to claim 1.

[12] An adhesive sheet having a resin film and a resin layer made of a cured product of the polyimide resin composition according to claim 1 laminated on one or both surfaces of the resin film.