JP5166364B2 - Polyimide resin composition and metal laminate using the same - Google Patents

Description

  The present invention relates to a polyimide resin composition and a method for producing the same, a metal laminate having a resin layer obtained from the resin composition, an adhesive sheet, and the like.

  Polyimide is excellent in heat resistance, chemical resistance, mechanical strength, electrical characteristics, and the like, and is therefore used in aircraft structural materials and cable coating materials. Polyimide is also often used as a heat-resistant adhesive in the electronic field such as flexible printed circuit boards and semiconductor packages.

  Such polyimide heat-resistant adhesives are required to have low-temperature adhesiveness in addition to heat resistance in processing. A resin composition composed of a polyimide resin having a siloxane unit, an epoxy resin, and a phosphate ester plasticizer has been proposed as one having excellent low-temperature adhesiveness (see, for example, Patent Document 1). However, since components such as polyimide resin, epoxy resin, and plasticizer include aliphatic units, there is a problem that the thermal decomposition temperature is low.

  On the other hand, a resin having a specific polyamic acid and a bismaleimide compound has been proposed as one having sufficient adhesive strength and heat resistance (see, for example, Patent Documents 2 to 4). However, in order to obtain adhesiveness, a temperature of 300 ° C. or higher may be required, and the low-temperature adhesiveness is still insufficient.

  As an imide compound having a plurality of crosslinkable groups such as a maleimide group in a molecular chain, a compound having a skeleton in which benzene rings are bonded by a methylene group has been proposed (for example, see Patent Documents 5 and 6). However, it has not been known that these crosslinkable group-containing imide compounds are used in combination with other polyimide resins for bonding metal to metal or metal to resin.

  A resin composed of a specific bismaleimide compound and a polyamic acid has been proposed as one that improves low-temperature adhesion (see, for example, Patent Document 7). However, the resin layer of the metal laminate is required to have higher solder heat resistance and dimensional stability.

  That is, in recent years, lead-free solder having a higher melting point than that in the past has been used in electronic component mounting. For this reason, the substrate is required to have high solder heat resistance. In particular, rigid flex, flexible multilayer substrates, and the like are insufficient in reliability at conventional solder heat resistance temperatures, and therefore are required to have solder heat resistance at higher temperatures.

  When a flexible substrate is used for a chip-on-film (COF), an inner lead bonder or a flip chip bonder is used to connect the chip and the metal wiring at a high temperature of 300 ° C. or higher by Au—Au bonding or Au—Sn bonding. To do. For this reason, the flexible substrate used for COF is required to have high solder heat resistance that does not deform even at high temperatures. Further, in addition to the thinning of the flexible substrate, the density of the wiring has been increased, and the distance between the metal wirings has been reduced. For this reason, when the flexible substrate is processed (joined or the like) at a high temperature, problems such as contact between metal wirings due to deformation of the resin layer or the like are likely to occur. For this reason, the flexible substrate is required to have high dimensional stability.

JP-A-10-212468 JP-A-1-289862 JP-A-6-145638 Japanese Patent Laid-Open No. 6-192939 JP-A-62-131030 JP-A-63-88178 Japanese Patent Laid-Open No. 2004-209962

  However, a resin composition having solder heat resistance and dimensional stability that satisfies the above-mentioned requirements while having sufficient low-temperature adhesiveness has not yet been proposed. The present invention has been made in view of such circumstances, and is a polyimide resin composition that can be bonded under relatively low temperature thermocompression bonding conditions (has low temperature adhesiveness) and has high solder heat resistance and dimensional stability. The purpose is to provide goods.

〔一般式（１）において、
Ａは、下記式で表される基から選ばれる基であり、

（Ｘ_１〜Ｘ_６はそれぞれ、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＳＯ_２−または−ＮＨＣＯ−を表す）

Ｂは、下記式で表される基から選ばれる基である。

（Ｙ_１〜Ｙ_６はそれぞれ、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＳＯ_２−または−ＮＨＣＯ−を表す）〕

（Ｒ_１〜Ｒ_４はそれぞれ、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表し；Ｒ_５は、−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−または−ＣＯ−を表し；Ｒ_６は、水素原子またはフェニル基を表す）

〔一般式（２）において、ｎは０より大きく１０以下の実数を示し、異なるｎを有する化合物の混合物であってもよく、Ｚ_１〜Ｚ_３はそれぞれ、下記式で表される基から選ばれる基である

（Ｒ_７〜Ｒ_１０はそれぞれ、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表し；Ｒ_１１は−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−または−ＣＯ−を表し；Ｒ_１２は、水素原子またはフェニル基を表す）〕 The first of the present invention is the following polyimide resin composition.
[1] A polyimide having a repeating structural unit represented by the following general formula (1) and having a molecular end selected from a group represented by the following general formula (W1); A polyimide resin composition comprising: an imide oligomer represented.

[In general formula (1),
A is a group selected from the groups represented by the following formulae,

(X _{1 to} X ₆ are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —. Or represents -NHCO-)

B is a group selected from the groups represented by the following formulae.

(Y _{1 to} Y ₆ are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —. Or -NHCO-)

(R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₅ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) _2. - it represents or -CO- a; _{R 6} represents a hydrogen atom or a phenyl group)

[In General Formula (2), n represents a real number greater than 0 and 10 or less, and may be a mixture of compounds having different n, and Z _{1 to} Z ₃ are each selected from the groups represented by the following formulae: Group

(R _{7 to} R ₁₀ each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₁₁ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —. Or represents —CO—; R ₁₂ represents a hydrogen atom or a phenyl group)]

（Ｒ_１〜Ｒ_６は、前述の一般式（Ｗ１）におけるＲ_１〜Ｒ_６と同義である）
［３］ 前記一般式（１）で表されるポリイミド１００重量部に対し、
前記一般式（２）で表されるイミドオリゴマーを、５重量部以上１００重量部以下含有する、［１］または［２］に記載のポリイミド樹脂組成物。
［４］ ポリイミド樹脂組成物のガラス転移温度が、１００℃以上３５０℃以下である、［１］〜［３］のいずれかに記載のポリイミド樹脂組成物。
［５］ 前記一般式（２）において、
Ｚ_１〜Ｚ_３が、下記式で表される基のいずれかである、［１］〜［４］のいずれかに記載のポリイミド樹脂組成物。

［６］ 前記一般式（２）で表されるイミドオリゴマーにおけるｎが０より大きく６以下の実数であり、かつｎが０である化合物の含有率が４０〜６０モル％である、［１］〜［５］のいずれかに記載のポリイミド樹脂組成物。
［７］ 前記一般式（１）において、
Ａは、下記式で表される基から選ばれる基であり、

Ｂは、下記式で表される基から選ばれる基であり、

前記ポリイミドの分子末端は、下記式で表される基から選ばれる基である、

［１］または［２］に記載のポリイミド樹脂組成物。 [2] The polyimide resin composition according to claim 1, wherein the molecular terminal of the polyimide is a group selected from the group represented by the following general formula (W1 ^′ ).

(R _{1 to} R ₆ are synonymous with R _{1 to} R ₆ in General Formula (W1)).
[3] For 100 parts by weight of the polyimide represented by the general formula (1),
The polyimide resin composition according to [1] or [2], which contains 5 parts by weight or more and 100 parts by weight or less of the imide oligomer represented by the general formula (2).
[4] The polyimide resin composition according to any one of [1] to [3], wherein a glass transition temperature of the polyimide resin composition is 100 ° C. or higher and 350 ° C. or lower.
[5] In the general formula (2),
The polyimide resin composition according to any one of [1] to [4], wherein Z _{1 to} Z ₃ are any of groups represented by the following formulae.

[6] In the imide oligomer represented by the general formula (2), n is a real number greater than 0 and 6 or less, and the content of the compound in which n is 0 is 40 to 60 mol%. [1] -The polyimide resin composition in any one of [5].
[7] In the general formula (1),
A is a group selected from the groups represented by the following formulae,

B is a group selected from the groups represented by the following formulae,

The molecular terminal of the polyimide is a group selected from the group represented by the following formula:

The polyimide resin composition as described in [1] or [2].

The second of the present invention is a film containing a polyimide resin composition, a metal laminate, an adhesive sheet and the like.
[8] A film comprising the polyimide resin composition according to any one of [1] to [7].
[9] A metal laminate including a metal layer and a resin layer, wherein at least one of the resin layers is a layer obtained from the polyimide resin composition according to any one of [1] to [7]. , Metal laminate.
[10] The resin layer includes a polyimide film and a polyimide layer formed on one or both sides of the polyimide film, and the polyimide layer in contact with the metal layer is any one of [1] to [7]. The metal laminate according to [9], which is a layer obtained from the polyimide resin composition according to.
[11] An adhesive sheet having a resin film and a layer formed on one or both sides of the resin film and including the polyimide resin composition according to any one of [1] to [7].

〔一般式（９）中、
Ａは、下記式で表される基から選ばれる基であり、

（Ｘ_１〜Ｘ_６はそれぞれ、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＳＯ_２−または−ＮＨＣＯ−を表す）

Ｂは、下記式で表される基から選ばれる基であり、

（Ｙ_１〜Ｙ_６はそれぞれ、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＳＯ_２−または−ＮＨＣＯ−を表す）〕

（Ｒ_１〜Ｒ_４はそれぞれ、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表し；Ｒ_５は、−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−または−ＣＯ−を表し；Ｒ_６は、水素原子またはフェニル基を表す）

〔一般式（２）中、ｎは０より大きく１０以下の実数を示し、異なるｎを有する化合物の混合物であってもよく、
Ｚ_１〜Ｚ_３は、下記式で表される基から選ばれる基である

（Ｒ_７〜Ｒ_１０はそれぞれ、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表し；Ｒ_１１は、−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−または−ＣＯ−を表し；Ｒ_１２は、水素原子またはフェニル基を表す）〕
［１３］ ［１２］に記載のポリアミド酸溶液を加熱してイミド化するステップを含む、ポリイミド樹脂組成物の製造方法。
［１４］ 下記一般式（４）で表されるテトラカルボン酸二無水物と、下記一般式（５）で表されるジアミンとを、下記一般式（６）で表されるジカルボン酸無水物の存在下または非存在下において重縮合反応させることにより、前記一般式（９）で表されるポリアミド酸を得るステップと、

〔一般式（４）〜（６）中、
ＡおよびＢは、前記一般式（９）におけるＡおよびＢと同義であり、
Ｄは、下記式で表される基から選ばれる基である。

（Ｒ_１〜Ｒ_４はそれぞれ、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表し；Ｒ_５は、−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−または−ＣＯ−を表し；Ｒ_６は、水素原子またはフェニル基を表す）〕

前記ポリアミド酸溶液を加熱してイミド化するステップとを含む、ポリイミド樹脂組成物の製造方法であって、
前記テトラカルボン酸二無水物、前記ジアミン、および前記ジカルボン酸無水物の仕込み比を、下記式（Ａ）および式（Ｂ）を満たすようにする、［１３］に記載のポリイミド樹脂組成物の製造方法。

（Ｍ１：テトラカルボン酸二無水物のモル数、Ｍ２：ジアミンのモル数、Ｍ３：ジカルボン酸無水物のモル数） The third of the present invention is a polyamic acid solution and a method for producing a polyimide resin composition using the same.
[12] Polyamic acid containing a repeating unit represented by the general formula (9) and having a molecular end selected from the following general formula (W2); an imide oligomer represented by the general formula (2); A polyamic acid solution.

[In general formula (9),
A is a group selected from the groups represented by the following formulae,

(X _{1 to} X ₆ are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —. Or represents -NHCO-)

B is a group selected from the groups represented by the following formulae,

(Y _{1 to} Y ₆ are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —. Or -NHCO-)

(R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₅ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) _2. - it represents or -CO- a; _{R 6} represents a hydrogen atom or a phenyl group)

[In General Formula (2), n represents a real number greater than 0 and 10 or less, and may be a mixture of compounds having different n,
Z _{1 to} Z ₃ are groups selected from groups represented by the following formulae.

(R _{7 to} R ₁₀ each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₁₁ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) _2. - or represents _{-CO-; R 12} represents a hydrogen atom or a phenyl group)]
[13] A method for producing a polyimide resin composition, comprising a step of heating and imidizing the polyamic acid solution according to [12].
[14] A tetracarboxylic dianhydride represented by the following general formula (4) and a diamine represented by the following general formula (5) are converted into a dicarboxylic anhydride represented by the following general formula (6). Obtaining a polyamic acid represented by the general formula (9) by performing a polycondensation reaction in the presence or absence;

[In general formula (4)-(6),
A and B are synonymous with A and B in the general formula (9),
D is a group selected from the groups represented by the following formulae.

(R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₅ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) _2. — Represents —CO—; R ₆ represents a hydrogen atom or a phenyl group)]

Heating the polyamic acid solution to imidize, and a method for producing a polyimide resin composition,
Manufacture of the polyimide resin composition as described in [13] which makes the preparation ratio of the said tetracarboxylic dianhydride, the said diamine, and the said dicarboxylic anhydride satisfy the following formula (A) and a formula (B). Method.

(M1: number of moles of tetracarboxylic dianhydride, M2: number of moles of diamine, M3: number of moles of dicarboxylic acid anhydride)

  According to the present invention, it is possible to provide a polyimide resin composition that can be bonded under relatively low temperature thermocompression bonding conditions and that has high solder heat resistance and dimensional stability. For this reason, a polyimide resin composition is preferably applicable as an adhesive for flexible printed circuit boards, for example.

1. Polyimide resin composition The polyimide resin composition of the present invention has good adhesiveness by having a low elastic modulus in a relatively low bonding temperature region; and excellent by having a high elastic modulus in a high temperature region. Obtains solder heat resistance and dimensional stability. The polyimide resin composition of this invention contains the polyimide represented by General formula (1), and the imide oligomer shown by General formula (2).

The polyimide contained in the polyimide resin composition of the present invention has a repeating unit represented by the general formula (1).

A in the general formula (1) is selected from divalent groups represented by the following formula. X _{1 to} X ₆ in the following formulas are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO. _2- or -NHCO-. X _{1 to} X ₆ contained in a plurality of A may be the same or different from each other.

  A in the general formula (1) may be a divalent group derived from an aromatic diamine. Examples of aromatic diamines include m-phenylene diamine, o-phenylene diamine, p-phenylene diamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3 '-Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 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-hexafur Oropropane, 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-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4- Bis (4-aminophenyl) 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-aminophenyl sulfide) benzene, 1,3-bis (4-aminophenyl sulfide) benzene, 1,4-bis (4-aminophenyl sulfide) ) Benzene, 1,3-bis (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-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] ether, bis 4- (4-aminophenoxy) 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) phenyl] sulfide, bis [4- (3-Aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [3- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] 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) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] 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-hexaph Oropuropan, etc. 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane. These may be used alone or in combination of a plurality of types. Of these, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3) are provided because they give flexibility to the polyimide resin composition. -Aminophenoxy) benzene is more preferred, and 1,3-bis (3-aminophenoxy) benzene and 1,3-bis (4-aminophenoxy) benzene are more preferred.

  A in the general formula (1) is derived from another aliphatic diamine other than the divalent group derived from the aromatic diamine compound for the purpose of imparting flexibility to the polyimide. One or more valent groups may be included.

  Examples of other aliphatic diamines include 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, 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-aminoethyl) 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 Colebis (3-aminopropyl) ether, triethyleneglycolbis (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, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1 , 3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) Cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bibi Su (aminomethyl) bicyclo [2.2.1] heptane and the like. These aliphatic diamine compounds may be used alone or in combination of two or more.

B in the general formula (1) is selected from tetravalent groups represented by the following formula. Y _{1 to} Y ₆ in the following formulas are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO. _2- or -NHCO-. Y ₁ to Y ₆ contained in the plurality of B may be the same or different from each other.

  B in the general formula (1) may be a tetravalent group derived from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid 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-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) Benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) Phenyl dianhydride, and the like 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride. Among these, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, and the like are preferable.

  B in the general formula (1) is a group other than a tetravalent group derived from the tetracarboxylic dianhydride for the purpose of improving or modifying the performance within a range that does not impair the desired physical properties. One or more tetravalent groups derived from other tetracarboxylic dianhydrides may be contained.

  Examples of other tetracarboxylic dianhydrides include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyl Phenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3, 6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like are included. These other tetracarboxylic dianhydrides may be used alone or in combination of two or more. In addition, tetracarboxylic dianhydrides in which some or all of the hydrogen atoms on the aromatic ring of these other tetracarboxylic dianhydrides are substituted with a group selected from the group consisting of a fluoro group or a trifluoromethyl group It may be used.

As described above, the polyimide contained in the polyimide resin composition of the present invention has a repeating unit represented by the general formula (1), but the terminal is a group selected from the group represented by the formula (W1). . R _{1 to} R ₄ in Formula (W1) are each a hydrogen atom or a halogen atom having 1 to 3 carbon atoms. R ₅ in Formula (W1) is —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —, or —CO—. R ₆ in Formula (W1) is a hydrogen atom or a phenyl group.

The molecular terminal of the polyimide can be a monovalent group derived from a dicarboxylic acid anhydride and an amino group, except when it is an amino group (H ₂ N—). Examples of dicarboxylic anhydrides include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride Acid, cis-5-norbornene-exo-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydro Phthalic anhydride, endo-bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 2,3-diethyl maleic anhydride, 4-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride Acids etc. are included.

  The molecular terminal of the polyimide may contain a monovalent group derived from another dicarboxylic acid anhydride and an amino group in addition to the monovalent group derived from the dicarboxylic acid anhydride and an amino group. Good.

  Examples of other dicarboxylic acid anhydrides include itaconic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, cis-aconitic anhydride, isobutenyl succinic anhydride, 2-octen-1-ylsuccinic acid, 2-dodecene -1-yl succinic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride, etc. Is included. These dicarboxylic acid anhydrides may be used alone or in combination of two or more.

  The number of repeating units represented by the general formula (1) is an integer of 2 or more, and is not particularly limited as long as the viscosity of the polyamic acid described later is satisfied. m is preferably 20 to 2,000. The polyimide in the polyimide resin composition of the present invention may be a mixture of polyimides having different m.

The polyimide in the polyimide resin composition of the present invention is represented by the following formula from the viewpoint of suppressing the reaction between the terminal amino group at the time of adhesion (at the time of plasticization) and a highly reactive group in the crosslinking agent or polyimide. It is preferably end-capped with any of the groups. Especially, when the polyimide has a highly reactive carbonyl group in the molecular structure, it is preferable that the terminal of a polyimide is sealed. Specifically, X _{1 to} X ₆ contained in A in the repeating structural unit represented by the general formula (1) is —CO—, —COO—, —SO ₂ — or —NHCO—; or B When Y ₁ to Y ₆ contained in is —CO—, —COO—, —SO ₂ — or —NHCO—, the molecular terminal of the polyimide is any of the groups represented by the following formula (W1 ′) Preferably there is.

  When the molecular terminal of the polyimide is sealed with a group represented by the formula (W1 ′), the reaction between the terminal of the polyimide (particularly the amino terminal) and the carbonyl group in the polyimide molecular structure can be suppressed. By suppressing the reaction, the elastic modulus of the resin composition when the polyimide resin composition is heated and plasticized (during low-temperature bonding) can be sufficiently lowered. Therefore, for example, when a polyimide resin composition is laminated on a metal foil and heated to obtain a metal laminate, the heated polyimide resin composition is efficiently embedded in the metal foil, and high adhesion can be obtained. Moreover, the said terminal group also has crosslinking reactivity. Therefore, the elastic modulus of the cured product of the polyimide resin composition can be increased and the linear expansion coefficient can be reduced.

  The imide oligomer contained in the polyimide resin composition of the present invention has a function as a plasticizer that lowers the glass transition temperature of the polyimide resin composition and a function as a curing agent (crosslinking agent). The imide oligomer is represented by the general formula (2).

  N in the general formula (2) represents a real number greater than 0 and equal to or less than 10, but is preferably a real number greater than 0 and equal to or less than 6. The imide oligomer is usually a mixture of compounds having different n, and is preferably a mixture. When the imide oligomer is a mixture, the content of the compound with n = 0 in the mixture is preferably 60 mol% or less. The compound with n = 0 in the formula (2) is often difficult to dissolve in a solvent, and therefore its content is preferably suppressed.

Z _{1 to} Z ₃ in the general formula (2) are each selected from groups represented by the following formulae. In the case of having a plurality of Z ₂ (when n is 2 or more), Z ₂ may be the same as or different from each other. R < ₇ > -R < ₁₀ > in a following formula is a hydrogen atom, a halogen atom, or a C1-C3 alkyl group, respectively. R ₇ and R ₈ , and R ₉ and R ₁₀ may be the same as or different from each other. R ₁₁ in the following formula is —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ — or —CO—. R ₁₂ in the following formula is a hydrogen atom or a phenyl group.

However, when the molecular terminal of the polyimide is an amino group (—NH ₂ ), Z _{1 to} Z ₃ in the general formula (2) are preferably groups other than the group represented by the following formula.

Z _{1 to} Z ₃ in the general formula (2) are each preferably selected from the groups represented by the following formulae. Furthermore, the structure of Z _{1 to} Z ₃ can be appropriately selected depending on the processing conditions of the polyimide resin composition. For example, an imide oligomer in which Z _{1 to} Z ₃ constitute a maleimide group undergoes a crosslinking reaction at a relatively low temperature, and thus is suitable for a resin composition processed at a low temperature. Moreover, since the imide oligomer in which Z _{1 to} Z ₃ constitute a 4-phenylethynylphthalimide group undergoes a crosslinking reaction with polyimide at a relatively high temperature, it is suitable for a resin composition processed at a high temperature.

  The imide group of the imide oligomer represented by the general formula (2) may be bonded to any carbon of the benzene ring.

  The imide oligomer represented by the general formula (2) has more than two imide groups. In the polyimide resin composition containing the imide oligomer represented by the general formula (2), since the imide oligomer acts as a cross-linking agent, the cross-linking density of the cured product of the polyimide resin composition is increased, resulting in a high elastic modulus and a low linear expansion coefficient. A cured product having the following is obtained. Therefore, when a polyimide resin composition containing an imide oligomer represented by the general formula (2) is used as an adhesive layer, a metal laminate or adhesive sheet excellent in heat resistance and dimensional stability can be obtained. The imide oligomer represented by the general formula (2) includes a polyfunctional compound having three or more crosslinkable groups, and these have a branched structure in the molecule. Therefore, compared with the case where a bifunctional crosslinking agent is used, it is thought that the crosslink density of hardened | cured material increases more and the elasticity modulus of hardened | cured material becomes high. The reason why the elastic modulus becomes high is that molecular motion due to heat is suppressed, and CTE, which is a coefficient of thermal expansion, also decreases.

  The polyimide resin composition of the present invention contains 5 to 100 parts by weight of the imide oligomer represented by the general formula (2) with respect to 100 parts by weight of the polyimide represented by the general formula (1). Is more preferable, and it is more preferable that it is 15 to 85 weight part. By making content of an imide oligomer into the said range, the glass transition temperature of a polyimide resin composition can be fully lowered | hung, and it is suitable for the metal laminated body which requires low-temperature adhesiveness. Further, when the content of the imide oligomer is within the above range, the cured product does not become brittle.

  The polyimide resin composition may contain a thermoplastic resin or a thermosetting resin other than the polyimide as long as the object of the present invention is not impaired. Examples of thermoplastic resins include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polystyrene, polyvinyl acetate, ABS resin, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polycarbonate, PTFE, celluloid, polyarylate, Examples include polyether nitrile, polyamide, polysulfone, polyether sulfone, polyether ketone, polyphenylene sulfide, polyamide imide, polyether imide, modified polyphenylene oxide, and polyimide. Examples of the thermosetting resin include thermosetting polybutadiene, formaldehyde resin, amino resin, polyurethane, silicone resin, SBR, NBR, unsaturated polyester, epoxy resin, polycyanate, phenol resin, and polybismaleimide. These resins may be used alone or in combination of two or more according to the purpose. A method of blending or alloying a plurality of types of resins is not particularly limited, and a known method can be applied.

  The polyimide resin composition may further contain other components as long as the object of the present invention is not impaired. For example, the polyimide resin composition is a metal catalyst containing gallium, germanium, indium, or lead for the purpose of controlling the speed of the crosslinking reaction, such as promoting or suppressing the crosslinking reaction that proceeds by heat treatment; Transition metal catalysts containing manganese, nickel, cadmium, cobalt, chromium, iron, copper, tin or platinum; phosphorus compounds, silicon compounds, nitrogen compounds, sulfur compounds and the like may also be included. In addition, for the purpose of controlling the speed of the crosslinking reaction, the polyimide resin composition is irradiated with radiation such as infrared rays, ultraviolet rays, α, β and γ rays, electron beams or X-rays, plasma treatment, doping treatment, etc. You may give it.

  The polyimide resin composition may further contain a filler or an additive as long as the object of the present invention is not impaired. Examples of fillers or additives include wear resistance improvers such as graphite, carborundum, silica stone powder, molybdenum disulfide, and fluorine resins; flame retardant improvers such as antimony trioxide, magnesium carbonate, and calcium carbonate; Electrical property improvers such as clay and mica; 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, etc. In addition, glass beads, glass spheres, talc, diatomaceous earth, alumina, shirasu balun, hydrated alumina, metal oxides, colorants and pigments are included. These fillers or additives may be used alone or in combination of two or more.

  When the polyimide resin composition is used as an adhesive layer of a laminate for a flexible circuit board or an adhesive resin layer of an adhesive sheet, the glass transition temperature of the polyimide resin composition is preferably 100 ° C. or higher and 300 ° C. or lower. . In particular, in order to improve low-temperature adhesiveness, the glass transition temperature of the polyimide resin composition is more preferably 100 ° C. or higher and 240 ° C. or lower, and further preferably 100 ° C. or higher and 200 ° C. or lower.

The elastic modulus at the time of plasticization of the polyimide resin composition is preferably 1 × 10 ³ Pa or more and 1 × 10 ⁷ Pa or less; moreover, the embedding property to the adherend is improved and good adhesiveness is obtained. From 1 × 10 ⁴ Pa to 1 × 10 ⁶ Pa, it is more preferable.

  The elastic modulus at the time of plasticization is measured as follows, for example. An uncrosslinked film is obtained by baking the precursor varnish of the polyimide resin composition at 240 ° C. for 30 minutes after film casting. The elastic modulus of the obtained uncrosslinked film is measured up to 400 ° C. in a tensile mode and 1 Hz in a nitrogen atmosphere using RSA-III manufactured by TA Instruments. The minimum value of the elastic modulus observed in this temperature range is defined as the elastic modulus during plasticization (E'min).

  Since the polyimide resin composition of the present invention contains an imide oligomer, a low elastic modulus can be achieved in a relatively low temperature range (during plasticization), and a high elastic modulus can be achieved by heating and crosslinking. For this reason, when the polyimide resin composition of the present invention is applied to, for example, a resin layer in contact with the metal layer of the metal laminate, the resin layer and the metal layer can be bonded well at a relatively low temperature, and the resin layer at a high temperature. Deformation and dimensional change can be effectively suppressed.

  Furthermore, when the polyimide has a highly reactive group such as a carbonyl group in the molecular structure, it easily reacts with the terminal amino group of the polyimide. When such a reaction occurs, the elastic modulus is hardly lowered even when an imide oligomer is added when the resin composition is bonded at a low temperature. In the present invention, such a reaction can be suppressed and the low-temperature adhesiveness can be more reliably enhanced by using a polyimide resin composition in which terminal-capped polyimide and an imide oligomer are combined.

2. Polyamic acid solution The polyamic acid solution of the present invention is a solution containing a precursor of the polyimide resin composition. A polyamic acid solution contains the polyamic acid containing the repeating unit represented by General formula (9), the imide oligomer represented by the said General formula (2), and a solvent as needed.

  The polyamic acid used in the present invention includes a repeating unit represented by the general formula (9), and the molecular terminal is a group selected from the group represented by the general formula (W2).

A and B in the general formula (9) are the same as A and B in the general formula (1). Moreover, although the repeating number of the repeating unit represented by General formula (9) is an integer greater than or equal to 2, and it is preferable that it is 20-2000, it is set to the range with which the viscosity of a polyamic acid is satisfy | filled. Further, _R 1 to R ₆ in the formula (W2) is the same as _R 1 to R ₆ in the general formula (W1).

  The logarithmic viscosity ηinh of a solution containing polyamic acid at a concentration of 0.5 g / dl in N, N-dimethylacetamide is preferably 0.2 to 2.0 dl / g, and preferably 0.3 to 1.0 dl / g. g is more preferable, and 0.4 to 0.9 dl / g is still more preferable. The logarithmic viscosity ηinh can be measured using, for example, an Ubbelohde viscosity tube.

  When the logarithmic viscosity of the polyamic acid is within the above range, the thickness of the coating film can be easily made uniform in the polyamic acid solution coating step when a film or a metal laminate is produced. Moreover, the intensity | strength of the resin composition obtained by imidating the coating film of a polyamic-acid solution can be raised, and it becomes easy to shape | mold as a film or a metal laminated body.

  The content of the imide oligomer represented by the general formula (2) in the polyamic acid solution is 5 parts by weight with respect to 100 parts by weight of the polyimide obtained from the polyamic acid containing the repeating unit represented by the general formula (9). The amount is preferably 100 parts by weight or less and more preferably 15 parts by weight or more and 85 parts by weight or less.

  The polyamic acid solution may contain other optional components as necessary, similarly to the polyimide resin composition.

  The polyamic acid solution preferably contains a solvent from the standpoint of uniformly mixing the polyamic acid and the imide oligomer and adjusting to an appropriate viscosity. The solvent is not particularly limited, but is preferably an aprotic polar solvent, and more preferably an aprotic amide solvent. Examples of aprotic amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone and the like are included.

  The polyamic acid solution may further contain another solvent as necessary. Examples of such other solvents include benzene, toluene, o-xylene, m-xylene, p-xylene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromo. Toluene, p-bromotoluene, chlorobenzene, bromobenzene and the like are included. These other solvents may be contained alone or in combination of two or more.

  The viscosity of the polyamic acid solution of the present invention at 25 ° C. measured with an E-type viscometer is not particularly limited, but is in the range of 100 to 20000 mPa · S from the viewpoint of easy control of the coating thickness. Is preferred.

3. The manufacturing method of a polyimide resin composition The manufacturing method of a polyimide resin composition includes the step which heats the said polyamic acid solution and imidates.

  In the step of imidizing by heating the polyamic acid solution, the solvent is removed at a temperature at which the crosslinking reaction of the imide oligomer does not occur, and the polyamic acid is imidized (ring closure). The heating temperature is, for example, about 100 to 300 ° C., and the heating time is, for example, about 3 minutes to 12 hours. The imidization is usually performed at atmospheric pressure, but may be performed under pressure. The atmosphere when imidizing is not particularly limited, but is usually air, nitrogen, helium, neon, argon, or the like, preferably nitrogen or argon which is an inert gas.

  The polyamic acid containing the repeating unit represented by the general formula (9) includes, for example, a tetracarboxylic dianhydride represented by the following general formula (4) and a diamine represented by the following general formula (5), It can be obtained by polycondensation reaction. A and B in the following formula are the same as A and B in the general formula (1).

  It is preferable that the charging ratio of tetracarboxylic dianhydride and diamine satisfies the following formula (A).

M1: M2 = 0.000-0.999: 1.00 Formula (A)
(M1: number of moles of tetracarboxylic dianhydride, M2: number of moles of diamine)

  M1: M2 is preferably 0.92 to 0.995: 1.00, more preferably 0.95 to 0.995: 1.00, and 0.97 to 0.995: 1. More preferably, it is 00. By setting the charging ratio in such a range, the end of the polyamic acid becomes an amino group, and the molecular weight can be made such that the characteristics of the polyimide can be sufficiently extracted, and handling is easy.

  The polyamic acid whose terminal is sealed is represented by a tetracarboxylic dianhydride represented by the general formula (4), a diamine represented by the general formula (5), and the following general formula (6). It can be obtained by polycondensation reaction with dicarboxylic anhydride.

D in Formula (6) is selected from the groups represented by the following formula. _R 1 in formula to R ₆ are the same as _R 1 to R ₆ in the general formula (W1).

  The charging ratio of tetracarboxylic dianhydride, diamine and dicarboxylic anhydride preferably satisfies the above formula (A) and the following formula (B1) from the following viewpoints. Furthermore, it is more preferable that the charging ratio satisfies the formula (A) and satisfies the formula (B2); more preferably, the formula (A) and the formula (B3) are satisfied.

（Ｍ１：テトラカルボン酸二無水物のモル数、Ｍ２：ジアミンのモル数、Ｍ３：ジカルボン酸無水物のモル数）

(M1: number of moles of tetracarboxylic dianhydride, M2: number of moles of diamine, M3: number of moles of dicarboxylic acid anhydride)

  When the addition amount of the dicarboxylic acid anhydride represented by the general formula (6) is more than equimolar with respect to the number of terminal amino groups of the polyamic acid, the excess unreacted dicarboxylic acid anhydride is volatilized in the subsequent processing process. As a result, the manufacturing equipment may be contaminated. On the other hand, when the addition amount of the dicarboxylic acid anhydride is less than equimolar with respect to the number of terminal amino groups, the terminal amino groups remain unreacted. This is because this unreacted terminal amino group may cause a crosslinking reaction with a highly reactive carbonyl group in polyimide and prevent a decrease in elastic modulus when adhered to a metal foil or the like.

  The imide oligomer represented by the general formula (2) can be synthesized by a known method. For example, an amino oligomer represented by the following formula (n is the same as n in the general formula (2)) and a dicarboxylic anhydride may be reacted to imidize the amino group to form an imide oligomer. An amino oligomer represented by the following formula can be obtained from the market. The amino oligomer represented by the following formula is usually a mixture of compounds having different n, and is preferably a mixture.

In order to react an amino oligomer and a dicarboxylic acid anhydride to form an imide oligomer, for example, there are the following techniques, but there is no particular limitation.
(1) A polyimide is prepared by synthesizing an amic acid compound at a low temperature of 100 ° C. or lower, specifically, −20 to 70 ° C., preferably 0 to 60 ° C., and then imidizing by raising the temperature to 100 to 200 ° C. To obtain (thermal imidization)
(2) Method of chemically imidizing using an imidizing agent such as acetic anhydride after synthesizing an amic acid compound as in (1) above (chemical imidization)
(3) A method of synthesizing an amic acid compound in the same manner as in the above (1), and then imidating in the presence or absence of a catalyst in the presence of a solvent for azeotropic dehydration (azeotropic dehydration ring closure method)
(4) Method of imidizing by mixing amino oligomer and dicarboxylic acid anhydride and then immediately heating in the presence or absence of catalyst and / or azeotropic dehydration solvent (direct thermal imidization)

  The reaction between the amino oligomer and the dicarboxylic acid anhydride is preferably performed in an organic solvent. The organic solvent to be used is not limited as long as it does not affect the reaction between the amino oligomer and the dicarboxylic acid anhydride. For example, saturated hydrocarbons such as pentane, hexane, heptane, cyclohexane; benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, Ethers such as 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, anisole; Phenol, o-chlorophenol, m-c Rophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol Phenols such as 3,4-xylenol and 3,5-xylenol; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide Amides such as hexamethylphosphoramide; N-methyl-2-pyrrolidone; lactams such as N-methylcaprolactam; sulfur-containing solvents such as dimethyl sulfoxide, diphenyl sulfoxide, dimethyl sulfone, diphenyl sulfone and sulfolane; Examples include 3-dimethyl-2-imidazolidinone. These organic solvents may be used alone or in combination of two or more. Furthermore, the reaction organic solvent may coexist with other solvents.

  The amount of the reaction solvent used is not particularly limited and varies depending on the solvent type and composition used, but is 1 to 1000 parts by weight, preferably 3 to 1 part by weight of the raw material (amino oligomer or dicarboxylic acid anhydride). 100 parts by weight.

  The reaction between the amino oligomer and the dicarboxylic acid anhydride may be performed in the presence of an organic base catalyst or an acid catalyst. Examples of organic base catalysts include triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine 2,6-lutidine, quinoline, isoquinoline and the like are included, and pyridine and γ-picoline are preferable.

  The amount of these catalysts used is not particularly limited as long as the reaction rate is substantially improved. Preferably it is 0.01-1 times mole.

  The reaction time varies depending on the type of raw material used, the type of solvent, the type of catalyst, the type and amount of the solvent for azeotropic dehydration, the reaction temperature, etc., but as a guide, it is 1 to 24 hours, usually several hours It is. When performing direct thermal imidation, as a guide, the reaction is carried out until the distilled water reaches a theoretical amount (usually not all are recovered, so the recovery rate is 50 to 90%). Usually, it is about several hours. In this case, a method of removing water generated by imidization with an azeotropic agent such as toluene is general and effective.

  The method for isolating the imide oligomer that is the target product from the reaction mixture is not particularly limited, but when the target product is precipitated from the reaction solvent, it may be isolated by filtration or centrifugation.

4). Applications of the polyimide resin composition The polyimide resin composition of the present invention is used for various applications, but applications that require low temperature adhesion and dimensional stability during high temperature processing, such as dry films, adhesive sheets, metal laminates, etc. It is preferable to apply to.

1) Dry film The dry film contains the polyimide resin composition of the present invention. The dry film can be obtained, for example, by applying the polyamic acid solution on a substrate, removing the solvent and imidizing, and then peeling the obtained film from the substrate. Solvent removal and imidation of the polyamic acid solution are not particularly limited, but are preferably performed under reduced pressure or in an inert atmosphere such as nitrogen, helium, argon, or the like.

  As described above, the heating temperature is a temperature at which the imide oligomer contained in the polyamic acid solution does not undergo a crosslinking reaction, and may be a temperature that is not less than the boiling point of the solvent and at which the imidization reaction proceeds. For example, in the case of a polyamic acid synthesized in an aprotic amide solvent, the heating temperature for desolvation and imidization may be about 100 to 300 ° C., and the heating time is not particularly limited, Usually, it may be about 3 minutes to 12 hours.

  Examples of the substrate include a metal foil, an inorganic substrate such as glass, and various resin films. The thickness of the coating film of the polyamic acid solution is preferably adjusted so that the film thickness after desolvation and imidization is 1 mm or less, although it depends on the solid content concentration of the polyamic acid solution.

  Examples of the means for applying the polyamic acid solution include general application means such as a roll coater, a die coater, a gravure coater, a dip coater, a spray coater, a comma coater, a curtain coater, and a bar coater. These application means are appropriately selected according to the viscosity of the polyamic acid solution and the coating film thickness.

  Examples of the means for drying the polyamic acid solution include electric air or oil heated hot air, a roll support using infrared rays as a heat source, an air float type drying furnace, and the like. The dry atmosphere may be replaced with a gas other than air, such as nitrogen, argon, or hydrogen, depending on the purpose of preventing deterioration of the polyimide resin, discoloration due to oxidation of the metal foil, and the like.

2) Adhesive sheet The adhesive sheet has an adhesive layer containing at least the polyimide resin composition of the present invention. Furthermore, it is preferable that an adhesive sheet has a resin film and the contact bonding layer formed in the single side | surface or both surfaces, and the polyimide resin composition of this invention is contained in a contact bonding layer.

  The resin film is not particularly limited, but is preferably a polyimide film. Examples of the polyimide film include a film obtained by applying and drying a non-thermoplastic polyimide precursor varnish, a commercially available non-thermoplastic polyimide film, and the like. Specifically, Upilex S, Upilex SGA, Upilex SN (manufactured by Ube Industries, registered trademark / product name), Kapton H, Kapton V, Kapton EN (manufactured by Toray DuPont, registered trademark / product name), Apical AH, Apical NPI, Apical HP (manufactured by Kaneka Corporation, registered trademark / trade name) and the like are included.

  Similar to the dry film, the adhesive sheet can be obtained, for example, by applying a polyamic acid solution on a resin film, drying, and imidizing as necessary. The thickness of the adhesive layer is preferably 1 mm or less.

3) Metal laminate The metal laminate has a metal layer and a resin layer, and at least one of the resin layers is a layer obtained from the polyimide resin composition of the present invention.

  The metal layer is not particularly limited, but is preferably a metal selected from copper, copper alloy, stainless steel, stainless steel alloy, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, and the like. Among these, the metal layer is more preferably copper, a copper alloy, or a stainless steel foil. The metal layer may be a metal foil or may be formed on the resin layer by a sputtering method or the like.

  The thickness of the metal layer is not particularly limited as long as it can be used in a reel shape, but is preferably 0.1 μm or more and 150 μm or less, more preferably 2 μm or more and 150 μm or less, and 3 μm or more and 50 μm or less. More preferably, it is more preferably 3 μm or more and 35 μm or less, and most preferably 3 μm or more and 12 μm or less.

  The resin layer is preferably a polyimide layer. The resin layer is not particularly limited, and may be a single layer or a multilayer. When the resin layer is a multilayer polyimide layer, the components of the adjacent polyimide layers are preferably different from each other. That the components of the adjacent polyimide layers are different from each other specifically means that the components and compositions of the monomers are different. Further, at least one of the single-layer polyimide layer or the multilayer polyimide layer may contain a resin composition (mixture) composed of two or more different polyimides.

  When the resin layer is a multilayer polyimide layer, the resin layer has a polyimide film and a polyimide layer formed on one or both sides of the polyimide film, and the polyimide layer in contact with the metal layer is A layer obtained from the polyimide resin composition of the invention is preferred. This is because the layer obtained from the polyimide resin composition of the present invention is excellent in adhesion to the metal layer.

  The polyimide film is the same as the polyimide film described above. When a commercially available non-thermoplastic polyimide film is used as the polyimide film, the film thickness is usually 3 μm or more and 75 μm or less, preferably 7.5 μm or more and 40 μm or less. When a film obtained by applying and drying a precursor varnish of non-thermoplastic polyimide is used as the polyimide film, the film thickness is 0.1 μm or more and 40 μm or less, preferably 0.5 μm or more and 25 μm or less, more preferably 0.5 μm. It is 16 μm or less. The surface of these polyimide films may be subjected to plasma treatment, corona discharge treatment or the like.

  The polyimide layer in contact with the metal layer is a layer obtained from the polyimide resin composition of the present invention. Specifically, it is preferably a layer obtained by crosslinking reaction of an imide oligomer contained in the polyimide resin composition.

  The thickness of the polyimide layer in contact with the metal layer is preferably 0.1 μm or more and 20 μm or less, more preferably 0.1 μm or more and 10 μm or less, and further preferably 0.1 μm or more and 5 μm or less. If the total thickness of the polyimide layer becomes too large, the rigidity becomes high, so that it is not suitable for applications that require folding resistance and the like, and if it is too thin, the insulating properties and handling properties are lowered. For this reason, the total thickness of the resin layer of the metal laminate is preferably 3 μm or more and 75 μm or less, and more preferably 10 μm or more and 45 μm or less. 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.

  Although the polyimide metal laminated body of this invention is not restrict | limited in particular, For example, it can be manufactured with the following method.

(1) A method of thermocompression bonding a dry film containing the polyimide resin composition of the present invention and a metal foil.
(2) A method in which the polyamic acid solution (polyimide precursor varnish) of the present invention is applied onto a metal foil, dried and imidized.

  As described above, the dry film of (1) may be a single-layer polyimide layer or a multilayer polyimide layer. When the dry film is a multilayer polyimide layer, at least the polyimide layer in contact with the metal foil only needs to contain the polyimide resin composition of the present invention.

  Examples of the thermocompression bonding method in the method of (1) include a method of laminating between metal rolls or metal roll surfaces heated by dielectric heating or heating using oil or the like between rolls lined with rubber or the like. A method of hot pressing is included. The laminating method is suitable for the production of continuous roll products, and the hot pressing method is suitable for the production of cut sheet-like single-wafer products, and can be appropriately selected depending on the application.

  The atmosphere gas at the time of thermocompression bonding is, for example, air, nitrogen, argon or the like. The heating temperature is a temperature mainly corresponding to the glass transition temperature of the thermoplastic polyimide, and is usually 100 to 400 ° C, preferably 150 to 300 ° C. The heating time is, for example, 0.01 seconds to 15 hours. The heating pressure may be, for example, 0.1 to 30 MPa, and preferably 0.5 to 10 MPa.

  You may post-process using an autoclave etc. at the point which further improves the adhesive force of metal foil and a polyimide layer. The post-treatment temperature is usually 150 to 400 ° C, preferably 200 to 350 ° C. The treatment time is 1 minute to 50 hours, and the pressure is normal pressure to 3 MPa. In order to prevent oxidation of the metal foil, it is preferable to replace the inside of the autoclave apparatus with a vacuum or an inert gas such as nitrogen or argon.

  In the method (2), the drying temperature of the coating film of the polyamic acid solution may be in the temperature range of 60 to 600 ° C., but the temperature is preferably raised stepwise. By heating the coating film stepwise and drying, a polyimide layer having a uniform film thickness and excellent dimensional stability can be obtained without causing defects such as foaming and crushed skin. The drying time may be appropriately set in the range of 0.05 to 500 minutes. As the means for applying and drying the polyamic acid solution, the same means as described above can be used.

  The double-sided metal laminate in which the metal foil is laminated on both sides of the resin layer can be produced by either method (1) or (2), but is also produced by a method combining (1) and (2). sell. For example, the single-sided metal laminate (i) obtained by thermocompression bonding of the dry film and metal foil of (1) and the single-sided metal obtained by applying the polyamic acid solution of (2) to the metal foil, drying and imidization A laminate (ii) is prepared. Then, the dry film surface of the single-sided metal laminate (i) and the polyimide surface of the single-sided metal laminate (ii) are laminated by thermocompression bonding.

  Thus, by making the polyimide layer in contact with the metal layer a layer obtained from the polyimide resin composition of the present invention, it can be satisfactorily bonded to the metal layer at a relatively low temperature. For this reason, even if it does not become high processing temperature, a laminated board which has high adhesive strength can be obtained, without a void remaining in a metal and a polyimide interface. Furthermore, since the polyimide layer obtained from the polyimide resin composition of the present invention has a high elastic modulus at high temperatures, it is possible to suppress solder bulging and the like in an LSI chip, a component mounting process, a repair process, and the like that have severe operating temperature conditions. Furthermore, since the polyimide layer undergoes little deformation and dimensional change at high temperatures, it is possible to suppress wiring short-circuits and the like that occur as the substrate is made thinner and the wiring density is increased.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by this. Abbreviations of compounds used in Examples and Comparative Examples are as follows.

DMAc: N, N-dimethylacetamide APB: 1,3-bis (3-aminophenoxy) benzene BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride MA: maleic anhydride NDA: 5- Norbornene-2,3-dicarboxylic anhydride (nadic anhydride)
PEPA: 4-phenylethynyl phthalic anhydride

Polyamic acid was synthesized as follows.
(Synthesis Example 1)
Synthesis of Amine-Terminated Polyamic Acid A container equipped with a stirrer and a nitrogen introduction tube was charged with 793 g of DMAc as a solvent, and then 205 g of APB was charged and stirred at room temperature for dissolution. To this solution, 222 g of BTDA was charged and stirred at room temperature for 12 hours to obtain a polyamic acid varnish. The polyamic acid solid content in the obtained polyamic acid varnish was 35% by weight. The logarithmic viscosity of the polyamic acid varnish was 0.76 dl / g, and the E-type viscosity at 25 ° C. was 125000 mPa · S.

(Synthesis Example 2)
Synthesis of PEPA-terminated polyamide acid A container equipped with a stirrer and a nitrogen introduction tube was charged with 1375 g of DMAc as a solvent, and then 351 g of APB was charged and stirred at room temperature for dissolution. To this solution, 381 g of BTDA and 8.94 g of PEPA were charged and stirred at room temperature for 12 hours to obtain a polyamic acid varnish. The polyamic acid solid content in the obtained polyamic acid varnish was 35% by weight. The logarithmic viscosity of the polyamic acid varnish was 0.64 dl / g, and the E-type viscosity at 25 ° C. was 52000 mPa · S.

(Synthesis Examples 3 and 4)
Synthesis of NDA-terminated polyamic acid and MA-terminated polyamic acid Polyamic acid was synthesized in the same manner as in Synthesis Example 2 except that the dicarboxylic anhydride for terminal group introduction was changed to that shown in Table 1 below. The results are shown in Table 1 together with Synthesis Examples 1 and 2.

ＭＤＡ−ＣＲ（ｎの平均値＝１．０） (Synthesis Example 5)
Synthesis of MDA-CR-NI 10.1 g (0.1 mol) of MDA-CR having a structure represented by the following formula in a flask equipped with a stirrer, a nitrogen inlet tube, a Dean Stark, a condenser and a thermometer, and As a solvent, 200 g of DMAc was charged and dissolved by stirring while passing nitrogen gas. To this solution, 21.34 (0.13 mol) of nadic anhydride was added, and stirred for 1 hour under ice-cooling and then at room temperature for 12 hours. Thereafter, 1.90 g (0.01 mol) of p-toluenesulfonic acid monohydrate (hereinafter referred to as PTS) as a catalyst and 100 ml of toluene as an azeotropic dehydration solvent were charged, heated to 160 ° C., and reacted for 8 hours. At this time, evaporation of toluene and water occurs, some of them condense in the cooler and water and toluene are separated by Dean Stark, then only toluene is refluxed into the system, and part of the nitrogen gas flows From the upper part of the cooling pipe, it was distilled out of the system.

MDA-CR (average value of n = 1.0)

ＭＤＡ−ＣＲ−ＮＩ（ｎの平均値＝１．０） After cooling the reaction mixture, toluene was distilled off with an evaporator. Thereafter, the obtained solution was poured into 500 g of 3% sodium bicarbonate water and stirred for 3 hours, and then the precipitate was collected by filtration, washed with water, and dried to obtain 24.2 g of MDA-CR-NI represented by the following formula. (Yield 98%).

MDA-CR-NI (average value of n = 1.0)

(Synthesis Example 6)
Synthesis of MDA-BNI Synthesis was performed in the same manner as in Synthesis Example 5 except that MDA was used instead of MDA-CR to obtain MDA-BNI.

Example 1
The kneading machine bottle was charged with the polyamic acid varnish obtained in Synthesis Example 1 and the imide oligomer obtained in Synthesis Example 5. At this time, it prepared so that an imide oligomer might be 18 weight part with respect to 100 weight part of polyamic acid solid content in a polyamic acid varnish. This solution was mixed and dissolved in a kneader, and DMAc was appropriately added so that the viscosity at 25 ° C. in an E-type viscometer was 100 to 1000, whereby a light brown transparent polyamic acid solution (polyimide resin composition) was obtained. Product precursor varnish).

  The following tests are performed on the uncrosslinked film (dry film) or the crosslinked film obtained by casting and then baking the obtained solution, and the coefficient of linear expansion (CTE) and the elastic modulus after crosslinking (E ′ @ 350 ° C.) , And the elastic modulus during plasticization (E′min) were measured. These results are shown in Table 2.

1) Linear expansion coefficient (CTE)
The polyamic acid solution coating film was baked at 350 ° C. for 2 hours in a nitrogen atmosphere to produce a crosslinked film (thickness 70 μm). The crosslinked film was measured for a linear expansion coefficient in a range of 100 ° C. to 200 ° C. in a dry air atmosphere using a thermal analyzer TMA50 series manufactured by Shimadzu Corporation.

2) Elastic modulus after crosslinking (E '@ 350 ° C)
The post-crosslinking film obtained in 1) was measured for elastic modulus up to 400 ° C. in a tensile mode at 1 Hz under a nitrogen atmosphere using RSA-III manufactured by TA Instruments Inc. at 350 ° C. The storage elastic modulus was post-crosslinking elastic modulus (E ′ @ 350 ° C.).

3) Elastic modulus during plasticization (E'min)
The polyamic acid solution coating film was baked at 240 ° C. for 30 minutes to prepare an uncrosslinked film (dry film) (thickness: 70 μm). The elastic modulus of this uncrosslinked film was measured up to 400 ° C. in a tensile mode and 1 Hz in a nitrogen atmosphere using RSA-III manufactured by TA Instruments. And the minimum value of the storage elastic modulus measured in this range was made into the elastic modulus at the time of plasticization (E'min).

  The thickness after drying the above polyamic acid solution (precursor varnish of polyimide resin composition) on the both surfaces of a commercially available polyimide film (trade name: Kapton 80EN, manufactured by Toray DuPont Co., Ltd.) with a gravure coater is 2. Coating was carried out to 5 μm. The coating film is dried at 70 ° C. for 5 minutes, at 100 ° C. for 2 minutes, at 140 ° C. for 2 minutes, at 180 ° C. for 2 minutes, and at 220 ° C. for 10 minutes, so that uncrosslinked thermoplastic polyimide is formed on both sides of the polyimide film. A polyimide insulating film (resin layer) having a layer was obtained.

  The polyimide insulating film and a commercially available copper foil (manufactured by Furukawa Circuit Foil Co., Ltd., trade name: F1-WS, thickness 18 μm) were thermocompression bonded under the following conditions using a hand press. The thermoplastic polyimide layer of the polyimide insulating film and the copper foil were bonded to each other, heated to 360 ° C. at a rate of 2 ° C./min while being pressure-bonded at 8 MPa, and held for 4 hours for adhesion. Thereby, a polyimide metal laminate (double-sided metal laminate) was obtained. The dimensional accuracy and peel strength of the obtained polyimide metal laminate were measured. These results are shown in Table 2.

4) Dimensional change The above-mentioned double-sided metal laminate sample having a size of 10 cm × 10 cm was prepared, and after making holes in the four sides of the base material, the copper foils on both sides were removed by etching. This double-sided metal laminate sample was left for 24 hours in an atmosphere of 50% humidity and 23 ° C. Thereafter, the rate of change in the distance between the formed holes was measured. The dimensional change was calculated from the average value of the copper foil conveyance direction and the direction perpendicular thereto.

5) Peel strength The above-mentioned double-sided metal laminate sample having a length in the direction parallel to the metal foil transport direction of 50 mm and a width of 1 mm was prepared. This double-sided metal laminate sample was peeled off from the resin layer at a peeling rate of 50 mm / min in accordance with JIS C-6471 in an environment of 23 ° C. and 50% relative humidity, The stress at that time was measured.

(Examples 2 to 5)
A polyamic acid solution was prepared in the same manner as in Example 1 except that the type of polyamic acid or imide oligomer and the amount of imide oligomer added were changed as shown in Table 2, and the test was performed in the same manner. These results are shown in Table 2.

(Comparative Examples 1-4)
The test was conducted in the same manner as in Example 1 except that Synthesis Examples 1 to 4 were used as the polyamic acid and no imide oligomer was used. These results are shown in Table 2.

(Comparative Example 5)
Except for changing the imide oligomer to MDA-BNI obtained in Synthesis Example 6, an attempt was made to synthesize a polyamic acid solution in the same manner as in Example 1. However, since MDA-BNI does not dissolve, the following tests may be performed. I could not do it.

  The dry films of Examples 1 to 5 obtained by imidizing the polyamic acid solution of the present invention have an elastic modulus (E ′ @ 350 after crosslinking) as compared with the dry films of Comparative Examples 1 to 4 that do not contain an imide oligomer. C.) and the coefficient of linear expansion (CTE) was low.

  In particular, when the terminal group of the polyimide in the dry film is a phenylethynylphthalimide group or a nadicimide group, it has been found that the elastic modulus (E′min) during plasticization can be sufficiently lowered (Examples 1 and 2). And 4, see Comparative Examples 1-4). This is considered to be because the reaction between the amino group at the end of the polyimide and the carbonyl group in the polyimide structure could be suppressed during plasticization, and the low modulus effect was obtained by the addition of the imide oligomer.

  Moreover, the metal laminated body of Examples 1-5 which has the resin layer obtained from the polyimide resin composition of this invention has high peel strength and dimensional stability compared with the metal laminated body of Comparative Examples 1-4. I understood it.

By using the polyimide resin composition of the present invention, it is possible to satisfactorily adhere to the adherend at a relatively low temperature and to increase the dimensional stability during high-temperature processing. For this reason, the polyimide resin composition of this invention is preferably used for a heat resistant film, an adhesive sheet, a flexible printed circuit board (metal laminate), a semiconductor package, and the like.

Claims (12)

A polyimide having a repeating structural unit represented by the following general formula (1) and having a molecular end selected from a group represented by the following general formula (W1);
The polyimide resin composition containing the imide oligomer represented by the following general formula (2) ,
The number of repeating structural units represented by the general formula (1) contained in the polyimide is 20 to 2000,
Containing 5 parts by weight or more and 100 parts by weight or less of the imide oligomer with respect to 100 parts by weight of the polyimide;
The glass transition temperature of the polyimide resin composition is 100 ° C. or higher and 350 ° C. or lower,
The cross-linked product of the polyimide resin composition is a polyimide resin composition having a storage elastic modulus at 350 ° C. of 2.1 × 10 ^{7 to} 1.25 × 10 ⁸ Pa .

[In general formula (1),
A is a group selected from the groups represented by the following formulae,

(X _{1 to} X ₆ are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —. Or represents -NHCO-)
B is a group selected from the groups represented by the following formulae.

(Y _{1 to} Y ₆ are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —. Or -NHCO-)

(R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₅ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) _2. - it represents or -CO- a; _{R 6} represents a hydrogen atom or a phenyl group)

[In General Formula (2), n represents a real number greater than 0 and 10 or less, and may be a mixture of compounds having different n, and Z _{1 to} Z ₃ are each selected from the groups represented by the following formulae: It is a group

(R _{7 to} R ₁₀ each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₁₁ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —. Or represents —CO—; R ₁₂ represents a hydrogen atom or a phenyl group)] The polyimide resin composition of Claim 1 whose molecular terminal of the said polyimide is group chosen from the group shown by the following general formula (W1 ^' ).

In the general formula (2),
The polyimide resin composition according to claim 1 or 2 , wherein Z _{1 to} Z ₃ are any of the groups represented by the following formulae.

Formula (2) n in the imide oligomer represented by is greater than 6 real number from 0, and the content of the compounds wherein n is 0 is 40 to 60 mol%, of claim 1-3 The polyimide resin composition as described in any one. In the general formula (1),
A is a group selected from the groups represented by the following formulae,

B is a group selected from the groups represented by the following formulae,

The molecular terminal of the polyimide is a group selected from the group represented by the following formula:

The polyimide resin composition according to claim 1. The film containing the polyimide resin composition as described in any one of Claims 1-5 . A metal laminate comprising a metal layer and a resin layer, wherein at least one of the resin layers is a layer obtained from the polyimide resin composition according to any one of claims 1 to 5. body. The said resin layer has a polyimide film and the polyimide layer formed in the one or both surfaces of the said polyimide film, The said polyimide layer which contact | connects the said metal layer is as described in any one of Claims 1-5 . The metal laminated body of Claim 7 which is a layer obtained from a polyimide resin composition. The adhesive sheet which has a resin film and the layer which is formed in the single side | surface or both surfaces of the said resin film, and contains the polyimide resin composition as described in any one of Claims 1-5 . A polyamic acid containing a repeating unit represented by the general formula (9) and having a molecular end selected from the following general formula (W2);
And imide oligomer represented by the general formula (2), only contains,
Containing 5 parts by weight or more and 100 parts by weight or less of the imide oligomer with respect to 100 parts by weight of the polyimide obtained from the polyamic acid,
The polyamic acid is a polyamic acid solution having a logarithmic viscosity of 0.2 to 2.0 dl / g when polyamic acid is dissolved in N, N-dimethylacetamide at a concentration of 0.5 g / dl .

[In general formula (9),
A is a group selected from the groups represented by the following formulae,

(X _{1 to} X ₆ are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —. Or represents -NHCO-)
B is a group selected from the groups represented by the following formulae,

(Y _{1 to} Y ₆ are each a single bond, —O—, —S—, —CO—, —COO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —. Or -NHCO-)

(R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₅ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) _2. - it represents or -CO- a; _{R 6} represents a hydrogen atom or a phenyl group)

[In General Formula (2), n represents a real number greater than 0 and 10 or less, and may be a mixture of compounds having different n,
Z _{1 to} Z ₃ are groups selected from the groups represented by the following formulae,

(R _{7 to} R ₁₀ each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₁₁ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) _2. - or represents _{-CO-; R 12} represents a hydrogen atom or a phenyl group)] The manufacturing method of a polyimide resin composition including the step of heating and imidating the polyamic-acid solution of Claim 10 . A tetracarboxylic dianhydride represented by the following general formula (4) and a diamine represented by the following general formula (5) in the presence of a dicarboxylic acid anhydride represented by the following general formula (6) or A polycondensation reaction in the absence to obtain a polyamic acid represented by the general formula (9);

[In general formula (4)-(6),
A and B are the same as A and B in the general formula (9),
D is a group selected from the groups represented by the following formulae.

(R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; R ₅ represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) _2. — Represents —CO—; R ₆ represents a hydrogen atom or a phenyl group)]
Heating the polyamic acid solution to imidize, and a method for producing a polyimide resin composition,
The production of the polyimide resin composition according to claim 11 , wherein a charging ratio of the tetracarboxylic dianhydride, the diamine, and the dicarboxylic acid anhydride satisfies the following formulas (A) and (B). Method.

(M1: number of moles of tetracarboxylic dianhydride, M2: number of moles of diamine, M3: number of moles of dicarboxylic acid anhydride)