JP2007137960A - Bisimide or bisisoimide compound and resin composition comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition suitable for interlayer insulation of a multi-layered flexible printed circuit board exhibiting excellent workability and adhesion before curing and exhibiting excellent heat resistance, adhesion and electrical performance after curing. <P>SOLUTION: The resin composition comprises a polyimide or a polyamic acid and a bisimide or a bisisoimide compound represented by formula (1). (One of the A and B is = O and the other of the A and B is = NAr<SP>1</SP>R<SP>1</SP>; R<SP>1</SP>, R<SP>2</SP>, Ar<SP>1</SP>, X<SP>1</SP>and X<SP>2</SP>are each a specific organic group). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyimide resin composition containing polyimide and a bisimide compound or a bisisoimide compound, and a heat-resistant adhesive, varnish, film, film laminate, metal laminate, and electronic circuit obtained using the resin composition. And a cured product thereof. The present invention also relates to novel bisimide compounds and bisisoimide compounds.

  In recent years, small electronic devices such as mobile phones, digital still cameras, and PDAs have become more functional, thinner, and lighter. Accordingly, electronic components and boards mounted on electronic devices have also become highly functional and highly functional. There has been a demand for higher performance and higher density. Specifically, multi-layer printed wiring boards that can route three-dimensional wiring by laminating printed wiring boards are being actively developed. For example, the B2it method (abbreviation of Buried Bump Interconnection Technology) is known. The interlayer connection technology to be used corresponds to the high density of wiring (see, for example, Patent Document 1). That is, the copper foil with bumps and the uncured insulating layer are alternately laminated, pressed under a predetermined temperature and pressure condition, and the insulating layer is penetrated by the bump, whereby the lower wiring layer and the upper layer through the insulating layer Electrical connection with the wiring layer is provided as appropriate. Then, by repeating these connections, multilayering is possible.

  In these techniques, it is necessary to reliably penetrate the insulating layer with the bump and to protrude the bump head from the insulating layer. In general, these interlayer insulating materials are polyimide films, liquid crystal polymer films, polyphenylene sulfide films, polyether ether ketone films, epoxy-modified polyimide films, etc., or sheet-like interlayer insulating materials. Polyphenylene sulfide films, polyether ether ketone films, and the like have high lamination temperatures due to their high glass transition temperatures, and are difficult to use for general printed wiring boards. In addition, the resin “flow” is poor, and when the bump penetrates the insulating layer, the bump is deformed, and the bump height and the protrusion amount of the bump head are likely to vary. In addition, the bumps are not sufficiently filled with resin, and further, the conductive layer and the insulating layer below are deformed, resulting in insufficient adhesion and electrical reliability.

  Therefore, the insulating layer has a low glass transition temperature when the bump penetrates the insulating layer, that is, when pressing is performed at a predetermined temperature and pressure, and then the glass transition temperature is shifted to a high temperature side by curing, When forming a further upper conductive layer and an insulating layer (when pressing is performed at a predetermined temperature and pressure conditions for the bump to penetrate the insulating layer), it is desirable that the insulating layer does not deform and is sealed when pressed. Since it will be in a state, it is desirable that it is a polyimide resin composition film with little residual solvent and strong adhesive strength.

  As a method for improving the moldability of polyimide, an aromatic polyimide resin composition comprising an aromatic polyimide and an acetylene-terminated polyimide / isoimide oligomer has been reported (for example, see Patent Document 2). Specifically, it has been reported that the moldability is greatly improved by mixing polyimide obtained from pyromellitic anhydride, 4,4'-diaminodiphenyl ether, and ceramide (manufactured by Kanebo NSC). However, these resin compositions are molding materials and are not suitable as interlayer insulating materials for multilayer flexible wiring boards. Furthermore, the time required for thermosetting the composite material can be shortened, and (a) a rigid terminal-modified imide macromer, (b) a flexible terminal-modified imide oligomer, and (c) an unsaturated group can be suitably used as the matrix resin. A terminal-modified imide oligomer composition containing a reactive monomer having a hydrogen atom has been reported (for example, see Patent Document 3). These resins are also reinforcing agents and matrix resins for composite materials, and are not suitable for electronic materials.

JP 2001-015920 A JP-A-2-222451 JP-A-4-363360

  The object of the present invention is to provide a resin composition exhibiting excellent processability and adhesiveness before curing and exhibiting excellent heat resistance, adhesiveness, and electrical properties after curing, particularly for interlayer insulation for multilayer flexible printed wiring boards. The object is to provide a suitable resin composition.

  The present invention includes polyimide or polyamic acid and the following general formula (1):

(In the formula, one of A and B is ═O, the other is ═NAr ¹ R ¹ , and Ar ¹ is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or the same Or a divalent group of a polycyclic compound in which two or more different aromatic compounds are connected to each other directly or by a bridging member, and R ¹ is at least one carbon having 2 to 36 carbon atoms A monovalent organic group containing a carbon double bond or a carbon-carbon triple bond, and X ¹ and X ² are independently a single bond, —O—, —CO—, —COO—, —OCO; —, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, wherein R ² is an alkanediyl group having 2 to 18 carbon atoms or a monocyclic having 6 to 36 carbon atoms. Formula or condensed polycyclic aromatic compounds, or two or more of the same or different aromatic compounds may be directly or A bivalent radical of a polycyclic compound linked to one another, and wherein a bridge member, -O by personnel -, - CO -, - COO -, - OCO -, - SO 2 -, - CH 2 -, -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- ) and a heat resistant adhesive comprising the resin composition. The present invention relates to an agent, a varnish, a film, a metal laminate, and a polymer laminate.

  The resin composition of the present invention is obtained by mixing polyimide (or polyamic acid) and the thermosetting bisimide or bisisoimide compound represented by the general formula (1), and is uncured and in the form of a film. Can be. By mixing the bisimide or bisisoimide compound represented by the general formula (1), the glass transition temperature before curing of the polyimide resin composition of the present invention is that of a polyimide (or polyamic acid) not mixed with such a compound. It shifts to a lower temperature side than the glass transition temperature. As a result, the resin composition of the present invention is in a high flow state and is in a state where it can be easily processed and bonded. That is, the resin composition of the present invention can be easily penetrated through the bump, filled with the resin at the base of the bump, and bonded in the temperature range from the glass transition temperature to the curing temperature. Thereafter, a glass transition temperature of the polyimide resin composition of the present invention is obtained by performing a heat treatment (curing treatment) at 180 to 450 ° C. and crosslinking the unsaturated groups of the bisimide or bisisoimide compound linearly and / or three-dimensionally. , The glass transition temperature of the polyimide not mixed with the bisimide or bisisoimide compound is shifted to a higher temperature side. As a result, the cured product of the resin composition of the present invention is excellent in heat resistance, adhesiveness, electrical characteristics and the like, and is particularly suitable for an interlayer insulating material for multilayer printed wiring boards.

  First, the thermosetting bisimide or bisisoimide compound of the present invention will be described. The thermosetting bisimide or bisisoimide compound is the following general formula (1):

(In the formula, one of A and B is ═O, the other is ═NAr ¹ R ¹ , and Ar ¹ is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or the same Or a divalent group of a polycyclic compound in which two or more different aromatic compounds are connected to each other directly or by a bridging member, and R ¹ is at least one carbon having 2 to 36 carbon atoms A monovalent organic group containing a carbon double bond or a carbon-carbon triple bond, and X ¹ and X ² are independently a single bond, —O—, —CO—, —COO—, —OCO; —, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, wherein R ² is an alkanediyl group having 2 to 18 carbon atoms or a monocyclic having 6 to 36 carbon atoms. Formula or condensed polycyclic aromatic compounds, or two or more of the same or different aromatic compounds may be directly or A bivalent radical of a polycyclic compound linked to one another, and wherein a bridge member, -O by personnel -, - CO -, - COO -, - OCO -, - SO 2 -, - CH 2 A bisimide compound represented by —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, or a positional isomer thereof. In the production of these compounds, a tetracarboxylic dianhydride and an amine component are first reacted to produce the corresponding bisamic acid. The production of bisamidic acid is not particularly limited and may be a known method, and is usually performed in a solvent.

  The tetracarboxylic dianhydride used in the production of the bisimide or bisisoimide compound is represented by the following general formula (9):

Wherein X ¹ and X ² are each independently a single bond, —O—, —CO—, —COO—, —OCO—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ — and R ² is an alkanediyl group having 2 to 18 carbon atoms, a divalent group of a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or the same or A divalent group of a polycyclic compound in which two or more different aromatic compounds are connected to each other directly or by a cross-linking member, where the cross-linking members are -O-, -CO-, -COO- , —OCO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —).

The “alkanediyl group having 2 to 18 carbon atoms” in R ² may be linear or branched. Preferred are alkanediyl groups having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene and the like. Most preferably, ethylene is used.

The “divalent group of a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms” in R ² is an unsubstituted alkyl group, alkoxyl group or halogen atom even if it is unsubstituted. The hydrogen atom on the aromatic may be substituted with a substituent selected from Preferably, it is a bivalent group of a monocyclic or condensed polycyclic aromatic compound having 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenylene, naphthalenediyl, anthracenediyl, phenanthrene diyl, etc. Can be mentioned. Most preferred is o-, m- or p-phenylene.

The “divalent group of a polycyclic compound in which two or more of the same or different aromatic compounds are connected to each other directly or by a bridging member” in R ² refers to a monocyclic or condensed polycyclic aromatic compound, is directly or bridge member (here a bridge member, -O -, - CO -, - COO -, - OCO -, - SO 2 -, - CH 2 -, - C ( A divalent group of a polycyclic compound interconnected by CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. Examples of divalent groups of preferred polycyclic compounds are those wherein two or more monocyclic aromatic compounds mentioned in the preceding paragraph, in particular o-, m- or p-phenylene, can be linked directly or by a bridging member. And a divalent group of a polycyclic compound linked to, for example, biphenyl-4,4′-diyl, biphenyl-2,2′-diyl and the like.

  Specific examples of the tetracarboxylic dianhydride represented by the general formula (9) include the following formula (10):

(Wherein, m is represented by an integer of 0 to 4), and the hydrogen atom on the aromatic is selected from an alkyl group having 1 to 6 carbon atoms, an alkoxyl group, or a halogen atom It may be substituted with a substituent. These compounds are either commercially available or commercially available reagents such as trimellitic anhydride, halophthalic anhydride and commercially available dihydric alcohols, phenols or bisphenols according to conventional methods. Although it can obtain easily by making it react, from a viewpoint of availability, following formula (11):

の使用が望ましい。また、上記二無水物を２種類以上混合して用いても良い。

Is desirable. Two or more of the above dianhydrides may be mixed and used.

  The amine component has the following general formula (12):

(In the formula, Ar ¹ represents a divalent group of a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or two or more of the same or different aromatic compounds directly or by a cross-linking member. A monovalent group containing at least one carbon-carbon double bond or carbon-carbon triple bond having 2 to 36 carbon atoms, wherein R ¹ is a divalent group of a polycyclic compound linked to an organic group, and wherein a bridge member, -O -, - CO -, - COO -, - OCO -, - SO 2 -, - CH 2 -, - C (CH 3) 2 - or -C (CF ₃ ) ₂ —).

In Ar ¹ , “a divalent group of a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms” and “two or more of the same or different aromatic compounds are linked directly or by a cross-linking member. The “divalent group of the polycyclic compound” has the same meaning as in R ² listed in the above paragraph, but preferably Ar ¹ is represented by the following formula (13):

(In the formula, Y represents a single bond, —O—, —CO—, —COO—, —OCO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ — or —C (CF _{3 2} ), which may be the same or different.

The “monovalent organic group containing at least one carbon-carbon double bond or carbon-carbon triple bond having ₂ to ₃₆ carbon atoms” in R ¹ is specifically C _{2 to} C _36. - _alkenyl, C 2 _{-C 36} - _alkynyl, C 6 _{-C 34} - aryl _-C 2 _{-C 30} - _alkenyl, C 2 _{-C 30} - alkenyl _-C 6 _{-C 34} - aryl _{group, C} 6 ~ A C ₃₄ -aryl-C ₂ -C ₃₀ -alkynyl group or a C ₂ -C ₃₀ -alkynyl-C ₆ -C ₃₄ -aryl group, preferably a C ₂ -C ₃₆ -alkynyl group or C ₆ -C _34. - alkynyl group, more _preferably, C 2 -C ₆ - - aryl _-C 2 _{-C 30} alkynyl group - alkynyl or _C 6 _{-C 18} - aryl _-C 2 -C _6.

Therefore, the “organic group having ₁ to ₃₄ carbon atoms” in R when R ¹ is represented by the general formula (2) is, for example, a C _{1 to} C ₃₄ -alkyl group or a C _{6 to} C ₃₄ -aryl group. C ₁ -C ₂₈ -alkyl-C ₆ -C ₃₃ -aryl group or C ₆ -C ₃₃ -aryl-C ₁ -C ₂₈ -alkyl group, preferably C ₁ -C ₃₄ -alkyl group or C ₆ -C ₃₄ - aryl group, more _preferably, C 2 -C ₆ - alkynyl or _C 6 _{-C 18} - aryl radical, in particular phenyl. In particular, R ¹ is represented by the following formula (14):

The thing represented by these is preferable. Therefore, specific examples of the amine compound represented by the general formula (12) include 3-aminophenylacetylene, 4-aminophenylacetylene, 3-phenylethynylaniline, 4-phenylethynylaniline, 3-naphthylethynylaniline, 4-naphthylethynylaniline, 3-anthracenylethynylaniline, 4-anthracenylethynylaniline, etc. are mentioned, and the hydrogen atom on the aromatic is substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxyl group, or a halogen atom. May be. From the viewpoint of easy availability, it is desirable to use 3-aminophenylacetylene, 4-aminophenylacetylene, 3-phenylethynylaniline, and 4-phenylethynylaniline. Two or more of the above amine compounds may be mixed and used.

  The solvent used for the reaction of bisamidic acid is not particularly limited as long as it is an inert solvent for the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetra Methylurea, tetrahydrofuran and the like can be used alone or in a mixed form. Particularly preferred are N, N-dimethylacetamide, N-methyl-2-pyrrolidone and tetrahydrofuran. Further, these solvents may be used by mixing benzene, toluene, xylene, mesitylene, chlorobenzene, diglyme, triglyme and the like in an arbitrary ratio. The reaction is usually carried out at a solute concentration of 5 to 80%.

  Next, the imidization reaction is performed by dehydrating the bisamic acid obtained by the above reaction by a known method. For example, the chemical imidization method is not particularly limited to the bisamic acid solution obtained by the above reaction, but is not limited to acetic anhydride, trifluoroacetic anhydride, polyphosphoric acid, phosphorus pentoxide, phosphorus pentachloride, chloride. Dehydration is performed by using a dehydrating agent such as thionyl alone or in combination of two or more. A catalyst such as pyridine may be used. In the thermal imidization method, a solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, diglyme, and triglyme is mixed with the bisamic acid solution obtained in the above reaction at an arbitrary ratio, heated, and generated by ring closure. The water is drained while draining the water out of the system. These solvents may be used alone or in combination of two or more. On the other hand, the isoimidization reaction is performed by dehydrating the bisamic acid obtained by the above reaction by a known method. For example, dehydrating agents such as trifluoroacetic anhydride and N, N-dicyclohexylcarbodiimide are used alone or in combination of two or more for dehydration. A catalyst such as pyridine may be used.

  Here, “isoimide” corresponds to a positional isomer of imide, and is represented by the following formula (15):

In the molecule, it has a structure shown in (2), and it undergoes a transition in the molecule at a temperature of 200 to 300 ° C. to become an imide.

  The bisimide compound or bisisoimide compound according to the present invention may be used as a powder by pouring into a solvent such as water or alcohol after completion of imidization or isoimidation, reprecipitation, taking out the crystals by filtration and drying. An isoimidating agent such as urea may be removed by filtration and used as a solution.

  In the bisimide compound or bisisoimide compound of the present invention, in particular, the following formulas (3) and (4):

The thing represented by these is preferable. These compounds are new and are part of the object of the present invention.

  Next, the resin composition of the present invention can be produced by mixing the bisimide compound or bisisoimide compound obtained as described above with polyimide or polyamic acid.

  Next, polyimide and polyamic acid will be described. The polyimide and polyamic acid used in the present invention are represented by the following general formula (16):

  And the following general formula (17):

(In the formula, n is a number of 20 or more, Ar ⁶ is a tetracarboxylic acid residue, and Ar ⁷ is a diamine residue).

There is no restriction | limiting in particular in manufacture of a polyimide and / or a polyamic acid, A well-known method may be sufficient, and it is normally performed in a solvent. It is produced by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine in a polar solvent. Specific examples of the tetracarboxylic dianhydride used here (that is, those that form a tetracarboxylic acid residue of Ar ⁶ ) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic acid dianhydride 3,4'-oxydiphthalic dianhydride, 3,3'-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4 '-Diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 1, 2, 7, - like naphthalene tetracarboxylic dianhydride. The polyimide of the present invention is preferably solvent-soluble and varies depending on the molecular weight and the type of diamine selected, but pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,4'-oxydiphthalic acid Dianhydride, 3,3′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4 The use of dicarboxyphenyl) hexafluoropropane dianhydride is desirable. Two or more of the above dianhydrides may be mixed and used.

Examples of aromatic diamines (ie, those that form a diamine residue of Ar ⁷ ) have one aromatic group; p-phenylenediamine, m-phenylenediamine, p-aminobenzylamine, m- Aminobenzyldiamine, diaminotoluenes, diaminoxylenes, diaminonaphthalenes, diaminoanthracenes and the like having two aromatic groups; 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3 ′ -Diaminobiphenyl, o-tolidine, m-tolidine, o-dianisidine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 3,3 ′ -Diaminodiphenyl ketone, 2,2-bis (4-aminophenoxy) propane, 2,2-bis (3-aminophenoxy) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, etc. Having three aromatic groups; 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, , 3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) It has 4 or more aromatic groups such as benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,3-bis (3-aminobenzoyl) benzene, 9,9-bis (4-aminophenyl) fluorene. 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) Phenyl] ether, 4,4′-bis (4-aminophenoxy) benzophenone, 4,4′-bis (3-aminophenoxy) benzophenone, 1 4-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 1,4- Bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 1,3-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 4,4′-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] biphenyl, 4,4′-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl Biphenyl, 4,4′-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] diphenylsulfone, 4,4′-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl ] Diphenyl sulfone etc. are mentioned. The polyimide of the present invention is desirably solvent-soluble and varies depending on the molecular weight and the type of tetracarboxylic dianhydride selected. In consideration of availability, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] Use of sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene Is preferred. Two or more diamine compounds may be mixed and used.

Furthermore, the following general formula (18):

(In the formula, p is an integer mixed value of 0 to 20, R ⁵ represents a methyl group, an isopropyl group, a phenyl group or a vinyl group, and R ⁶ represents a hydrocarbon group having 1 to 7 carbon atoms such as methylene. , Ethylene, trimethylene, tetramethylene, phenylene, etc.) may be copolymerized in the range of 1 to 50 mol%.

  The solvent used for the reaction of the polyimide and / or polyamic acid is not particularly limited as long as it is an inert solvent for the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, Dimethyl sulfoxide, tetramethyl urea, tetrahydrofuran and the like can be used alone or in a mixed form. Particularly preferred are N, N-dimethylacetamide and N-methyl-2-pyrrolidone. Further, these solvents may be used by mixing benzene, toluene, xylene, mesitylene, chlorobenzene, diglyme, triglyme and the like in an arbitrary ratio. The reaction is usually carried out at a solute concentration of 5 to 80%.

  Next, the imidization reaction is performed by dehydrating the polyamic acid obtained by the above reaction by a known method. For example, the chemical imidization method is not particularly limited to the polyamic acid solution obtained by the above reaction, but acetic anhydride, trifluoroacetic anhydride, polyphosphoric acid, phosphorus pentoxide, phosphorus pentachloride, chloride Dehydration is performed by using a dehydrating agent such as thionyl alone or in combination of two or more. A catalyst such as pyridine may be used. In the thermal imidization method, a solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, diglyme, and triglyme is mixed in an arbitrary ratio to the polyamic acid solution obtained by the above reaction, heated, and produced by ring closure. The water is drained while draining the water out of the system. These solvents may be used alone or in combination of two or more.

  The resin composition of the present invention preferably contains a polyimide or polyamic acid obtained as described above and a thermosetting bisimide compound or a thermosetting bisisoimide compound in a weight ratio of 99/1 to 20/80. In particular, those containing at a weight ratio of 95/5 to 40/60 are preferred.

  Furthermore, in order to improve adhesiveness, heat resistance, etc., the following general formulas (5) to (8) are added to the polyimide resin composition or the polyamic acid resin composition obtained as described above:

(In the formula, n is a number of 0 to 20, R ³ and R ⁴ are independently hydrogen or a phenyl group, and Ar ² and Ar ⁴ are independently a tetracarboxylic acid having 6 to 36 carbon atoms. An acid residue, that is, a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or a polycyclic compound in which two or more of the same or different aromatic groups are connected to each other directly or by a bridging member Ar ³ and Ar ⁵ are independently a diamine residue having 6 to 36 carbon atoms, that is, a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, the same or A divalent group of a polycyclic compound in which two or more different aromatic groups are connected to each other directly or by a cross-linking member, where the cross-linking members are -O-, -CO-, -COO- _{, -OCO -, - SO 2 -} , - CH 2 -, - C (CH 3) 2 - or -C CF _{3) 2} - imide oligomer or iso imide oligomer 95 / 5-5 / 95 having a crosslinkable group represented by a is), preferably 90 / 10-20 / 80, more preferably 80/20 It can be added at a mixing ratio of 40/60.

  As a method for producing an imide oligomer and an isoimide oligomer having a crosslinkable group, first, a corresponding amic acid oligomer is produced. There is no restriction | limiting in particular in manufacture of an amic acid oligomer, A well-known method may be sufficient and it is normally performed in a solvent. An aromatic tetracarboxylic dianhydride, an aromatic diamine, and an amine-based or acid-based molecular end-capping agent having a crosslinkable group are reacted in a polar solvent. Specific examples of the tetracarboxylic dianhydride used here include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyl. Tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, 3,3 '-Oxydiphthalic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,2,7,8-naphthalenetetracarboxylic dianhydride Na And the like. Note that the diamine oligomer and / or isoimide oligomer glass transition temperature is 250 ° C. or lower, preferably 200 ° C. or lower from the viewpoint of resin flowability, and considering the availability, the diamine to be used. Although it depends on the type of compound and the target molecular weight, 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid, considering the availability, etc. Dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,4 It is desirable to use -dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride. Two or more of the above dianhydrides may be mixed and used.

  Examples of aromatic diamines include those having one aromatic group; p-phenylenediamine, m-phenylenediamine, p-aminobenzylamine, m-aminobenzyldiamine, diaminotoluenes, diaminoxylenes, diaminonaphthalenes , Diaminoanthracenes and the like having two aromatic groups; 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, o-tolidine, m-tolidine, o-dianisidine 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4, , 4'-Diaminodiphenylsulfone 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 2,2-bis Those having three aromatic groups such as (4-aminophenoxy) propane, 2,2-bis (3-aminophenoxy) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane; 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) Benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,3-bis (4- Those having four or more aromatic groups such as minobenzoyl) benzene, 1,3-bis (3-aminobenzoyl) benzene, 9,9-bis (4-aminophenyl) fluorene; 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 4,4′-bis (4-Aminophenoxy) benzophenone, 4,4′-bis (3-aminophenoxy) benzophenone, 1,4-bis [4- (2-, 3 -Or 4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 1,4-bis [3- (2-, 3- or 4-Aminophenoxy) benzoyl] benzene, 1,3-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 4,4′-bis [4- (2-, 3- or 4 -Aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (2-, 3- or 4 -Aminophenoxy) benzoyl] biphenyl, 4,4′-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] biphenyl, 4,4 -Bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] diphenylsulfone, 4,4'-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] diphenylsulfone, etc. It is done. In view of resin flowability, the glass transition temperature of the imide oligomer or isoimide oligomer is 250 ° C. or lower, preferably 200 ° C. or lower, and the tetracarboxylic acid to be used in consideration of availability. Depending on the type of dianhydride and the target molecular weight, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) Benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4 '-Bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ - (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) use of fluorene are preferred. Two or more diamine compounds may be mixed and used.

  Examples of molecular end-capping agents having a crosslinkable group include 4-ethynyl phthalic anhydride, 3-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, 3-phenyl as acid-based molecular end capping agents. Ethynyl phthalic anhydride, ethynyl naphthalene dicarboxylic acid anhydride, phenyl ethynyl naphthalene dicarboxylic acid anhydride, ethynyl anthracene dicarboxylic acid anhydride, phenyl ethynyl anthracene dicarboxylic acid anhydride, 4-naphthylethynyl phthalic anhydride, 3-naphthylethynyl phthalic anhydride Naphthylethynylnaphthalenedicarboxylic anhydride, naphthylethynylanthracene dicarboxylic acid anhydride, 4-anthracenyl ethynyl phthalic anhydride, 3-anthracenylethynyl phthalic anhydride, anthracenylethynylnaphthalenedicarboxylic acid anhydride, ant It includes such cell nil ethynyl anthracene dicarboxylic acid anhydride, hydrogen atoms on aromatic, alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group, an alkoxyl group, may be substituted with a halogen atom. In consideration of availability, 4-phenylethynyl phthalic anhydride and 4-ethynyl phthalic anhydride are preferably used. Further, two or more of the above acid anhydrides may be mixed and used.

  Specific examples of the amine-based molecular end-capping agent include 3-aminophenylacetylene, 4-aminophenylacetylene, 3-phenylethynylaniline, 4-phenylethynylaniline, 3-naphthylethynylaniline, 4-naphthylethynylaniline, 3- Anthracenyl ethynyl aniline, 4-anthracenyl ethynyl aniline, etc. are mentioned, and the hydrogen atom on the aromatic is substituted with an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group, an alkoxyl group, or a halogen atom. May be. In view of availability, it is desirable to use 3-aminophenylacetylene, 4-aminophenylacetylene, 3-phenylethynylaniline, and 4-phenylethynylaniline. Two or more of the above compounds may be mixed and used.

  The target molecular weight of the imide oligomer or isoimide oligomer corresponds to the precursor amic acid oligomer.

  The amount of the molecular end-capping agent having a crosslinkable group varies depending on the molecular weight of the target amic acid oligomer, but usually 1 to the number of moles difference between tetracarboxylic dianhydride and diamine compound. The number of moles is double, desirably 1.5 to 4 times. When the number of moles of tetracarboxylic dianhydride is larger, an amine-based molecular terminal blocking agent is used, and when the number of moles of the diamine compound is larger, an acid-based molecular terminal blocking agent is used.

  The solvent used for the production of the amic acid oligomer is not particularly limited as long as it is an inert solvent for the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, Tetramethylurea, tetrahydrofuran and the like can be used alone or in a mixed form. Particularly preferred are N, N-dimethylacetamide and N-methyl-2-pyrrolidone. Further, these solvents may be used by mixing benzene, toluene, xylene, mesitylene, chlorobenzene, diglyme, triglyme and the like in an arbitrary ratio. The reaction is usually carried out at a solute concentration of 5 to 80%.

  Next, imidization and isoimidization of an amic acid oligomer will be described. The imidization reaction is performed by dehydrating the amic acid oligomer obtained by the above reaction by a known method. For example, the chemical imidization method is not particularly limited to the amic acid oligomer solution obtained by the above reaction, but acetic anhydride, trifluoroacetic anhydride, polyphosphoric acid, phosphorus pentoxide, phosphorus pentachloride, Dehydration is performed by using a dehydrating agent such as thionyl chloride alone or in combination of two or more. A catalyst such as pyridine may be used. In the thermal imidization method, a solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, diglyme, and triglyme is mixed in an arbitrary ratio to the amic acid oligomer solution obtained by the above reaction, heated, and then ring-closed. Dehydration is performed while the generated water is discharged out of the system. These solvents may be used alone or in combination of two or more. The isoimidization reaction is performed by dehydrating the amic acid oligomer obtained by the above reaction by a known method. For example, dehydration is performed by using a dehydrating agent such as trifluoroacetic anhydride or N, N-dicyclohexylcarbodiimide alone or in combination of two or more. A catalyst such as pyridine may be used.

  The imide oligomer or isoimide oligomer according to the present invention may be used as a powder after pouring into a solvent such as water or alcohol after completion of imidation or isoimidization, reprecipitation, taking out the crystals by filtration and drying. A by-product of an isoimidating agent such as dicyclohexylurea may be removed by filtration and used as a solution.

  The resin composition of the present invention comprises a polyimide or polyamic acid obtained as described above, and, if desired, a resin composition containing an imide oligomer and / or an isoimide oligomer having a crosslinkable group, What contains a thermosetting bisimide compound and / or a bisisoimide compound at a weight ratio of 99/1 to 20/80 is desirable, and a thing containing a weight ratio (solid content) of 95/5 to 40/60 is particularly preferred, and varnish Or in powder form.

  The heat-resistant adhesive of the present invention can be prepared from the resin composition of the present invention in the form of varnish or powder. The solvent used for the preparation of the heat-resistant adhesive is not particularly limited as long as it has no chemical reactivity with each component and is soluble. For example, lower alcohols (eg methanol, ethanol, propanol, isopropanol, butanol etc.), lower alkanes (eg pentane, hexane, heptane, cyclohexane etc.), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone etc.) Halogenated hydrocarbons (eg, dichloromethane, carbon tetrachloride, fluorobenzene, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.) or esters (methyl acetate, ethyl acetate, butyl acetate, etc.), etc. May be used alone or in a mixed form. The concentration of the resin composition of the present invention contained in the heat-resistant adhesive is not particularly limited and is appropriately selected according to the solubility of each component, the usage state of the heat-resistant adhesive, and the like, for example, 5 to 80% Preferably, the solute concentration is Further, various fillers or additives may be mixed within a range not impairing the object of the present invention.

  Similarly, the varnish of the present invention can be prepared from the resin composition of the present invention in the form of varnish or powder. The solvent used for the preparation of the varnish is not particularly limited as long as it is soluble in each component, and may preferably be a reaction solvent used for adjusting each component. As the solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, tetrahydrofuran and the like can be used alone or in a mixed form. Particularly preferred are N, N-dimethylacetamide, N-methyl-2-pyrrolidone and tetrahydrofuran. Further, these solvents may be mixed with a solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, diglyme and triglyme in an arbitrary ratio. Moreover, after completion | finish of reaction of each component, the solution obtained by the appropriate process may be mixed and a varnish may be prepared. The concentration of the resin composition of the present invention contained in the varnish is not particularly limited and is appropriately selected according to the solubility of each component, the manner of use of the varnish, and the like, for example, a solute concentration of 5 to 80%. Is preferred.

  A film can also be produced from the resin composition of the present invention. Usually, the varnish containing the resin composition of the present invention is applied to a substrate such as glass, aluminum, copper, stainless steel, PET film, polyimide film, etc., and the solvent is dried to obtain a desired thickness, preferably 1 μm. It can be obtained as a film having a thickness of ˜200 μm, more preferably 1 μm to 100 μm. The obtained film is appropriately subjected to a curing treatment at 180 to 450 ° C. to obtain a cured product.

  A metal foil to be a conductive layer such as a copper foil is laminated on at least one surface of a film obtained from the resin composition of the present invention, and a desired temperature condition, for example, 180 ° C. to 200 ° C., a desired pressure condition, for example, A metal laminate can be obtained by pressing at 5 MPa. Furthermore, the obtained metal laminate is appropriately subjected to a curing treatment at 200 to 450 ° C. to obtain a cured product as desired. Moreover, the metal laminated body which consists of a multilayer can be manufactured by laminating | stacking the metal laminated body hardened | cured material obtained in this way and the film obtained from the resin composition of this invention, and repeatedly pressing.

  Furthermore, the aromatic polymer metal laminated body which concerns on this invention laminates | stacks an aromatic polymer and copper foil via the heat resistant adhesive which consists of a resin composition of this invention. The aromatic polymer of the present invention only needs to have at least one benzene ring in the repeating unit of the main chain and have insulating properties. For example, polyimide, polysulfone, polyphenylene sulfide, polyaryl ether ketone, polycarbonate, liquid crystal Examples thereof include a polymer or polybenzoxazole.

  In the method for producing an aromatic polymer metal laminate of the present invention, for example, first, a laminate of an aromatic polymer or a metal foil and the heat-resistant adhesive of the present invention is produced. A heat-resistant adhesive obtained as described above on an aromatic polymer having a thickness of 1 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 75 μm, or a metal foil serving as a conductive layer such as a copper foil. The varnish is coated so that the thickness after drying the solvent is 0.1 to 100 μm, preferably 1 to 30 μm, more preferably 1 to 10 μm, and the solvent is dried. After obtaining an aromatic polymer or metal foil / heat-resistant adhesive laminate, a laminate comprising an insulating layer / adhesive layer / conductive layer is obtained by further thermal lamination with the metal foil or aromatic polymer. Can do. The heat-resistant adhesive according to the present invention has extremely good adhesion to aromatic polymers and metal foils without the need for surface treatment such as chemical treatment, sandblast treatment, and plasma treatment, which have been conventionally performed to improve adhesion. Indicates. However, it is also possible to perform surface treatment for the purpose of improving the wettability of the aromatic polymer surface, eliminating the repellency of the heat-resistant adhesive coating film, and obtaining a uniform thickness, especially plasma treatment. It is preferable to obtain a uniform coating thickness.

  The thickness of the metal foil, particularly preferably the copper foil, is 0.1 to 100 μm, desirably 0.5 to 36 μm, and more desirably 1 to 18 μm. When it is thick, it becomes difficult to make fine wiring such that the line / space is 25 μm / 25 μm or less, and when it is too thin, handling becomes difficult when laminating.

  The temperature of the thermal laminate is 100 to 300 ° C, desirably 120 to 250 ° C, more desirably 120 to 200 ° C. When the laminating temperature exceeds 300 ° C., wrinkles occur in the manufactured flexible laminate due to the difference in dimensional change with copper foil, heat-resistant adhesive, and aromatic polymer, resulting in poor appearance, poor insulation, poor conduction, etc. May be defective. Furthermore, oxidation of the copper foil is inevitable.

  For example, when laminating an ultrathin copper foil (0.1 to 5 μm) and an aromatic polymer, an ultrathin copper foil with a PET film support is used. However, in general, since the use temperature range of the PET film is 190 ° C. or lower, when laminating using a normal thermoplastic polyimide adhesive, a temperature of 250 ° C. or higher is required, and the heat shrinkage of the PET is reduced. Large and warped. There is also a problem that the PET film melts and contaminates the device. On the other hand, when the heat-resistant adhesive of the present invention is used, it is possible to laminate at 190 ° C. or lower, and it is possible to laminate with a copper foil with a PET film support, which facilitates the production of an ultrathin copper foil laminate. .

  Further, the heat-resistant adhesive of the present invention is applied to the varnish so that the thickness after drying the solvent is 0.1 to 100 μm, desirably 1 to 30 μm, more desirably 1 to 10 μm on at least one surface of the aromatic polymer film. A further aromatic polymer film is laminated on the aromatic polymer / heat-resistant adhesive laminate obtained by coating the substrate and drying the solvent, and adhesion is performed, or a film-like aromatic polymer / heat-resistant adhesive is used. An aromatic polymer laminated body and a cylindrical aromatic polymer can be obtained by making a laminated body into a cylindrical shape and performing adhesion.

  In order to clarify aspects of the present invention, examples and comparative examples are shown below, but the present invention is not limited to only the examples shown here.

Synthesis example 1
Synthesis of polyamic acid and soluble polyimide; 31.0215 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride, 2,2-bis [4- (4-aminophenoxy) phenyl] propane 41 in a four-necked flask 0.0508 g (0.1 mol) and 408.4 g of N-methyl-2-pyrrolidone (NMP) were charged and stirred at room temperature for 4 hours to obtain a polyamic acid solution having a solute concentration of 15% and a viscosity of 80,000 mPa · s. . 40.8 g of xylene was added to the polyamic acid solution thus obtained, and then the flask was heated at 200 ° C. and refluxed for 8 hours while distilling out the water from the imidization together with xylene. The solution was cooled to room temperature to obtain a soluble polyimide solution having a solute concentration of 15% and a viscosity of 60,000 mPa · s.

Synthesis example 2
Synthesis of isoimide oligomer: 4,4′-oxydiphthalic dianhydride 12.4086 g (0.04 mol), 1,3-bis (3-aminophenoxy) benzene 23.3866 g (0.08 mol) in a four-necked flask 4-phenylethynyl phthalic anhydride (19.8568 g, 0.08 mol) and NMP254.0 g were charged and stirred in a nitrogen stream at room temperature for 3 hours. While cooling the flask to 5 ° C., a solution obtained by dissolving 33.0 g (0.16 mol) of dicyclohexylcarbodiimide (DCC) in 61.3 g of NMP was added dropwise from a dropping funnel over 1 hour. After returning to room temperature and stirring for 3 hours, dicyclohexylurea (DCU) by-produced in the reaction was filtered off to obtain an isoimide oligomer having a solution concentration of 15%.

Example 1
Synthesis of bisimide compound represented by the above formula (3); 41.0287 g (0.1 mol) of ethylene glycol bis (trimellitate) dianhydride, 365.3 g of N-methyl-2-pyrrolidone, xylene 36. 5 g was charged and dissolved in a nitrogen stream. 23.4296 g (0.2 mol) of 3-aminophenylacetylene was injected from the dropping funnel and stirred at room temperature for 4 hours to synthesize a yellow amic acid solution. Subsequently, the flask was heated to 200 ° C. and refluxed for 8 hours while distilling out the water by imidation out of the system together with xylene. The mixture was cooled to room temperature to precipitate crystals, filtered, and dried to obtain a bisimide compound represented by the formula (3) (yield 70%, purity 99%). NMR and IR charts are shown in FIGS.

Example 2
Synthesis of adhesive and adhesive film; Soluble polyimide obtained as in Synthesis Example 1 and Example 1 and thermosetting bisimide were mixed at a solute weight ratio of 80:20, and the solute concentration was It was diluted with NMP so as to be 15% to obtain a varnish having a viscosity of 10,000 mP · s. The obtained varnish was applied onto aluminum which had been subjected to a release treatment so that the thickness after drying was 25 μm, and dried at 160 ° C. for 4 minutes to obtain a film.

Example 3
Synthesis of adhesive and adhesive film; Soluble polyimide obtained in Synthesis Example 1 and Synthesis Example 2 and thermosetting isoimide oligomer were mixed at a solute weight ratio of 50:50, and The bisimide compound obtained in Example 1 was mixed so as to be 20 wt% with respect to the total solid content of the varnish, diluted with NMP so that the solute concentration became 15%, and the viscosity was 6,500 mP · s. The varnish was obtained.

Example 4
Preparation of polyimide film metal laminate: 12 μm thick copper foil (3EC-VLP manufactured by Mitsui Kinzoku Co., Ltd.) was laminated on both sides of the polyimide resin composition film obtained in Example 2, and 30 at a pressure of 180 ° C. and 5 MPa. Press for a minute. A part of this laminate was cut out and the peel strength with the copper foil was measured to be 0.9 kN / m. Further, the remaining laminate was heat-treated at 250 ° C. and a pressure of 5 MPa for 10 minutes. The peel strength of the laminate after the heat treatment was 1.0 kN / m. It was 255 degreeC when the glass transition temperature of the polyimide resin composition after heat processing was measured by DSC.

Example 5
Preparation of polyimide film metal laminate: 50 μm thick Kapton 200EN was coated with the varnish obtained in Example 3 so that the thickness of the adhesive layer after drying was 2 μm, and dried at 160 ° C. for 4 minutes, A film sample was obtained. When the obtained film sample and a copper foil having a thickness of 9 μm (CF-T9FZ-SV manufactured by Fukuda Metal Co., Ltd.) were laminated and laminated at a temperature of 175 ° C., lamination was possible. The metal laminate thus obtained was cured for 90 seconds at a temperature of 380 ° C. under vacuum, and when peel measurement was performed, it was 1.1 kN / m adhesive strength.

Example 6
Preparation of polyimide laminate: 50 μm thick Kapton 200EN was coated with the varnish obtained in Example 3 so that the thickness of the adhesive layer after drying was 2 μm, dried at 160 ° C. for 4 minutes, and film sample Got. When the obtained film sample and Kapton 200EN having a thickness of 50 μm were laminated and laminated at a temperature of 175 ° C., lamination was possible. The metal laminate thus obtained was cured for 90 seconds at a temperature of 350 ° C. under vacuum, and peel measurement was performed. As a result, the adhesive strength was 2.0 kN / m.

Comparative Example 1
A film was prepared in the same manner as in Example 2 using only the soluble polyimide varnish obtained in Synthesis Example 1. Although it was pressed with a copper foil in the same manner as in Example 4, adhesion to the copper foil was impossible.

Comparative Example 2
A bisimide compound having no triple bond at both ends was synthesized in the same manner as in Example 1 except that aniline was used instead of 3-aminophenylacetylene, and a crosslinkable group was synthesized in the same manner as in Example 2. The polyimide resin composition film which does not have was obtained. Adhesion with the copper foil was attempted in the same manner as in Example 4, but sufficient adhesive strength was not obtained (peel strength 0.1 kN / m or less).

  The polyimide resin composition of the present invention is excellent in meltability and fluidity at relatively low temperatures, and has good workability at low temperatures. Moreover, the cured product obtained by crosslinking and curing by heat treatment is excellent in adhesiveness, solder heat resistance, and electrical characteristics, and particularly in the interlayer insulating material of the multilayer printed wiring board and the flexible metal laminate. Suitable as heat resistant adhesive.

The ¹ H-NMR chart of the compound (compound represented by Formula (3)) obtained in Example 1 is shown. The IR chart of the compound (compound represented by Formula (3)) obtained in Example 1 is shown.

Claims (20)

Polyimide and the following general formula (1):

(In the formula, one of A and B is = O and the other is = NAr ¹ R ¹ ;
Ar ¹ is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or a polycyclic compound in which two or more of the same or different aromatic compounds are connected to each other directly or by a bridging member. A divalent group,
R ¹ is a monovalent organic group having 2 to 36 carbon atoms and containing at least one carbon-carbon double bond or carbon-carbon triple bond;
X ¹ and X ² are each independently a single bond, —O—, —CO—, —COO—, —OCO—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ). ₂ −
R ² represents an alkanediyl group having 2 to 18 carbon atoms, a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or two or more of the same or different aromatic compounds directly or as a cross-linking member. A divalent group of polycyclic compounds linked together by
Here, the term “crosslinking member” means —O—, —CO—, —COO—, —OCO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. Is)
The polyimide resin composition characterized by including the bisimide compound or bisisoimide compound represented by these.   The polyimide resin composition according to claim 1, comprising polyimide and a bisimide compound or bisisoimide compound in a weight ratio of 95/5 to 40/60. Polyamic acid and the following general formula (1):

(In the formula, one of A and B is = O and the other is = NAr ¹ R ¹ ;
Ar ¹ is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or a polycyclic compound in which two or more of the same or different aromatic compounds are connected to each other directly or by a bridging member. A divalent group,
R ¹ is a monovalent organic group having 2 to 36 carbon atoms and containing at least one carbon-carbon double bond or carbon-carbon triple bond;
X ¹ and X ² are each independently a single bond, —O—, —CO—, —COO—, —OCO—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ). ₂ −
R ² represents an alkanediyl group having 2 to 18 carbon atoms, a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or two or more of the same or different aromatic compounds directly or as a cross-linking member. A divalent group of polycyclic compounds linked together by
Here, the term “crosslinking member” means —O—, —CO—, —COO—, —OCO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. Is)
The polyamic acid resin composition characterized by including the bisimide compound or bisisoimide compound represented by these.   The polyamic acid resin composition according to claim 3, comprising a polyamic acid and a bisimide compound or a bisisoimide compound in a weight ratio of 95/5 to 40/60. R ¹ is represented by the following general formula (2):

The resin composition according to claim 1, wherein R is a group represented by the formula: R is hydrogen or an organic group having 1 to 34 carbon atoms.   6. The resin composition according to claim 5, wherein R is hydrogen.   R is a phenyl group, The resin composition of Claim 5 characterized by the above-mentioned. The following formulas (3) and (4):

The bisimide compound and bisisoimide compound which are represented by these.   Furthermore, the imide oligomer or isoimide oligomer which has a crosslinkable group is included, The resin composition of any one of Claims 1-7 characterized by the above-mentioned. An imide oligomer or an isoimide oligomer having a crosslinkable group is represented by the following general formulas (5) to (8):

(Wherein n is a number from 1 to 20,
R ³ and R ⁴ are independently hydrogen or a phenyl group,
Ar ² and Ar ⁴ are each independently a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or two or more of the same or different aromatic groups are connected to each other directly or by a bridging member A tetravalent group of the obtained polycyclic compound,
Ar ³ and Ar ⁵ are each independently a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, wherein two or more of the same or different aromatic groups are directly connected to each other by a cross-linking member. A divalent group of the polycyclic compound,
Here, the term “crosslinking member” means —O—, —CO—, —COO—, —OCO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. Is)
The resin composition of Claim 9 selected from these.   The resin composition according to any one of claims 1 to 7, and an imide oligomer or an isoimide oligomer having a crosslinkable group in a weight ratio of 95/5 to 20/80. The resin composition as described.   A heat resistant adhesive comprising the resin composition according to any one of claims 1 to 7 and 9 to 11.   The varnish containing the resin composition of any one of Claims 1-7 and 9-11.   The film obtained by apply | coating the varnish of Claim 13 to a base material, and drying.   The metal laminated body formed by laminating | stacking metal foil on the at least single side | surface of the film of Claim 14.   The metal laminated body formed by laminating | stacking metal foil on the at least single side | surface of the insulating layer which consists of an aromatic polymer through the heat resistant adhesive of Claim 12.   The metal laminate according to claim 16, wherein the aromatic polymer is selected from polyimide, polysulfone, polyphenylene sulfide, polyaryl ether ketone, polycarbonate, liquid crystal polymer or polybenzoxazole.   The metal laminate according to claim 17, wherein the surface of the aromatic polymer is plasma-treated.   The electronic circuit using the metal laminated body of any one of Claims 15-18. An aromatic polymer laminate or a cylindrical aromatic polymer obtained by laminating a further aromatic polymer film on at least one surface of the aromatic polymer film via the heat-resistant adhesive according to claim 12.

Images