JP4199654B2 - Resin composition and metal laminate - Google Patents

Description

  The present invention relates to a resin composition excellent in low-temperature adhesion and maintaining excellent low-temperature adhesion even after high-temperature heat treatment, and a metal laminate using the same.

  Polyimide has excellent heat resistance, chemical resistance, mechanical strength, electrical properties, etc., so it can be used not only in the aviation field where heat resistance is required, but also in the electronic field such as flexible printed circuit boards and semiconductor packages. Many adhesive adhesives are applied.

  In recent years, polyimide heat-resistant adhesives have been required to have low-temperature adhesive properties in addition to heat resistance in processing. For example, Patent Document 1 reports a resin composition comprising a polyimide resin having a siloxane unit, an epoxy resin, and a phosphoric ester plasticizer as an example having excellent low-temperature adhesiveness. However, in this case, since the polyimide resin, epoxy resin, plasticizer, and any component contain an aliphatic unit, the thermal decomposition temperature is lowered and there is a problem in terms of heat resistance.

  On the other hand, as a resin having sufficient adhesive strength and heat resistance, a resin composed of a specific polyamic acid and a bismaleimide compound disclosed in Patent Document 2, Patent Document 3, and Patent Document 4 has been developed. However, some of them require a temperature of 300 ° C. or higher for adhesion, and many are still insufficient from the viewpoint of low-temperature adhesion. It was something that stayed.

Polyamic acid formed by blending a specific bismaleimide compound is excellent in low-temperature adhesion, but as a method for producing a metal laminate, a non-thermoplastic polyamic acid varnish and other polyamic acid varnishes are laminated on the core layer. However, when a polyamic acid varnish compounded with a bismaleimide compound is laminated on the top layer, high temperature treatment is required to remove the residual solvent in the core layer, so that the curing reaction of bismaleimide proceeds during drying and the polyimide layer foams. In other words, the glass transition point (Tg) shifts to a high temperature as the resin is further cured, resulting in a significant decrease in adhesiveness.
JP-A-10-212468 Japanese Unexamined Patent Publication No. 01-289862 JP-A-6-145638 Japanese Patent Laid-Open No. 6-192939

  The objective of this invention is providing the resin composition for polyimide laminated bodies which is excellent in low-temperature adhesiveness, suppresses resin hardening at the time of high-temperature heat processing, and maintains the low-temperature adhesiveness outstanding after heat processing.

  The present inventors have excellent low-temperature adhesiveness by blending a polyamic acid and / or polyimide with a bismaleimide compound having a specific structure in which the peak of an exothermic peak indicating thermosetting is 290 ° C. or higher in DSC measurement. And it discovered that the heat-resistant adhesive which suppresses resin hardening at the time of a high temperature heat processing, and maintains the low-temperature adhesiveness after heat processing was obtained, and came to complete this invention.

That is, the present invention is as follows.
(1) Polyamide acid and / or polyimide is represented by the general formula (1)

(In the formula, m represents an integer of 1 or more, X may be the same or different each independently, and may be a hydrocarbon group, an ester group, an amide group, O, CO, SO ₂ , S, C ( CF ₃ ) ₂ or direct connection, R 1 is the same or different, and represents a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group, and the substitution positions are independent of each other), and in DSC measurement, A resin composition comprising a bismaleimide compound having a peak of an exothermic peak indicating thermosetting of 290 ° C. or higher.
(2) A metal laminate having a structure in which a polyimide layer made of the resin composition described in (1) is formed on one or both sides of one or more polyimide films, and a metal is laminated on one or both sides of the polyimide layer. .

  The resin composition of the present invention has excellent low-temperature adhesiveness due to its low glass transition point (Tg), and suppresses thermal curing of the resin in the course of high-temperature heat treatment by using a bismaleimide compound having a high thermosetting temperature. This maintains excellent low-temperature adhesiveness even after high-temperature heat treatment, and can be suitably used particularly as a heat-resistant adhesive for use in the electronic field. It is possible to provide a metal laminate that can be processed without losing low-temperature adhesiveness even through a high-temperature process and that has high adhesive strength.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a polyamic acid and / or a polyimide having a general formula (1)

(In the formula, m represents an integer of 1 or more, X may be the same or different each independently, and may be a hydrocarbon group, an ester group, an amide group, O, CO, SO ₂ , S, C ( CF ₃ ) ₂ or direct connection, R 1 is the same or different, and represents a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group, and the substitution positions are independent of each other), and in DSC measurement, The present invention relates to a resin composition comprising a bismaleimide compound having a peak of an exothermic peak indicating thermosetting of 290 ° C. or higher.

  Examples of the halogen atom represented by R1 in the general formula (1) include a chlorine atom and a fluorine atom, and examples of the hydrocarbon group include a lower alkyl group such as a methyl group and an ethyl group, a vinyl group and an allyl group. Examples include lower alkenyl groups, aralkyl groups such as benzyl groups and phenethyl groups, aryl groups such as phenyl groups and naphthyl groups, alkoxy groups such as methoxy groups and ethoxy groups, and halogenated alkyl groups such as trifluoromethyl groups. , Preferably a hydrogen atom.

m represents an integer of 1 or more, preferably 1-7. X represents a hydrocarbon group, an ester group, an amide group, O, CO, SO ₂ , S or C (CF ₃ ) ₂ , preferably a 1-methylethyl group or O (ether bond).

  Specific examples of the bismaleimide compound represented by the general formula (1) include 1,3-bis (3- (3-maleimidophenoxy) phenoxy) benzene, bis (3- (3- (3-maleimidophenoxy) phenoxy) Phenyl) ether, 1,3-bis (3- (3- (3-maleimidophenoxy) phenoxy) phenoxy) benzene, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (4- (3-maleimidophenoxy) phenyl) propane, 4,4′-bis (3-maleimidophenoxy) biphenyl, 2,2-bis (4- (3-maleimidophenoxy) phenyl) -1,1,1, 3,3,3-hexafluoropropane, 1,3-bi (su (1- (4- (4-maleimidophenoxy) phenyl) -1-methylethyl) benzene Zen, 1,3-bis (1- (4- (3-maleimidophenoxy) phenyl) -1-methylethyl) benzene, 1,4-bis (1- (4- (4-maleimidophenoxy) phenyl) -1 -Methylethyl) benzene, 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane, 1- (4- (4-maleimidophenoxy) Phenyl) -4- (1- (4- (4-maleimidophenoxy) phenyl) -1-methylethyl) -1-methylcyclohexane, 2,2-bis (4- (1- (4- (4-maleimidophenoxy) ) Phenyl) -1-methylethyl) phenyl) propane, bis (4- (3-maleimidophenoxy) phenyl) ketone, bis (4- (3-maleimidophenoxy) phenyl) sulfur Bis (4- (3-maleimidophenoxy) phenyl) sulfone, 2,2-bis (3-methyl-6- (1-methylethyl) -4- (3-methyl-6- (1-methylethyl) ) -4-maleimidophenoxy) phenyl) propane and the like, preferably 2,2-bis (4- (3-maleimidophenoxy) phenyl) propane, 1,3-bis (1- (4- (4 -Maleimidophenoxy) phenyl) -1-methylethyl) benzene, 2,2-bis (3-methyl-6- (1-methylethyl) -4- (3-methyl-6- (1-methylethyl) -4 -Maleimidophenoxy) phenyl) propane, 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane and the like. It is not limited.

  These bismaleimide compounds can be produced by condensing and dehydrating a corresponding diamine compound and maleic anhydride, for example, by the method described in JP-A-4-99764.

  Further, in the resin composition of the present invention, it is essential to have an exothermic peak due to thermosetting at 290 ° C. or higher when DSC measurement of the compound represented by the general formula (1) is performed. The exothermic peak temperature is preferably in the range of 300 to 400 ° C, more preferably 300 to 350 ° C. When the exothermic peak position is less than 290 ° C., the resin is excessively cured during the heating process for removing the residual solvent, and sufficient adhesion cannot be obtained. Moreover, when the exothermic peak position exceeds 400 ° C., the heat resistance may decrease.

  In the case of producing the resin composition of the present invention, the blending ratio of the bismaleimide compound represented by the general formula (1) to the polyimide is not particularly limited, but the total mass of the polyamic acid which is a polyimide precursor is not limited. Is preferably 0.1 to 70% by mass, and more preferably 0.1 to 50% by mass. If the blending amount of the bismaleimide compound is less than 0.1% by mass, the effect of improving the soldering heat resistance may not be seen, and if it exceeds 70% by mass, the adhesive strength of the metal foil tends to decrease.

  The polyamic acid and / or polyimide used in the resin composition of the present invention is not particularly limited, but is preferably represented by general formula (2) and general formula (3), respectively.

(In the formula, n represents an integer of 0 or more, each Y may be the same or different independently, and may be an ester group, an amide group, O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or direct connection, and A is a tetravalent organic group, and R2 is the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydroxyl group. Each having a repeating structural unit represented by the following general formula (4) and general formula (5):

(Wherein, l represents an integer of 1 to 7. R2 is the same or different and represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydroxyl group, and the substitution positions of the respective benzene rings are independent of each other; Two heteroatoms that are the same or different from each other and bonded to the same benzene ring selected from an oxygen atom and a nitrogen atom are in the ortho or meta position relative to at least one benzene ring, and A is a tetravalent organic group. A group having a repeating structural unit represented by general formula (6), and more preferably, general formula (6) and general formula (7), respectively.

(In the formula, l represents an integer of 1 to 7, and the same or different two heteroatoms bonded to the same benzene ring selected from an oxygen atom and a nitrogen atom are in the ortho-position or meta of at least one benzene ring. A represents a tetravalent organic group.), And more preferably, each has the general formula (8) and the general formula (9).

(Wherein, l and A have the same meanings as described above).

In general formula (2)-(3), n shows an integer greater than or equal to 0, Preferably it is 0-6, More preferably, it is 0-4. In general formula (4)-(9), l shows the integer of 1-7, Preferably it is 1-5, More preferably, it is 1-3. Y may independently be the same or different, and may be an ester group, an amide group, O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or Direct connection is indicated, preferably O, CO, C (CH ₃ ) ₂ or direct connection.

  In the general formulas (2) to (5), R2 is the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydroxyl group, and the substitution positions of the benzene rings are independent of each other, preferably The substitution position of the benzene ring is a compound bonded at the ortho or meta position.

  The tetravalent organic group represented by A in the general formulas (2) to (9) is not particularly limited, but specific examples include aliphatic groups having 2 to 27 carbon atoms and cyclic aliphatic groups. A monovalent aromatic group, a condensed polycyclic aromatic group, a tetravalent organic group selected from the group consisting of non-condensed polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a bridging member, etc. Preferably, general formula (10)

(In the formula, Z represents an ester group, an amide group O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) _2, or a direct bond).

  The blending method of the bismaleimide compound into the polyamic acid includes (a) a method of adding the bismaleimide compound to the polyamic acid solution, and (b) during polymerization of the polyamic acid, for example, a diamine compound or tetracarboxylic dianhydride. Examples thereof include, but are not limited to, a method of adding at the time of polymerization or in the middle of polymerization, and (c) a method of mixing a polyamic acid powder and a bismaleimide compound with solids.

  Further, after the polyamic acid is dehydrated and imidized into a polyimide solution in advance, a bismaleimide compound may be blended.

  The polyamic acid represented by the general formula (2) is represented by the general formula (11).

(Wherein n, Y and R2 have the same meaning as described above) and the general formula (12)

(In the formula, A represents the same meaning as described above.) A resin composition obtained by reacting a tetracarboxylic dianhydride represented by the formula, and a resin composition obtained by dehydrating imidation of a resin composition comprising this polyamic acid. The thing is also a thing of this invention.

  Specific examples of the aromatic diamine compound represented by the general formula (11) include, for example, bis (3- (3-aminophenoxy) phenyl) ether and 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene. 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′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 4,4'-diaminobenzopheno 3,4′-diaminobenzophenone, 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-aminophenoxy) 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 can be mentioned, but are not limited thereto.

  In the general formula (12), A represents a tetravalent organic group. Specifically, for example, an aliphatic group having 2 to 27 carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, or a condensed group. A polyvalent aromatic group or a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a bridging member is shown.

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

  Specific examples of 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 bistrimellitic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)- 1,1,1,3,3,3-hexafluoropropane dianhydride and the like can be mentioned. Preferably, for example, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 1,2-bis (3,4-dicarboxybenzoyl) benzene dianhydride, 1,3-bis (3,4-dicarboxybenzoyl) benzene Anhydride, 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 dianhydride, 3,4'-bis ((3,4-dicarboxy) phenoxy) benzophenone dianhydride, 4,4'-bis ((3,4-dicarboxy) phenoxy) benzophenone A dianhydride etc. are mentioned. These may be used alone or in combination of two or more.

  As a method for producing a polyamic acid according to the present invention, any method including a known method that can produce a polyamic acid can be applied. Among these, it is preferable to perform the reaction in an organic solvent. Examples of the solvent used in such a reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,2-dimethoxyethane and the like.

  The concentration of the reaction raw material in this reaction is usually 2 to 50% by mass, preferably 10 to 50% by mass, and the reaction temperature is usually 60 ° C. or less, preferably 50 ° C. or less. The reaction pressure is not particularly limited, and can be sufficiently carried out at normal pressure. Moreover, although reaction time changes with the kind of reaction raw material, the kind of solvent, and reaction temperature, 0.5 to 24 hours is sufficient normally. By such a polycondensation reaction, a polyamic acid represented by the general formula (2) is produced.

  The polyimide represented by the general formula (3) is obtained by suspending or dissolving a diamine component and an acid dianhydride component in an organic solvent, and reacting under heating at 130 to 300 ° C. to form and dehydrate the polyamic acid. It can be obtained by carrying out imidization at the same time.

  The resin composition of the present invention can be used for other resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenyl as long as the object of the present invention is not impaired. An appropriate amount of sulfide, modified polyphenylene oxide group, polyamideimide, polyetherimide, epoxy resin or the like can also be blended.

  The method for producing a film comprising the resin composition of the present invention is not particularly limited. For example, (a) a polyamic acid solution is applied on a substrate (glass plate, metal plate or heat-resistant resin film). And (b) a method in which a polyimide solution is applied on a substrate (glass plate, metal plate or heat-resistant resin film) and then heated.

  Moreover, an adhesive insulating tape can also be comprised by having the adhesive bond layer and heat resistant film which consist of the resin composition mentioned above. The adhesive insulating tape has a single-sided tape in which the adhesive layer is formed only on one side of the heat-resistant film, a double-sided tape in which the adhesive layer is formed on both sides of the heat-resistant film, and other arbitrary layers. Composed.

  In order to produce an adhesive insulating tape from the resin composition for a polyimide metal laminate of the present invention, a solution containing the resin composition described above may be applied to one or both sides of a 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 heat resistant resin films such as polyimide, polyphenylene sulfide, polyether, polyether ketone, polyether ether ketone, and polyethylene terephthalate, epoxy resin-glass cloth, epoxy resin-polyimide-glass cloth, and the like. Although a composite heat-resistant film etc. are mentioned, the film which consists of a polyimide resin especially 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 laminate of the present invention comprises an adhesive layer and a metal foil composed of the above-described resin composition as essential components, but as an intermediate layer between the adhesive layer and the metal foil, from other resin compositions. The adhesive layer or non-adhesive layer may be a single layer or multiple layers.

  Further, in the metal laminate of the present invention, a resin composition obtained by blending a bismaleimide compound having a peak of an exothermic peak indicating thermosetting of 290 ° C. or higher in the DSC measurement represented by the general formula (1). What is necessary is just to include in at least one layer, and you may have the resin layer formed by mix | blending the said compound with multiple layers.

  In order to produce the metal laminate of the present invention, a solution containing the resin composition described above as an example may be applied to a metal foil and dried. At that time, the thickness after coating is preferably in the range of 0.5 to 100 μm. If it is less than 0.5 μm, sufficient adhesive strength may not be obtained, and if it exceeds 100 μm, the adhesion may not be improved greatly.

As the types of metal foil, all known metal foils and alloy foils can be applied, but rolled copper foil, electrolytic copper foil, copper alloy foil, stainless steel foil are from the viewpoint of cost, thermal conductivity, rigidity, etc. Is preferred.
The thickness of the metal foil is not limited as long as it can be used in the form of a tape, but 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 or both sides of one or more polyimide films, and the polyimide layer has a structure in which a metal is laminated on one or both sides. The layer is a resin composition containing a bismaleimide compound having a thermosetting temperature of 250 ° C. or higher represented by the general formula (1).

  The polyimide film is preferably a non-thermoplastic polyimide film, and specifically, a composition synthesized from a specific diamine and a specific tetracarboxylic dianhydride can be used. Examples of specific diamines include o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminophenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, and the like. . These may be used alone or in combination of two or more.

  Examples of specific tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic An acid etc. are mentioned. These may be used alone or in combination of two or more.

  A commercially available non-thermoplastic polyimide film can also be used as the non-thermoplastic polyimide film. For example, Upilex (registered trademark) S, Upilex (registered trademark) SGA, Upilex (registered trademark) SN (trade name), Kapton (registered trademark) H, Kapton (registered trademark) V, Kapton (registered) Trademark) EN (trade name, manufactured by Toray DuPont Co., Ltd.), Apical (registered trademark) AH, Apical (registered trademark) NPI, Apical (registered trademark) HP (trade name, manufactured by Kaneka Chemical Co., Ltd.), etc. It is done. The surface of the non-thermoplastic polyimide may be subjected to plasma treatment, corona discharge treatment or the like. The thickness of the non-thermoplastic polyimide layer is not particularly limited depending on the purpose, but a range of 5 to 250 μm can be suitably used.

  Furthermore, you may laminate | stack the non-thermoplastic polyimide from which a structure differs on the side which does not laminate | stack a thermoplastic polyimide layer of a commercially available non-thermoplastic polyimide film.

  In the present invention, a peelable protective film, a carrier film, or a carrier metal foil may be provided on the polyimide film, the adhesive insulating tape, or the adhesive layer of the metal laminate. Examples of the protective film and carrier film include polyethylene, polyethylene terephthalate, and polypropylene. Examples of the carrier metal foil include rolled copper foil, electrolytic copper foil, copper alloy foil, and stainless steel foil. The thickness is 1 to 200 μm, preferably 10 to 100 μm. The 90 ° peel adhesion strength with the adhesive layer is preferably in the range of 0.01 to 10 kN / m.

  The polyimide metal laminate provided by the present invention maintains excellent adhesion even after high-temperature heat treatment. By laminating a polyimide compounded with bismaleimide on the uppermost layer of the metal laminate formed by laminating one or a plurality of polyamic acid varnishes, an excellent effect is exhibited in removing the residual solvent. However, since the removal of the residual solvent requires a temperature that is significantly higher than the curing temperature of the bismaleimide compound that has been used conventionally, the curing reaction of the bismaleimide proceeds during the removal of the residual solvent, and the foaming of the resin layer and glass It has become a problem that the low temperature adhesiveness is lowered due to the high temperature shift of the transition point (Tg). In the present invention, the peak of an exothermic peak indicating thermosetting is 290 ° C. or higher in DSC measurement on polyimide, and by adding bismaleimide having a specific structure, it is easy to remove the residual solvent, and high-temperature treatment Later, it became possible to provide a resin composition that has no poor appearance such as foaming of the resin layer and maintains high low-temperature adhesiveness.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, the physical property of the polyimide in an Example was measured with the following method.

  Thermosetting temperature: Measured with a differential scanning calorimeter (manufactured by Mac Science Co., Ltd., DSC3100) under a temperature rising condition of 5 ° C./min.

  Glass transition temperature (Tg): Measured with a differential scanning calorimeter (manufactured by Mac Science Co., Ltd., DSC3110) under the temperature rising condition of 5 ° C / min.

  90 ° peel adhesion strength: Measured according to IPC-TM-650 method, 2, 4, 9.

Example 1
In a vessel equipped with a stirrer and a nitrogen introducing tube, 5.75 g of 1,3-bis (3-aminophenoxy) benzene, 6.24 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and N, N-dimethylacetamide (35.90 g) was inserted, and the mixture was stirred at 50 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, the system temperature was lowered to room temperature, and 2.11 g of 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (exothermic peak 300 ° C.) was added and dissolved at room temperature.

  After taking a part of the obtained bismaleimide compound-containing polyamic acid solution and casting it on a glass plate, it was heated from 50 ° C. to 250 ° C. at a heating rate of 7 ° C./min, then held at 250 ° C. for 30 minutes, A film having a thickness of 20 μm was obtained. The obtained polyimide film had a glass transition temperature (Tg) of 169 ° C. Similarly, a portion of the obtained bismaleimide compound-containing polyamic acid solution is taken, cast on a glass plate, heated from 50 ° C. to 270 ° C. at a heating rate of 7 ° C./min, and then at 270 ° C. for 30 minutes. This was retained to obtain a film having a thickness of 20 μm. The resulting polyimide film had a glass transition temperature (Tg) of 175 ° C.

  Also, roll the coater so that the thickness after drying the thermoplastic polyamic acid solution and non-thermoplastic polyamic acid solution on commercially available rolled copper foil (BYH-22B-T manufactured by Nikko Materials Co., Ltd.) becomes 3 μm and 7 μm, respectively. Applied and laminated. A part of the resulting bismaleimide compound-containing polyamic acid solution was applied to this uppermost layer with a roll coater so that the thickness after drying was 3 μm, and it was 115 ° C. for 2 minutes, 150 ° C. for 2 minutes, and 180 ° C. Temporary drying was performed for 2 minutes at 240 ° C. for 2 minutes and at 265 ° C. for 2 minutes in an air float type drying furnace. Further, in order to remove the residual solvent, heat drying was performed at 300 ° C. for 1 minute, and it was confirmed that the residual solvent was 0.3% or less, which is a region having no practical problem.

In order to evaluate low-temperature adhesiveness, this polyimide metal laminate was used as a commercially available copper foil (BYH-22B-T manufactured by Nikko Materials Co., Ltd.) and a pulse bonder (manufactured by Kell Co., Ltd., TC-1320UD) at 190 ° C. A polyimide metal laminate was obtained by thermocompression bonding at 3 MPa for 2 seconds. A 90 ° peel test was conducted according to IPC-TM-650 method, 2, 4 and 9 using the obtained test piece, and the result was 2.2 kN / m.
Example 2
Implemented except that the bismaleimide compound was 2,2-bis (3-methyl-6- (1-methylethyl) -4- (3-methyl-6- (1-methylethyl) -4-maleimidophenoxy) phenyl) propane Polymerization, blending and evaluation were carried out in the same manner as in Example 1. The results are also shown in Table 1.

Example 3
Polymerization and blending in the same manner as in Example 1 except that the bismaleimide compound was 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane. Evaluation was performed. The results are also shown in Table 1.

Example 4
The bismaleimide compound was converted to 1- (4- (4-maleimidophenoxy) phenyl) -4- (1- (4- (4- (maleimidophenoxy) phenyl) -1-methylethyl) -1-methylcyclohexane (exothermic peak 305 The polymerization, blending and evaluation were carried out in the same manner as in Example 1. The results are also shown in Table 1.

Comparative Example 1
Polymerization, blending, and evaluation were performed in the same manner as in Example 1 except that the type of the bismaleimide compound was changed to 1,3-bis (3-maleimidophenoxy) benzene (exothermic peak 287 ° C. by DSC measurement). The results are also shown in Table 1.

Comparative Example 2
Polymerization, blending, and evaluation were performed in the same manner as in Example 1 except that the bismaleimide compound was not blended. The results are also shown in Table 1. The peel adhesion strength is 0 kN / m and does not adhere at all.

note
* 1) BAPP-BMI: 2,2-bis (4- (3-maleimidophenoxy) phenyl) propane
BMI-1: 2,2-bis (3-methyl-6- (1-methylethyl) -4- (3-methyl-6- (1-methylethyl) -4-maleimidophenoxy) phenyl) propane
BMI-2: 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane
BMI-A: 1- (4- (4-maleimidophenoxy) phenyl) -4- (1- (4- (4- (maleimidophenoxy) phenyl) -1-methylethyl) -1-methylcyclohexane
APB-BMI: 1,3-bis (3-maleimidophenoxy) benzene
* 2) BMI properties
* 3) Weight ratio of bismaleimide compound to total resin weight
* 4) Film properties

  In addition to the excellent low-temperature adhesiveness due to the low Tg, the resin composition of the present invention uses a bismaleimide compound having a high thermosetting temperature, thereby suppressing the thermosetting of the resin in the process of high-temperature heat treatment. It maintains excellent low-temperature adhesion even after heat treatment, and can be suitably used particularly as a heat-resistant adhesive for use in the electronic field. It is possible to provide a metal laminate that can be processed without losing low-temperature adhesiveness even through a high-temperature process and that has high adhesive strength.

Claims (2)

A base material layer;
A first polyimide layer formed on the substrate layer;
A second polyimide layer formed on the first polyimide layer;
A metal laminate comprising a metal foil layer formed on the second polyimide layer,
The first polyimide layer and the second polyimide layer are respectively formed by applying a first resin composition and a second resin composition containing polyamic acid or polyimide, and then heat-treating; and
The second resin composition is prepared by adding 2,2-bis (4- (3-maleimidophenoxy) phenyl) propane, 2,2-bis (3-methyl-6- (1- Methylethyl) -4- (3-methyl-6- (1-methylethyl) -4-maleimidophenoxy) phenyl) propane, 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1, 1,3,3,3-hexafluoropropane and 1- (4- (4-maleimidophenoxy) phenyl) -4- (1- (4- (4- (maleimidophenoxy) phenyl) -1-methylethyl) A metal laminate comprising one or more bismaleimide compounds of -1-methylcyclohexane. Forming a layer of the first resin composition containing polyamic acid or polyimide on the base material layer;
Forming a layer of a second resin composition containing polyamic acid or polyimide on the layer of the first resin composition;
Heat-treating the layer of the first resin composition and the layer of the second resin composition;
Heat-pressing a metal foil on the heat-treated second resin composition layer, and
The second resin composition is prepared by adding 2,2-bis (4- (3-maleimidophenoxy) phenyl) propane, 2,2-bis (3-methyl-6- (1- Methylethyl) -4- (3-methyl-6- (1-methylethyl) -4-maleimidophenoxy) phenyl) propane, 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1, 1,3,3,3-hexafluoropropane and 1- (4- (4-maleimidophenoxy) phenyl) -4- (1- (4- (4- (maleimidophenoxy) phenyl) -1-methylethyl) The manufacturing method of a metal laminated body formed by mix | blending any one or more bismaleimide compounds of -1-methylcyclohexane.