KR100517233B1 - Polyimide resin and polyimide-metal clad laminate - Google Patents

Abstract

A heat-resistant resin composition having excellent low temperature adhesiveness, and a lead-free solder, an Au-Sn bonding used for COF mounting, or a polyimide metal laminate having excellent solder heat resistance in which blister does not easily occur during Au-Au bonding To provide.

General formula (1) to polyamic acid, polyimide, or polyamic acid and polyimide

(Wherein m represents an integer of 0 or more, X may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond, and R1 is the same or different, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, and the substitution positions of the benzene rings are each independently a resin composition composed of a bismaleimide compound represented by A metal laminate and a resin composition thereof, which are laminated on at least one side of a metal foil.

Description

Metal laminate {POLYIMIDE RESIN AND POLYIMIDE-METAL CLAD LAMINATE}

The present invention relates to a resin laminate for a metal laminate and a polyimide laminate, which is excellent in low temperature adhesiveness and excellent in solder heat resistance.

Polyimide has excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and the like, and is widely used as a heat resistant adhesive used in an electronic field represented by a flexible printed circuit board, a semiconductor package, and the like, as well as in the aviation field where heat resistance is required.

In recent years, the polyimide heat resistant adhesives have been required to have a low temperature adhesive property in addition to processing and heat resistance.

As excellent low-temperature adhesiveness, for example, Patent Document 1 reports a resin composition composed of a polyimide resin having an siloxane unit, an epoxy resin, and a phosphate ester plasticizer. However, in this case, since a polyimide resin, an epoxy resin, a plasticizer, any component, and an aliphatic unit are contained, the thermal decomposition temperature falls and there is a problem from the viewpoint of heat resistance.

On the other hand, resins composed of specific polyamic acid and bismaleimide compounds disclosed in Patent Document 2, Patent Document 3, and Patent Document 4, etc. have been developed as having sufficient adhesive strength and heat resistance. In addition, in view of low temperature adhesiveness, there are still many insufficiencies, and in this patent publication, only a film is manufactured as the use.

On the other hand, in view of environmental preservation in recent years, lead-free solder has been used for mounting electronic components, and solder heat resistance is also used in the mounting of chips and components or in the process of disassembling chips or components called repairs. Excellent polyimide metal laminates are desired. In addition, it has been pointed out that the reliability of the solder heat temperature, which has been conventionally required in applications called rigid flex or flexible multilayer boards, is insufficient, and higher temperature heat resistance is desired. When a metal laminate is used for a chip-on-film (hereinafter sometimes abbreviated as COF), an Au-Au bonding or Au-Sn is used at a high temperature of 300 ° C. or higher using an inner lead bonder or a flip chip bonder. By bonding, the chip and the metal wiring are joined. Therefore, even when used for COF, the base material which is excellent in solder heat resistance is desired.

Currently, as a COF base material, the polyimide metal laminated plate obtained by spattering a metal in the polyimide film which is a non-thermoplastic polyimide has been mainly used (refer patent document 5). However, in the case of the spatter method, productivity is apt to deteriorate by the pinhole of a metal layer, and the metal laminated board without a pinhole is desired.

Patent Document 1: Japanese Patent Application Laid-Open No. 10-212468

Patent Document 2: Japanese Patent Application Laid-Open No. 01-289862

Patent Document 3: Publication No. 6-145638

Patent Document 4: Japanese Patent Application Laid-Open No. 6-192639

Patent Document 5: Japanese Patent Application Laid-Open No. 07-070762

 An object of the present invention is to provide a resin composition for polyimide laminate having excellent low temperature adhesiveness.

On the other hand, the present invention provides a polyimide metal laminated plate having no pinholes and excellent solder heat resistance, and further, a blister for lead-free solder, Au-Sn bonding used for COF mounting, or Au-Au bonding. It does not generate | occur | produce easily, and the polyimide metal laminated board which is excellent in solder heat resistance is provided.

The inventors of the present invention considered a rolled copper foil or a flexible circuit board in which an electrolytic copper foil and a polyimide were laminated as a polyimide metal laminated plate without a pinhole. However, when a polyimide is used as an adhesive, depending on the polyimide to be used, foaming is performed. The present inventors have found out that there is a problem in the present invention, and as a result of studying the results, by blending a specific bismaleimide compound with polyamic acid, polyimide, or polyamide and polyimide, excellent low-temperature adhesiveness and solder heat resistance It was found that the above problems can be solved, and the present invention has been completed.

That is, this invention is as showing below.

(1) General formula (1) to polyamic acid, polyimide, or polyamic acid and polyimide

(Wherein m represents an integer of 0 or more, X may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond, and R1 is the same or different, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, and the substitution positions of the benzene rings are each independently a resin composition composed of a bismaleimide compound represented by And laminated on at least one side of the metal foil.

(2) The metal laminated body of (1) description whose metal laminated body is a structure in which the polyimide layer was formed in the single side | surface or both surfaces of one or more layers of polyimide films, and metal was laminated | stacked on the single side | surface or both sides in this polyimide layer.

(3) The polyamic acid and the polyimide are represented by General Formula (2) and General Formula (3), respectively.

(Wherein n represents an integer of 0 or more, Y may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , and C (CF ₃ ) ₂ or a direct bond, A is a tetravalent organic group, R 2 is the same or different, represents a hydrogen atom, a halogen atom, a hydrocarbon group, and the positions of substitution of the benzene rings are each independently a repeating structural unit; Metal laminate of (1) substrate which has a.

(4) The tetravalent organic group represented by A is a general formula (4)

(Wherein Z represents O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond.) The metal laminate of (3).

(5) General formula (1) to polyamic acid, polyimide, or polyamic acid and polyimide

(Wherein m represents an integer of 0 or more, X may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond, wherein R ₁ is the same or different and represents a hydrogen atom, a halogen atom, a hydrocarbon group, and the positions of substitution of the benzene rings are each independently; The resin composition for polyimide metal laminated bodies made into.

Hereinafter, the present invention will be described in detail.

The present invention relates to polyamic acid, polyimide, or polyamic acid and polyimide, in general formula (1)

(Wherein m represents an integer of 0 or more, X may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond, and R1 is the same or different and represents a hydrogen atom, a halogen atom, a hydrocarbon group, and the substitution positions of the benzene rings are each independently a polyimide laminate comprising a mixture of bismaleimide compounds The resin composition for a body and this resin composition are laminated | stacked on the at least single side | surface of metal foil, It is related with the metal laminated body characterized by the above-mentioned.

In general formula (1), m represents the integer of 0 or more, Preferably it is 0-6, More preferably, it is 0-4. X may be the same as or different from each other independently, and represents O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) _2, or a direct bond, and preferably O , C (CH ₃ ) ₂ , a direct bond. R1 is the same or different, and represents a hydrogen atom, a halogen atom, and a hydrocarbon group, and the substitution positions of the benzene rings are each independent of each other. Preferably, the substituted position of the benzene ring is a compound bonded to the ortho or meta position.

Although there is no restriction | limiting in particular in the polyamic acid and polyimide of this invention, Preferably, they are respectively General formula (2) and General formula (3).

(Wherein n represents an integer of 0 or more, Y may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ represents a direct bond, and A is a tetravalent organic group, R 2 is the same or different, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, and the positions of substitution of the benzene rings are each independently a repeating structural unit; And preferably have the general formula (5) and the general formula (6)

(Wherein l represents an integer of 1 to 7. R2 is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group, and the positions of substitution of the benzene ring are each independently independent of each other and are the same selected from an oxygen atom and a nitrogen atom. Two heteroatoms which are bonded to the benzene ring are the same or different at least one benzene ring in ortho-position or meta-position, and A has a repeating structural unit represented by tetravalent organic group), More preferably, general formula (7) and general formula (8), respectively

(Wherein l represents an integer of 1 to 7 and two identical or different heteroatoms bonded to the same benzene ring selected from an oxygen atom and a nitrogen atom are each selected from the ortho position or the meta position with respect to the at least one benzene ring). In addition, A has a repeating structural unit represented by a tetravalent organic group), and more preferably, General formula (9) and General formula (10), respectively.

(Wherein l and A represent the same meaning as described above).

In general formula (2)-(3), n represents the integer greater than or equal to 0, Preferably it is 0-6, More preferably, it is 0-4. In General Formula (5)-(10), l represents the integer of 1-7, Preferably it is 1-5, More preferably, it is 1-3. In addition, Y may be the same as or different from each other independently, and represents O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond, preferably O , CO, C (CH ₃ ) ₂ , a direct bond.

In General Formulas (2) to (6), R2 is the same or different and represents a hydrogen atom, a halogen atom, or a hydrocarbon group, and the substitution positions of the benzene ring are each independently of each other, and preferably, the substitution position of the benzene ring is an ortho position. Or a compound bound to a meta position.

Although the tetravalent organic group represented by A in General formula (2)-(10) does not have a restriction | limiting in particular, For example, a C2-C27 aliphatic group, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group , A tetravalent organic group selected from the group consisting of non-condensed polycyclic aromatic groups interconnected by an aromatic group directly or by a crosslinking agent, and is preferably represented by General Formula (4).

(Wherein Z represents O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond.).

In the general formulas (1) to (3), (5) and (6), examples of the halogen atom represented by R1 and R2 include a chlorine atom and a fluorine atom. Examples of the hydrocarbon group include a methyl group and an ethyl group. Lower alkyl groups, lower alkenyl groups such as vinyl and aryl groups, aralkyl groups such as benzyl and phenethyl groups, aryl groups such as phenyl and naphthyl groups, alkoxy groups such as methoxy groups and ethoxy groups, and halogenated alkyl groups such as trifluoromethyl groups Etc. can be mentioned.

As a specific example of the bismaleimide compound represented by General formula (1), 1, 3-bis (3- maleimide phenoxy) benzene, bis (3- (3- maleimide phenoxy) phenyl) ether, 1, 3 -Bis (3- (3-maleimidephenoxy) phenoxy) benzene, bis (3- (3- (3-maleimidephenoxy) phenoxy) phenyl) ether, 1,3-bis (3- (3 -(3-maleimide phenoxy) phenoxy) phenoxy) benzene, N, N'-p-phenylenebismaleimide, N, N'-m-phenylenebismaleimide, bis (4-maleimidephenyl Methane, N, N'-4,4'-diphenyletherbismaleimide, N, N'-3,4'-diphenyletherbismaleimide, N, N'-3,3'-diphenylketone Bismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (4- (3-maleimidephenoxy) phenyl) propane, 4-4'-bis (3-maleimidephenoxy) biphenyl, 2,2-bis (4- (3-maleimidephenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4 -(3-maleimidephenoxy) phenyl) ketone, bis (4- (3-maleimidephenoxy) Carbonyl) sulfide, bis (4- (3-maleimidophenoxy) phenyl) sulfone, etc. but are not limited to these.

These bismaleimide compounds can be produced by condensation and dehydration reaction of the corresponding diamine compounds and maleic anhydride, for example, by the method described in JP-A 4-99764.

Moreover, when manufacturing the metal laminated body of this invention, although the compounding ratio to a polyimide of a bismaleimide compound does not have a restriction | limiting in particular, It is preferably 0.1-70 with respect to the total weight of the polyamic acid which is a precursor of a polyimide. It is weight%, More preferably, it is 0.1-50 weight%. When the compounding quantity of the bismaleimide compound is less than 0.1% by weight, there is little effect in improving the solder heat resistance, which is the object of the present invention, and when it exceeds 70% by weight, the adhesive strength of the metal foil tends to decrease.

As a compounding method of a bismaleimide compound to polyamic acid, (i) the method of adding a bismaleimide compound to a polyamic-acid solution, (ii) at the time of superposition | polymerization of polyamic acid, a diamine compound or tetracarboxylic acid, The method of adding an anhydride at the time of loading or in the middle of superposition | polymerization, (i) The method of mixing the powder of a polyamic acid and a bismaleimide compound as a solid, etc. are mentioned, but it is not limited to these.

The polyamic acid may be dehydrated in advance to form a polyimide solution, and then a bismaleimide compound may be blended.

Polyamic acid represented by General formula (2) is General formula (11)

In the formula, n, Y, and R 2 represent the same meaning as described above. The diamine compound and the general formula (12)

It is obtained by making tetracarboxylic dianhydride shown by (wherein A represents the same meaning as the above), and the resin composition which dehydrated the resin composition obtained from this polyamic acid also belongs to this invention.

As a specific example of the aromatic diamine compound represented by General formula (9), it is (3- (3-aminophenoxy) phenyl) ether, 1, 3-bis (3- (3-amino phenoxy) phenoxy) benzene, for example. , Bis (3- (3- (3-aminophenoxy) phenoxy) phenyl) ether, 1,3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene, o- Phenylenediamine, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 3,4'-diaminobenzo Phenone, bis (4-aminophenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (3-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, 1,3-bis ( 4- (4-aminophenoxy) -α, α-dimethylbenzyl) benzene, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, 1,3-bis (1- (4- (4-a Nophenoxy) phenyl) -1-methylethyl) benzene, 1,4-bis (1- (4- (4-aminophenoxy) phenyl) -1-methylethyl) benzene, 1,4-bis (1- (4- (3-aminophenoxy) phenyl) -1-methylethyl) benzene, 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, and the like, It is not limited.

In the formula (12), A represents a tetravalent organic group, and specifically, for example, an aliphatic group having 2 to 27 carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is directly or Tetravalent organic groups selected from the group consisting of non-condensed polycyclic aromatic groups interconnected by a bridging member.

There is no restriction | limiting in particular in the tetracarboxylic dianhydride represented by General formula (12), By using the conventionally well-known tetracarboxylic dianhydride, the polyimide which has various glass transition temperatures can be obtained.

Specific examples of the tetracarboxylic dianhydride include, for example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, oxy-4,4'-diphthalic dianhydride, 2,2 -Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, ethylene glycol bistrimeric dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1 , 3,3,3-hexafluoropropane anhydride and the like, and preferably, for example, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4, 4'-benzophenonetetracarboxylic dianhydride, 1,2-bis (3,4-dicarboxybenzoyl) benzene dianhydride, 1,3-bis (3,4-dicarboxybenzoyl) benzene dianhydride, 1,4 -Bis (3,4-dicarboxybenzoyl) benzene dianhydride, 2,2'-bis ((3,4-dicarboxy) phenoxy) benzophenone dianhydride, 2,3'-bis ((3,4- Dicarboxy) phenoxy) benzophenone dianhydride, 2,4'-bis ((3,4-dicarboxy) phenoxy) benzophenone dianhydride, 3,3'-bis ((3,4-dicarboxy) phenoxy Benzophenone Water, 3,4'-bis ((3,4-dicarboxy) phenoxy) benzophenone dianhydride, 4,4'-bis ((3,4-dicarboxy) phenoxy) benzophenone dianhydride, etc. Can be. These can be used individually or in mixture of 2 or more types.

In this invention, as a manufacturing method of a polyamic acid, all the methods which can manufacture a polyamic acid are applicable including a well-known method. Especially, it is preferable to make reaction in an organic solvent. Examples of the solvent that can be used in such a reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,2-dimethoxyethane and the like. .

In this reaction, the concentration of the reaction raw material is usually 2 to 50% by weight, preferably 10 to 50% by weight. Reaction temperature is 60 degrees C or less normally, Preferably it is 50 degrees C or less. The reaction pressure is not particularly limited and can be sufficiently performed at normal pressure. Moreover, although reaction time changes with kinds of reaction raw material, a kind of solvent, and reaction temperature, 0.5-24 hours is enough normally. By this polycondensation reaction, the polyamic acid represented by the general formula (2) is produced.

The polyimide represented by General formula (3) responds to polyamic acid by imidating this polyamic acid by heating at 100-400 degreeC, or chemically imidating using imidating agents, such as an acetic anhydride. A polyimide having a repeating structural unit can be obtained.

Moreover, by making it react at 130-250 degreeC, production | generation of a polyamic acid and a heat | fever imidation reaction advance simultaneously, and the polyimide of this invention can be obtained. That is, the polyimide in this invention can be obtained by suspending or dissolving a diamine component and an acid dianhydride component in an organic solvent, making it react under the heating of 130-250 degreeC, and simultaneously producing | generating a polyamic acid and dehydrating it. .

The resin composition for the polyimide metal laminate of the present invention may be used in other resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, without departing from the object of the present invention. It is also possible to mix an appropriate amount of polyether ketone, polyether ether ketone, polyphenyl sulfide, modified polyphenylene oxide group, polyamideimide, polyetherimide, epoxy resin and the like.

It is also possible to produce a film from the resin composition for polyimide metal laminate of the present invention, and the method is not particularly limited. For example, (i) the polyamic acid solution may be a substrate (glass plate, metal plate or heat resistance). A resin film), followed by heating and imidization; (ii) a polyimide solution is coated on a substrate (glass plate, metal plate or resin film having heat resistance), and then heated. have.

Moreover, the adhesive insulating tape which has the adhesive bond layer which consists of the resin composition mentioned above, and a heat resistant film can also be comprised. The adhesive insulating tape is constituted with any other layer, in addition to the one-sided tape in which the adhesive layer is formed only on one side of the heat resistant film, and the double-sided tape in which the adhesive layer is formed on both sides of the heat resistant film.

To prepare an adhesive insulating tape from the resin composition for polyimide metal laminate of the present invention, a solution containing the resin composition described above may be applied to one or both surfaces of the heat resistant film and dried. In that case, the thickness after application | coating is 0.5-100 micrometers, Preferably it is 1-30 micrometers.

Examples of the heat resistant film include films of heat resistant resins such as polyimide, polyphenylene sulfide, polyether, polyether ketone, polyether ether ketone, polyethylene terephthalate, epoxy resin-glass cross, ethoxy resin-polyimide-glass Although composite heat-resistant films, such as a cross, etc. are mentioned, Especially the film which consists of polyimide resin is preferable from a viewpoint of heat resistance or dimensional stability. The thickness of the heat resistant film is preferably 5 to 130 µm, more preferably 12.5 to 75 µm.

The metal laminated body of this invention should just laminate | stack the resin composition which mix | blended the bismaleimide compound mentioned above on at least one side of metal foil. As an example of this specific manufacturing method, the varnish containing the thermoplastic polyimide which the bismaleimide compound represented by General formula (1) was mix | blended with the non-thermoplastic polyimide film, or the polyamic acid which is a precursor of this thermoplastic polyimide, for example. The method of apply | coating, drying, and hardening | curing to form a thermoplastic polyimide layer, and also the method of manufacturing by thermopressing the said surface of a metal to the surface of a thermoplastic polyimide layer is mentioned.

The metal laminate of the present invention contains the adhesive layer and the metal foil made of the resin composition described above as essential components, but the adhesive layer or the non-adhesive layer made of another resin composition is a single layer or a multilayer between the adhesive layer and the metal foil. May exist.

In addition, in the metal laminated body of this invention, what is necessary is just to contain at least one layer of the resin composition which mix | blends the bismaleimide compound represented by General formula (1), and the number formed by mix | blending the said several layer compound. You may have a strata.

What is necessary is just to apply | coat the solution containing the resin composition mentioned above to metal foil, and drying it as an example, in producing the metal laminated body of this invention. At this time, the thickness after application is preferably in the range of 0.5 to 100 µm. If it is less than 0.5 micrometer, sufficient adhesive force may not be obtained, and when it exceeds 100 micrometers, adhesiveness may not improve much much.

As a kind of metal foil, all the well-known metal foil and alloy foil are applicable, but a rolled copper foil, an electrolytic copper foil, copper alloy foil, stainless steel foil is suitable from a viewpoint of cost, heat conductivity, rigidity, etc. In addition, the thickness of the metal foil is not limited as long as it is a thickness that can be used on a tape, but may be preferably 2 to 150 µm. More preferably, it is 2-105 micrometers.

In the metal laminate of the present invention, more preferably, a polyimide layer is formed on one side or both sides of one or more layers of polyimide films, and the polyimide layer has a structure in which a metal is laminated on one side or on both sides. A mid layer is a resin composition containing the bismaleimide compound represented by General formula (1).

As a polyimide film, Preferably it is a non-thermoplastic polyimide film, Specifically, the composition synthesize | combined from specific diamine and specific tetracarboxylic dianhydride can be used. As examples of specific diamines, ο-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminophenylether, 3,4'-diaminophenylether, 3,3'- Diamino phenyl ether etc. are mentioned. You may use these individually or 2 types or more.

Examples of the specific tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid Etc. can be mentioned. These may use individual or 2 types or more.

As the non-thermoplastic polyimide film, a commercially available non-thermoplastic polyimide film can also be used. For example, Eupyrex (registered trademark) S, Eupyrex (registered trademark) SGA, Eupyrex (registered trademark) SN (manufactured by Ubeheung Sangsan Co., Ltd.), kafton (registered trademark) H, kafton (registered trademark) V, Kafton (registered trademark) EN (Toray-Dupont Co., Ltd. brand name), Apical (registered trademark) AH, Apical (registered trademark) NPI, Apical (registered trademark) HP (manufactured by Kanebuchi Chemical Co., Ltd.) Etc. can be mentioned. The surface of the non-thermoplastic polyimide may be subjected to plasma treatment, corona discharge treatment, or the like.

Although the thickness of a non-thermoplastic polyimide layer does not have a restriction | limiting in particular according to the objective, The range of 5-250 micrometers can be used suitably.

In addition, a non-thermoplastic polyimide having a different structure may be laminated on the side of the commercially available non-thermoplastic polyimide film not laminated with the thermoplastic polyimide layer.

In the present invention, an insulating protective film, a carrier film and a carrier metal foil may be provided on the adhesive layer of the polyimide film, the adhesive insulating tape or the metal laminate. Polyethylene, polyethylene terephthalate, polypropylene, etc. are mentioned as a protective film and a carrier film, A rolled copper foil, an electrolytic copper foil, copper alloy foil, stainless steel foil etc. are mentioned as carrier metal foil. The thickness is 1 to 200 µm, preferably 10 to 100 µm. Moreover, it is preferable that the 90 degree insulation adhesive strength with an adhesive bond layer is a range of 0.01-10 kN / m.

The polyimide metal laminate provided by the present invention has a remarkable effect of having excellent solder heat resistance. Conventionally, a resin using bismaleimide is known as a heat resistant resin, but this refers to a so-called pyrolysis temperature and is not directly related to solder heat resistance. Specifically, as also in the prior art, the resin obtained by the bismaleimide and the diamine has a 5% weight reduction temperature around 400 ° C., while the polyimide has a high heat resistance around 500 ° C. even if it is a thermoplastic polyimide. However, the solder heat resistance of the metal laminated body using the thermoplastic polyimide conventionally used is about 260 degreeC or less at most, and cannot fully respond to the high temperature of the present use temperature. Therefore, as a countermeasure, an attempt was made to use a thermoplastic polyimide having a high glass transition temperature, but the lamination temperature with the metal foil became high, so that sufficient adhesive strength was not expressed by the conventional process, and the thermoplastic polyimide was uneven on the surface of the metal foil. There is a problem that cannot be completely filled, and a defect called void occurs. Therefore, in the present invention, by mixing the bismaleimide with the polyimide, the glass transition temperature is lowered, the lamination with the metal is facilitated, and the solder heat resistance can be improved by about 20 ° C. more conventionally.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Moreover, the physical property of the polyimide in an Example was measured by the following method.

Glass transition temperature (Tg): Differential scanning calorimeter (manufactured by McScience Co., Ltd., DSC3110) was measured under the conditions of 10 ° C / min temperature increase.

In addition, when Tg was not calculated | required by the DSC method, it calculated | required from the peak of the loss elastic modulus (E ") obtained by the solid-state viscoelastic apparatus RSAII (manufactured by Leometrics) at IHz and 5 degree-C / min temperature rising conditions.

90 ° C Insulation adhesion strength: measured according to IPC-TM-650 method 2,4,9.

In addition, the solder heat test in Examples was conducted under IPC-TM-650 (The Institute for Interconnecying and Packaging Electronic Circuits) No. It carried out based on 2.4.13. Solder temperature was performed at 240 degreeC, 260 degreeC, 280 degreeC, 300 degreeC, 320 degreeC, and 340 degreeC, and made the solder heat-resistant temperature the highest temperature which the discoloration of a blister, a metal, and a polyimide interface does not generate | occur | produce. In addition, the sample used was 85 degreeC, 85% of a relative humidity, and 50 hours of condition adjustment.

Example 1

In a vessel equipped with a stirrer and a nitrogen introduction tube, 12.00 g of 1,3-bis (3-aminophenoxy) benzene, 15.94 g of 1,3-bis (3-maleimidephenoxy) benzene and N, N-dimethylacetamide 48.70 g was added thereto, and the mixture was stirred at 50 ° C for 1 hour in a nitrogen atmosphere. Thereafter, the temperature in the system was lowered to room temperature, and 11.90 g of 3,3 ', 4,4',-benzophenonetetracarboxylic dianhydride was added thereto, paying attention to the increase in solution temperature, and then warmed up to 50 ° C for 4 hours. Stirred.

A part of the obtained bismaleimide compound-containing polyamic acid solution was taken, cast on a glass plate, and then heated at a temperature increase rate of 7 ° C./min from 50 ° C. to 270 ° C. to obtain a film having a thickness of 20 μm. The glass transition temperature (Tg) of the obtained polyimide film was 106 degreeC.

In addition, a part of the obtained bismaleimide compound-containing polyamic acid solution was cast on copper foil (manufactured by Nippon KK, SLP-35, thickness 35 µm), and then heated at a temperature increase rate of 7 ° C / min from 50 ° C to 270 ° C. To obtain a metal laminate having a polyimide thickness of 12 μm.

In order to evaluate low-temperature adhesiveness, this metal laminated body was made to copper foil (SLP-35, 35 micrometers in thickness) by the copper bonder (The Kale Co., Ltd. make, TC-1320UD), 190 degreeC, 3 Mpa, Heat compression was performed for 2 seconds. The obtained test piece was subjected to a 90 ° insulation test in accordance with IPC-TM-650 methods 2, 4 and 9 and found to be 1.6 kN / m.

Examples 2-4

Polymerization, compounding, lamination, and evaluation were performed in the same manner as in Example 1 except that the type and compounding amount of the diamine compound or bismaleimide compound were changed. The results are shown in Table 1. 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene and 1, 3-bis (3- (3-maleimidephenoxy) phenoxy) benzene was identified by ¹ H-NMR and FD-mass.

1,3-bis (3- (3-aminophenoxy) phenoxy) benzene: ¹ H-NMR (CD3SOCD3) δ: 5.24 (s, 4H), 6.12-6.16 (ddd, 2H, J = 7.83, 2.43, 0.82 Hz), 6.23 (t, 2H, J = 2.30 Hz), 6.33-6.37 (ddd, 2H, J = 7.83, 2.43, 0.82 Hz), 6.61 (t, 2H, J = 2.43 Hz), 6.67 (t, 1H, J = 2.43 Hz), 6.71-6.80 (m, 6H), 6.99 (t, 2H, J = 7.83 Hz), 7.35 (t, 2H, J = 7.83 Hz), 7.38 (t, 1H, J = 7.83 Hz), FD-mass 476 (M +)

1,3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene: ¹ H-NMR (CD3SOCD3) δ: 5.21 (s, 4H), 6.11-6.12 (ddd, 2H, J = 7.83, 2.16, 0.81 Hz), 6.21 (t, 8H, J = 2.16 Hz), 6.31-6.36 (ddd, 2H, J = 7.83, 2.16, 0.81 Hz), 6.67-6.82 (m, 13H), 6.98 (t, 8H, J = 8.10 Hz), 7.31-7.42 (m, 5H), FD-mass 660 (M +)

1,3-bis (3- (3-maleimidephenoxy) phenoxy) benzene: ¹ H-NMR (CDC13) δ: 6.72 (t, 3H, J = 2.30 Hz), 6.79-6.83 (dd, 6H, J = 7.83, 2.43 Hz), 7.05-7.08 (m, 5H), 7.12-7.16 (m, 5H), 7.34-7.51 (m, 5H), FD-mass 636 (M +)

Example 5

In a vessel equipped with a stirrer and a nitrogen introduction tube, 85.5 g of N, N-dimethylacetamide was added as a solvent, and 69.16 g of 1,3-bis (3-aminophenoxy) benzene was added thereto and dissolved at room temperature until dissolved. Stirred. Thereafter, 75.84 g of 3,3 ', 4,4',-benzophenonetetracarboxylic dianhydride was added and stirred at 60 ° C to obtain a polyamic acid solution. The content rate of polyamic acid was 15 weight%. 48.3 g of 1, 3-bis (3-maleimide phenoxy) benzene was added to 500 g of the obtained varnish, and it stirred at room temperature for 2 hours.

After drying a part of the bismaleimide compound containing polyamic-acid solution obtained by the method mentioned above using the commercially available polyimide resin film (The product made by Torre Dupont, brand name: Kafton (trademark) 150EN), The coating was applied to a thickness of 2 μm, dried at 115 ° C. for 2 minutes, at 150 ° C. for 2 minutes, at 180 ° C. for 2 minutes, at 240 ° C. for 2 minutes, and at 265 ° C. for 2 minutes. The insulating film which is a polyimide resin layer was obtained. After that, a metal foil and an insulating film were matched with a commercially available electrolytic copper foil (F0-WS 9 µm, manufactured by Furukawa Circuit Film Co., Ltd.) under a condition of a pressure of 1.5 MPa at 240 ° C. with a roll laminator, followed by a temperature in a batch autoclave. The polyimide metal laminate was obtained by annealing at 280 ° C. for 4 hours under a nitrogen atmosphere. The solder heat resistance temperature of the obtained polyimide metal laminated body was 320 degreeC. In addition, when the presence or absence of the voids of the copper foil and the polyimide interface was observed at 1250 times, the cross section and the surface of the copper foil were etched away, but no void was observed.

Examples 6-13

Polymerization, compounding, lamination and evaluation were carried out in the same manner as in Example 5 except that the kind and compounding amount of the diamine compound, the acid dianhydride and the bismaleimide were changed. The results are shown in Table 2. Here, the copper foil and the void of the polyimide interface were not observed in all the samples.

Example 14

In a vessel equipped with a stirrer and a nitrogen introduction tube, N, N-dimethylacetamide was added so that the content of polyamic acid was 15% by weight as a solvent, and p-phenylenediamine and 3,4'-oxydianiline were added thereto. Was added at a rate of 30 mol% and 70 mol% and stirred at room temperature until dissolved. Thereafter, 0.985 mol of the 3,3 ', 4,4',-benzophenone tetracarboxylic dianhydride was added with the mole number of the total diamine as 1, and stirred at 60 ° C to obtain a polyamic acid solution. 1, 3-bis (3-maleimide phenoxy) benzene was added to the obtained varnish so that it may become 40 weight% with respect to polyamic acid, and it stirred at room temperature for 2 hours.

A part of the obtained bismaleimide compound-containing polyamic acid solution was taken, cast on a glass plate, and then heated at a temperature increase rate of 7 ° C./min from 50 ° C. to 270 ° C. to obtain a film having a thickness of 20 μm. The glass transition temperature (Tg) of the obtained polyimide film was 220 degreeC.

In addition, a part of the obtained bismaleimide compound-containing polyamic acid solution using a commercially available polyimide resin film (manufactured by Torre Dupont Co., Ltd., trade name: Kafton (registered trademark) 150EN) was applied with an applicator, and the thickness after drying was 2 It apply | coated so that it might become micrometer, and it dried at the temperature increase rate of 7 degree-C / min from 50 degreeC to 270 degreeC, and obtained the insulating film whose one side is a thermoplastic polyimide resin layer. Thereafter, commercially available electrolytic copper foil (manufactured by Furugawa Circuit Film Co., F0-WS 9 µm) was laminated, dried at 130 ° C. for about 1 hour, and then pressed at a temperature of 300 ° C., a pressure of 2.5 MPa for 4 hours, and a metal foil and an insulating film. The matched polyimide metal laminate was obtained. The void of the interface of copper foil and a polyimide was not observed. Moreover, as a result of peeling experiment, it was 0.85 kN / m.

Example 15, 16

Polymerization, compounding, lamination and evaluation were carried out in the same manner as in Example 14 except that the kind and compounding amount of the diamine compound, the acid dianhydride and the bismaleimide were changed. The results are shown in Table 3. Here, the copper foil and the void of the polyimide interface were not observed in all the samples.

Comparative Example 1

Polymerization, mixing | blending, lamination | stacking, and evaluation were performed like Example 1 except not having mix | blended the bismaleimide compound. The results are shown in Table 1. The insulation adhesion strength was 0 kN / m, which did not adhere at all.

Comparative Example 2

In a vessel equipped with a stirrer and a nitrogen introduction tube, 85.5 g of N, N-dimethylacetamide was added as a solvent, and 69.16 g of 1,3-bis (3-aminophenoxy) benzene was added thereto and stirred at room temperature until dissolved. It was. Thereafter, 75.84 g of 3,3 ', 4,4',-benzophenone tetracarboxylic dianhydride was added and stirred at 60 ° C to obtain a polyamic acid solution. The content rate of polyamic acid was 15 weight%.

Using a commercially available polyimide resin film (manufactured by Torre Dupont, trade name: Kafton (registered trademark) 150EN), a part of the obtained polyamic acid solution was applied with a roll coater so as to have a thickness of 2 µm after drying. 2 minutes at 115 ° C., 2 minutes at 150 ° C., 2 minutes at 180 ° C., 2 minutes at 240 ° C., and 2 minutes at 265 ° C., followed by drying in an air-float drying furnace to obtain an insulating film having one side of a thermoplastic polyimide resin layer. . Thereafter, commercially available copper foil as in Example 5 was fitted with an insulating film with a metal foil and an insulating film under conditions of a pressure of 1.5 MPa at 240 ° C. with a roll laminator, and then annealed under a nitrogen atmosphere at a temperature of 280 ° C. for 4 hours in a batch autoclave. Was carried out to obtain a polyimide metal laminate. The solder heat resistance temperature of the obtained polyimide metal laminated body was 260 degreeC. In addition, voids of several micrometers to several tens of micrometers were observed in the copper foil and the polyimide interface.

Comparative Examples 3 to 5

Except not mixing a bismaleimide compound, it superposed | polymerized, mix | blended, laminated | stacked, and evaluated like Example 14, 15, and 16. The results are shown in Table 3. The insulation adhesion strength was 0 kN / m, which did not adhere at all, and void evaluation was not possible.

Table 1

TABLE 2

TABLE 3

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

APB5: 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene,

APB7: 1,3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene

DABP: 3,3'-diaminobenzophenone

m-BP: 4,4 '-(3-aminophenoxy) biphenyl

ODA: 4,4'-oxydianiline (4,4'-diaminodiphenyl ether)

3,4'-ODA: 3,4'- oxydianiline (3,4'- diamino diphenyl ether)

PPD: p-phenylenediamine

   * 2) BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride

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

ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride

PMDA: Pyromellitic Anhydride

   * 3) APB-BMI: 1,3-bis (3-maleimidephenoxy) benzene

APB5-BMI: 1,3-bis (3- (3-maleimidephenoxy) phenoxy) benzene

BMI-MP: N, N'-m-phenylenebismaleimide

BMI-S: Bis (4-maleimidephenyl) methane

The resin composition of the present invention is excellent in low temperature adhesiveness due to the Tg lowering effect and can be suitably used as a heat resistant adhesive for use in electronic fields.

In addition, according to the present invention, it is possible to obtain a laminated sheet having a high adhesive strength without voids remaining at the metal-polyimide interface even without using a high processing temperature, and for mounting LSI chips and components with strict use temperature conditions. Also in a process and these repair processes, a blister does not generate | occur | produce well and the polyimide metal laminated board excellent in solder heat resistance can be provided.

Claims (5)

General formula (1) to polyamic acid, polyimide, or polyamic acid and polyimide (Wherein m represents an integer of 0 or more, X may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond, and R 1 is the same or different, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, and the substitution positions of the benzene rings are each independently a resin composition formed by mixing a bismaleimide compound represented by And laminated on at least one side of the metal foil. The metal laminate according to claim 1, wherein a polyimide layer is formed on one side or both sides of at least one polyimide film, and a metal is laminated on one side or both sides of the polyimide layer. The polyamic acid and the polyimide according to claim 1, wherein the polyamic acid and the polyimide are represented by general formula (2), general formula (3), general formula (2) and general formula (3), respectively. (Wherein n represents an integer of 0 or more, Y may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , and C (CF ₃ ) ₂ or a direct bond, A is a tetravalent organic group, R 2 is the same or different, represents a hydrogen atom, a halogen atom, a hydrocarbon group, and the positions of substitution of the benzene rings are each independently a repeating structural unit; Metal laminate having a. The tetravalent organic group represented by A according to claim 3 is a general formula (4). (Wherein Z represents O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond.). General formula (1) to polyamic acid, polyimide, or polyamic acid and polyimide (Wherein m represents an integer of 0 or more, X may be the same or different independently of each other, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or a direct bond, wherein R1 is the same or different and represents a hydrogen atom, a halogen atom, and a hydrocarbon group, and the substitution positions of the benzene rings are each independently; The resin composition for polyimide metal laminated bodies to be.