JP4967494B2 - Method for producing heat-resistant polyimide metal laminate - Google Patents

Description

  The present invention relates to a method for producing a polyimide metal laminate having excellent heat resistance.

  Aromatic polyimide films provided with metal wiring are widely used as applications for electronic devices such as cameras, personal computers and liquid crystal displays.

Many methods for producing aromatic polyimide films provided with metal wiring have been reported. As a metal foil laminated polyimide film obtained by laminating a metal foil on a thermocompression bonding polyimide film having a multilayer structure, Patent Document 1 discloses a thermocompression bonding aromatic polyimide on at least one surface of a highly heat-resistant aromatic polyimide layer. A flexible metal foil laminate in which a thermocompression-bonding multilayer polyimide film and a metal foil, which are laminated and integrated by a casting film forming method, are laminated by thermocompression-cooling under pressure using a double belt press. Is disclosed.
Patent Document 2 discloses a flexible laminate having a metal foil on one or both sides of an insulating resin layer, the insulating resin layer comprising a plurality of polyimide resin layers, and at least one polyimide resin layer in contact with the metal foil. Is formed by a high elastic resin layer having a storage elastic modulus at 250 ° C. of 1 × 10 ⁸ Pa or more, and the thickness ratio of the high elastic resin layer in the insulating resin layer is in the range of 3 to 45%. A flexible laminate is disclosed.
JP-A-12-103010 JP 2005-288811 A

  Polyimide metal laminates used in COF (Chip On Film, Chip On Flex) and FPC (Flexible Printed Circuit Board) used in the field of electronic materials are subjected to high-temperature processes such as solder float in the mounting process, so they have high heat resistance. Is required. In order to improve this heat resistance, an all-polyimide metal laminate in which polyimide and metal foil are bonded together without using an adhesive has been studied.

When manufacturing a polyimide metal laminate from a metal foil and polyimide by a lamination method, as a means of improving the heat resistance of the polyimide metal laminate, a method of increasing the glass transition temperature of polyimide or increasing the modulus of elasticity in a high temperature region Can be considered. However, these methods require a laminating apparatus at a higher temperature and a higher pressure, which causes problems such as higher cost of the apparatus, discoloration of the metal foil, and lowering of productivity.
In this invention, it is providing the polyimide metal laminated board which can be manufactured simply and has the outstanding solder heat resistance, and its manufacturing method.

In this invention, the polyimide metal laminated board which can be manufactured simply and was excellent in heat resistance, and these manufacturing methods were examined. As a result, when using a polyimide copolymer obtained by copolymerizing a component that yields a crystalline polyimide and a component that yields an amorphous polyimide as the thermoplastic polyimide that is in direct contact with the metal foil, It has been considered to utilize the fact that the characteristics of non-crystallinity and crystallinity change, the non-crystallinity is obtained in a normal manufacturing method, and the crystallization proceeds by holding at a temperature higher than the glass transition temperature.
In other words, when laminating polyimide and metal foil directly by lamination, a relatively low temperature is required when using non-crystalline properties with a large decrease in elastic modulus above the glass transition temperature of polyimide and good fluidity.・ Lamination can be performed under pressure, but the crystallinity is low and the fluidity is inferior at a temperature lower than the glass transition temperature. Therefore, it is necessary to perform lamination under high temperature and pressure. There is inferior productivity and the cost of production equipment etc. becomes high. Therefore, as a thermoplastic polyimide that is in direct contact with the metal foil used in the metal laminate obtained by laminating metal foil and polyimide by the laminating method by heat and pressure, it exhibits mainly non-crystallinity at the time of lamination. It has been found that a metal laminate having excellent productivity and excellent heat resistance can be obtained by using a polyimide that mainly exhibits crystallinity during use.

The first of the present invention uses a non-crystalline thermoplastic polyimide copolymer obtained by copolymerizing a component capable of obtaining a crystalline polyimide from a measurement of dynamic viscoelasticity and a component capable of obtaining a non-crystalline polyimide. And
A polyimide metal laminate is manufactured by laminating a heat-resistant polyimide film and a metal foil using a laminating apparatus through an amorphous thermoplastic polyimide copolymer layer from measurement of dynamic viscoelasticity,
Furthermore, the polyimide metal laminate was heated, and the amorphous thermoplastic polyimide copolymer was changed from the dynamic viscoelasticity measurement to the thermoplastic polyimide copolymer showing crystallinity from the dynamic viscoelasticity measurement. It is a manufacturing method of the heat resistant polyimide metal laminated board made into.
Preferably, the present invention uses an amorphous thermoplastic polyimide copolymer obtained by copolymerizing a component capable of obtaining a crystalline polyimide and a component capable of obtaining an amorphous polyimide from dynamic viscoelasticity measurement. ,
Heat-resistant polyimide film and metal foil are measured by dynamic viscoelasticity measurement and non-crystalline thermoplastic polyimide polyimide is measured by dynamic viscoelasticity measurement. A polyimide metal laminate is manufactured by laminating above the glass transition temperature of the copolymer,
Furthermore, the polyimide metal laminate is heated to a temperature higher than the glass transition temperature of the amorphous thermoplastic polyimide copolymer from the measurement of dynamic viscoelasticity, and the amorphous thermoplastic polyimide copolymer from the measurement of dynamic viscoelasticity. Is a thermoplastic polyimide copolymer exhibiting crystallinity, which is a method for producing a heat-resistant polyimide metal laminate.

The second of the present invention uses an amorphous thermoplastic polyimide copolymer obtained by copolymerizing a component capable of obtaining a crystalline polyimide and a component capable of obtaining an amorphous polyimide from the measurement of dynamic viscoelasticity. And
A polyimide metal laminate is manufactured by laminating a heat-resistant polyimide film and a metal foil with a laminating device through an amorphous thermoplastic polyimide copolymer layer,
Further, by heating the polyimide metal laminate, the amorphous thermoplastic polyimide copolymer having a crystallinity of 3% or less calculated from the X-ray diffraction intensity of the thermoplastic polyimide copolymer alone by the transmission method is 3% or less. A method for producing a heat-resistant polyimide metal laminate, characterized in that the coalescence is a thermoplastic polyimide copolymer having a crystallinity calculated from the X-ray diffraction intensity by the Ruland method exceeding 3%. .
More preferably, the present invention uses a non-crystalline thermoplastic polyimide copolymer obtained by copolymerizing a component capable of obtaining a crystalline polyimide and a component capable of obtaining a non-crystalline polyimide from the measurement of dynamic viscoelasticity. And
Lamination of polyimide metal by bonding heat-resistant polyimide film and metal foil to the glass transition temperature of amorphous thermoplastic polyimide copolymer or higher using laminating device via amorphous thermoplastic polyimide copolymer layer Manufacturing the board,
Furthermore, the polyimide metal laminate is heated to a temperature higher than the glass transition temperature of the amorphous thermoplastic polyimide copolymer, and the crystal calculated by the Randland method from the X-ray diffraction intensity in the transmission method of the thermoplastic polyimide copolymer alone. A non-crystalline thermoplastic polyimide copolymer having a degree of crystallinity of 3% or less is converted into a thermoplastic polyimide copolymer exhibiting crystallinity with a crystallinity degree exceeding 3% calculated from the X-ray diffraction intensity by the Rand method. It is the manufacturing method of the heat resistant polyimide metal laminated board characterized by having performed.

Preferred embodiments of the first and second production methods of the present invention are shown below. A plurality of these aspects can be combined.
1) Thermoplastic polyimide copolymer
A component containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene, from which a crystalline polyimide is obtained by measuring dynamic viscoelasticity;
Heat obtained by copolymerizing a component containing 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene to obtain an amorphous polyimide It must be a plastic polyimide copolymer.
2) Heat the polyimide metal laminate in an inert gas atmosphere.

  Judgment of non-crystallinity and crystallinity of a thermoplastic polyimide copolymer can be made by measuring dynamic viscoelasticity.

Judgment of the non-crystallinity and crystallinity of the thermoplastic polyimide copolymer can be made based on the crystallinity calculated by the Ruland method from the X-ray diffraction intensity of the thermoplastic polyimide copolymer alone by the transmission method.
The non-crystalline thermoplastic polyimide copolymer preferably has a crystallinity calculated by the Ruland method from the X-ray diffraction intensity of the thermoplastic polyimide copolymer alone, preferably 3% or less, more preferably 2%. Or less, more preferably 1% or less, particularly preferably 0%,
The crystalline thermoplastic polyimide copolymer preferably has a degree of crystallinity calculated by the Ruland method from the X-ray diffraction intensity of the thermoplastic polyimide copolymer alone, exceeding 3%, more preferably 2 %, More preferably more than 1%, particularly preferably more than 0%.

  The method for producing a heat-resistant polyimide metal laminate of the present invention can be laminated at a relatively low temperature by using an amorphous thermoplastic polyimide copolymer for the pressure-bonding layer, and then the thermoplastic polyimide copolymer is By heating until it has crystallinity, a heat-resistant polyimide metal laminate having excellent heat resistance can be obtained.

As the heat-resistant polyimide film, an aromatic polyimide film having excellent heat resistance or a non-thermocompression-bonding aromatic polyimide film used as a substrate material for electronic components such as printed wiring boards, flexible printed boards, TAB, COF, and COB may be used. And an acid dianhydride component (for example, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4-hydroquinone dibenzoate-3) constituting the polyimide film , 3 ′, 4,4′-tetracarboxylic dianhydride as a main component, preferably these acid dianhydride components are at least 70 mol% or more, more preferably 80 mol% or more, more preferably Acid dianhydride component containing 90 mol% or more) and diamine component (p-phenylenediamine, 4,4-diamino) Those containing diphenyl ether, m-tolidine, 4,4′-diaminobenzanilide as main components, preferably these diamine components are at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more. And a polyimide containing an acid component and a diamine component constituting the polyimide film.
Specific examples of the heat-resistant polyimide film include a polyimide film used as a material for electronic components such as a printed wiring board, a flexible printed circuit board, and a TAB tape, such as a trade name “UPILEX (S or R)” (manufactured by Ube Industries, Ltd.). ), Trade name “Kapton” (manufactured by Toray DuPont, DuPont), trade name “Apical” (manufactured by Kaneka Chemical Co., Ltd.) and the like, and acid components and diamine components constituting these films The polyimide etc. which are obtained or contain the acid component and diamine component which comprise this polyimide film can be mentioned.

As the heat-resistant polyimide film, polyimide having at least one of the following characteristics can be used. (These features can be combined with any number of features.)
1) In the case of a single polyimide film, the glass transition temperature is 200 ° C. or higher, more preferably 300 ° C. or higher.
2), especially those having a linear expansion coefficient (50 to 200 ° C.) (MD) of 5 × 10 ^{−6 to} 20 × 10 ⁻⁶ cm / cm / ° C.,
3) The tensile elastic modulus (MD, ASTM-D882) is 300 kg / mm ² or more,
4) Non-thermoplastic polyimide can be used.

As the metal foil, a metal foil such as an alloy such as copper, aluminum, gold or stainless steel can be used, and a copper foil such as a rolled copper foil or an electrolytic copper foil is preferable.
As the metal foil, any surface roughness can be used, but those having a surface roughness Rz of 0.5 μm or more are preferable. Further, it is preferable that the surface roughness Rz of the metal foil is 7 μm or less, particularly 5 μm or less. Such metal foils, such as copper foils, are known as VLP, LP (or HTE).
The thickness of the metal foil is not particularly limited, but is preferably 1 to 35 μm, more preferably 3 to 25 μm, and particularly preferably 8 to 20 μm.
When the thickness of the metal foil is 5 μm or less, a metal foil with a carrier, such as a copper foil with an aluminum foil carrier, can be used.

The thermoplastic polyimide copolymer of the thermoplastic polyimide copolymer layer is a thermoplastic polyimide obtained by copolymerizing a component that yields a crystalline polyimide and a component that yields an amorphous polyimide from dynamic viscoelasticity measurements. It is a copolymer.
The thermoplastic polyimide copolymer layer or the thermoplastic polyimide copolymer has a thermocompression bonding property or a heat fusion property with the metal foil.

（但し、一般式（１）において、Ｘは一般式（２）で示す群から選択された４価の基を示す。）

（但し、一般式（２）において、Ｒ_１は、一般式（３）から選ばれる２価の基を示す。）

As the tetracarboxylic dianhydride used for the thermoplastic polyimide copolymer, a known tetracarboxylic dianhydride can be used, and the tetracarboxylic dianhydride represented by the general formula (1) is used as a main component, As long as the properties of the present invention are not impaired, known tetracarboxylic dianhydrides other than the tetracarboxylic dianhydrides shown in the general formula (1) can be used, and preferably in the tetracarboxylic dianhydrides, the general formula The tetracarboxylic dianhydride shown in (1) is preferably used in an amount of 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

(In the general formula (1), X represents a tetravalent group selected from the group represented by the general formula (2).)

(However, in General Formula (2), R ₁ represents a divalent group selected from General Formula (3).)

As a specific example of tetracarboxylic dianhydride used for thermoplastic polyimide copolymer,
Pyromellitic anhydride,
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride,
Oxydiphthalic dianhydride, diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, bis (3,4-di Carboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,
p-phenylenebis (trimellitic acid monoester acid anhydride), p-biphenylenebis (trimellitic acid monoester acid anhydride),
m-terphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, p-terphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride,
1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxy) Phenoxy) biphenyl dianhydride,
2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid A dianhydride etc. can be mentioned. These can be used alone or in combination of two or more.

  As the tetracarboxylic dianhydride, in addition to the compound represented by the general formula (1), an aliphatic, alicyclic or silicon-containing tetracarboxylic dianhydride may be used as long as the characteristics of the present invention are not impaired. it can.

（但し、一般式（４）において、Ｙは一般式（５）で示す群から選択された２価の基を示す。）

（但し、一般式（５）において、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、直結、−Ｏ−，−Ｓ−，−ＣＯ−，−ＳＯ_２−，−ＣＨ_２−，−Ｃ（ＣＨ_３）_２−及び−Ｃ（ＣＦ_３）_２−から選ばれる２価の基を示し、
Ｍ_１〜Ｍ_４、Ｍ’_１〜Ｍ’_４、Ｌ_１〜Ｌ_４、Ｌ’_１〜Ｌ’_４及びＬ”_１〜Ｌ”_４は、−Ｈ，−Ｆ，−Ｃｌ，−Ｂｒ，−Ｉ，−ＣＮ，−ＯＣＨ₃，−ＯＨ，−ＣＯＯＨ，−ＣＨ_３，−Ｃ_２Ｈ_５，−ＣＦ_３を示す。
Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立して、同一であっても、異なってもよく、
Ｍ_１〜Ｍ_４、Ｍ’_１〜Ｍ’_４、Ｌ_１〜Ｌ_４、Ｌ’_１〜Ｌ’_４及びＬ”_１〜Ｌ”_４は、それぞれ独立して、同一であっても、異なってもよい。） As the diamine, an aromatic diamine compound having 2 to 4 benzene rings can be suitably used. The diamine represented by the general formula (4) is used as a main component, and the general formula ( Known diamines other than the diamine shown in 4) can be used. Preferably, in the diamine, the diamine shown in the general formula (4) is 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more. Particularly preferably, 90 mol% or more can be used.

(However, in General Formula (4), Y represents a divalent group selected from the group represented by General Formula (5).)

(In the general formula (5), R ₂ , R ₃ , R ₄ and R ₅ are directly connected, —O—, —S—, —CO—, —SO ₂ —, —CH ₂ —, —C ( A divalent group selected from CH ₃ ) ₂ — and —C (CF ₃ ) ₂ —;
M _{1 to} M ₄ , M ′ _{1 to} M ′ ₄ , L _{1 to} L ₄ , L ′ _{1 to} L ′ ₄ and L ″ _{1 to} L ″ ₄ are represented by —H, —F, —Cl, —Br, — shows _{I, -CN, -OCH 3, -OH} , -COOH, -CH 3, -C 2 H 5, and -CF _3.
R ₂ , R ₃ , R ₄ and R _{5 may} each independently be the same or different,
M _{1 to} M ₄ , M ′ _{1 to} M ′ ₄ , L _{1 to} L ₄ , L ′ _{1 to} L ′ ₄ and L ″ _{1 to} L ″ ₄ are independently the same or different. Also good. )

As a specific example of diamine,
p-phenylenediamine, o-phenylenediamine,
3,3′-dichlorobenzidine, 3,3′-dimethylbenzidine, 2,2′-dimethylbenzidine, 3,3′-dimethoxybenzidine,
3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,3′-diamino-4,4′-dichlorobenzophenone 3,3′-diamino-4,4′-dimethoxybenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 2,2-bis (3-aminophenyl) ) Propane, 2,2-bis (4-aminophenyl) propane, , 2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3 Hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide,
1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino) Phenoxy) -4-trifluoromethylbenzene,
3,3′-diamino-4- (4-phenyl) phenoxybenzophenone, 3,3′-diamino-4,4′-di (4-phenylphenoxy) benzophenone, 1,3-bis (3-aminophenyl sulfide) Benzene, 1,3-bis (4-aminophenylsulfide) benzene, 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis ( 4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene,
1,3-bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) Isopropyl) benzene,
3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4 -Aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [ 4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) Phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [3- (3-aminophenoxy) phenyl] sulfur Bis [3- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [3- (3 -Aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-amino Phenoxy) phenyl] methane, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, 2, -Bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, Examples include 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane. These can be used alone or in combination of two or more.

  As the diamine, in addition to the compound represented by the general formula (5), diamines such as aliphatic, alicyclic, and silicon-containing diamines can be used as long as the characteristics of the present invention are not impaired.

The determination method of the component from which a crystalline polyimide is obtained from the measurement of dynamic viscoelasticity, and the component from which an amorphous polyimide is obtained is shown.
As an example, the determination method in the case where the thermoplastic polyimide copolymer is a polyimide obtained from three kinds of acid components (acid dianhydrides) (a1, a2, a3) and two kinds of diamine components (b1, b2) is as follows. Shown in
Acid component a1 and diamine component b1 component (polyimide c1), acid component a1 and diamine component b2 component (polyimide c2),
Acid component a2 and diamine component b1 component (polyimide c3), acid component a2 and diamine component b2 component (polyimide c4),
Six types of polyimides (c1, c2, c3, c4, c5, c6) are synthesized from the acid component a3 and the diamine component b1 component (polyimide c5), the acid component a3 and the diamine component b2 component (polyimide c6).
The dynamic viscoelasticity of six types of polyimide (c1, c2, c3, c4, c5, c6) is measured, whether the six types of polyimide are crystalline polyimide or non-crystalline polyimide, When both a crystalline polyimide and an amorphous polyimide are included, it is a thermoplastic polyimide copolymer used in the present invention.
When the measurement result of the dynamic viscoelasticity is the pattern of FIG. 1A, it is determined as crystalline, and when it is the pattern of FIG. 1B, it is determined as non-crystalline.
When the thermoplastic polyimide copolymer has two types of acid components (acid dianhydride) and two types of diamine components, four types of polyimide can be synthesized and discriminated.

As a combination of an acid component and a diamine component that may give a crystalline polyimide,
1) pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, p-ter Such as phenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), p-biphenylenebis (trimellitic acid monoester acid anhydride), etc. An acid component;
2) The diamine component is one diamine nucleus diamine represented by general formula (5), two benzene nucleus diamines represented by general formula (5), 1,3-bis (4-aminophenyl) benzene, 1,4-bis. (4-aminophenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenyl sulfide) benzene, 1, 4-bis (4-aminophenylsulfide) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) Mention may be made of polyimides obtained from diamine components such as phenyl] ether.

  As a combination of an acid component and a diamine component that may yield an amorphous polyimide, a combination of an acid component and a diamine component that may yield the above-mentioned crystalline polyimide is excluded, as shown in the general formula (1). Mention may be made of the acid component, the diamines of benzene nuclei 3, 4 and 5 shown in the general formula (5) and the resulting polyimide.

In the case where the thermoplastic polyimide copolymer is an amorphous thermoplastic polyimide copolymer, the glass transition temperature is preferably a temperature at which the laminating apparatus is used, and is preferably in the range of 150 to 330 ° C, for example.
The thermoplastic polyimide copolymer can obtain polyimides having various different glass transition temperatures by combining an acid component and a diamine component, and in consideration of the laminate, for example, in the range of 150 to 330 ° C., further 170 to A range of 320 ° C, a range of 190 to 310 ° C, particularly a range of 210 to 300 ° C is preferable.

The thickness of the heat-resistant polyimide film may be appropriately selected according to the purpose of use, but can be used as, for example, an electronic substrate, and the thickness is preferably in the range of 4 to 150 μm in consideration of productivity, handleability and transportability. Furthermore, the range of 5-100 micrometers is preferable, and the range of 8-80 micrometers is especially preferable.
The thickness of the thermoplastic polyimide copolymer layer may be any thickness as long as the heat-resistant polyimide film and the metal foil can be bonded together, and may be appropriately selected according to the purpose of use. The range is 20 μm, more preferably 0.2 to 10 μm, more preferably 0.5 to 5 μm, and particularly preferably 1 to 3 μm.

As the laminating apparatus, one that can be pressurized, one that can be thermocompression-bonded under pressure, and one that can be thermocompression-bonded and cooled under pressure can be used. For example, a pair of crimping rolls (the crimping part is made of metal or ceramic sprayed metal) And any one made of resin), a double belt press, a hot press, and the like can be used. In particular, a thermodynamic pressure bonding and cooling can be performed under pressure, and among them, a hydraulic double belt press is particularly preferable. be able to.
As a laminating device, by using a pressure roll such as a metal roll or a double belt press, it is continuously crimped under pressure or heating, and a long polyimide metal laminate or a long heat-resistant polyimide metal Laminates can be manufactured.

  JP-A-2001-270039 and JP-A-2005-306002 can be referred to for the production conditions of a laminate of a metal foil and a polyimide film using a double belt press.

The polyimide metal laminate which is a material in the middle for producing the heat-resistant polyimide metal laminate of the present invention,
Using a laminator
1) A heat-resistant polyimide film, an amorphous thermoplastic polyimide copolymer film, and a metal foil,
2) A film having a non-crystalline thermoplastic polyimide copolymer layer on the surface of a heat-resistant polyimide film, and a metal foil,
Or
3) A heat-resistant polyimide film and a foil having a non-crystalline thermoplastic polyimide copolymer layer on the surface of the metal foil,
Crimping, preferably thermocompression bonding, more preferably thermocompression bonding above the glass transition temperature of the amorphous thermoplastic polyimide copolymer, more preferably amorphous thermoplastic polyimide copolymer glass It is thermocompression-bonded at a temperature not lower than the transition temperature and not higher than 420 ° C., particularly preferably 10 ° C., more preferably 20 ° C., particularly not lower than 30 ° C. higher than the glass transition temperature of the amorphous thermoplastic polyimide copolymer. A polyimide metal laminate, preferably a polyimide metal laminate having a thermoplastic polyimide copolymer layer exhibiting non-crystallinity from the measurement of dynamic viscoelasticity, can be produced by thermocompression bonding at a temperature of 5 ° C.
The thermocompression bonding time at or above the glass transition temperature of the amorphous thermoplastic polyimide copolymer may be a time during which the noncrystalline property of the thermoplastic polyimide copolymer remains noncrystalline, or heat It may be the time when the non-crystallinity of the plastic polyimide copolymer becomes crystalline. For example, it may be longer than 0 seconds, preferably 0.001 seconds or more, more preferably 0.05 seconds or more, more Preferably, it may be 0.1 seconds or longer.
The polyimide metal laminate is thermocompression bonded at a temperature not lower than the glass transition temperature of the thermoplastic polyimide copolymer and not higher than 420 ° C., particularly preferably 10 ° C. from the glass transition temperature of the thermoplastic polyimide copolymer, further 20 ° C., In particular, a polyimide metal laminate having excellent adhesion can be obtained by thermocompression bonding at a temperature of 30 ° C. or higher to 420 ° C. or lower.
The determination that the thermoplastic polyimide copolymer layer of the polyimide metal laminate plate is non-crystalline can be determined from the measurement result of the dynamic viscoelasticity of the resin portion obtained by removing the metal foil. Is difficult, it can be determined by preparing a thermoplastic polyimide copolymer film and measuring the film that has been heat-treated under lamination conditions.

The heat-resistant polyimide metal laminate of the present invention is obtained by heating the polyimide metal laminate, preferably in an inert gas atmosphere such as nitrogen or argon, and measuring the dynamic viscoelasticity or X-ray diffraction intensity. A thermoplastic polyimide copolymer layer exhibiting crystallinity is replaced with a thermoplastic polyimide copolymer layer exhibiting crystallinity by measurement of dynamic viscoelasticity.
In the heat-resistant polyimide metal laminate of the present invention,
The heating conditions for the polyimide metal laminate are: a thermoplastic polyimide copolymer layer that exhibits non-crystallinity from the measurement of dynamic viscoelasticity and X-ray diffraction intensity, and a crystallinity from the measurement of dynamic viscoelasticity and X-ray diffraction intensity. It is sufficient that the conditions can be changed to the thermoplastic polyimide copolymer layer shown, and the heating temperature, the heating time, the heating pressure, the heating atmosphere, and other environments can be selected as appropriate, for example, heat More than the glass transition temperature of the plastic polyimide copolymer, preferably 5 ° C., 10 ° C., 15 ° C., 20 ° C., 25 ° C., 30 ° C., 35 ° C. or 40 ° C. higher than the glass transition temperature of the thermoplastic polyimide copolymer Particularly preferred is 30 ° C. from the glass transition temperature of the thermoplastic polyimide copolymer, 40 ° C. or 50 ° C. to 150 ° C. from the glass transition temperature of the thermoplastic polyimide copolymer. When carried out at a temperature range higher than 0 ° C, 100 ° C, 90 ° C or 80 ° C, or 400 ° C or lower than the glass transition temperature, it is relatively short time, for example, 1 minute or more, preferably 3 minutes or more, more preferably 5 minutes. As mentioned above, it can carry out especially preferably in 10 minutes or more.

In the heat-resistant polyimide metal laminate of the present invention, the metal foil has a metal foil on one side or both sides.
In the heat-resistant polyimide metal laminate of the present invention,
Heating of the polyimide metal laminate can be performed using various known devices, and a heating device such as a furnace such as a hot air oven or an infrared heating furnace, an oven such as an inert oven, or a laminating device is appropriately selected. Can do.

A multilayer film having a thermoplastic polyimide copolymer layer on the surface of the heat-resistant polyimide film can be obtained by a known method.
Obtained by applying a thermoplastic polyimide copolymer or a solution of these precursors to a heat-resistant polyimide film or a non-thermoplastic polyimide precursor film, and heating for imidization as necessary. Can do.
The heat-resistant polyimide film is a heat-resistant polyimide film having a metal foil on one side, a heat-resistant polyimide film having a metal foil on one side via an adhesive layer, and a thermoplastic polyimide copolymer layer using the metal foil on one side in the present invention. The heat-resistant polyimide film which has it through can be used. If these are used, the laminated body which has metal foil on both surfaces can be obtained.

A foil having a thermoplastic polyimide copolymer layer on the surface of the metal foil can be obtained by a known method.
It can be obtained by applying a solution of a thermoplastic polyimide copolymer or a precursor thereof onto the surface of the metal foil, and heating for imidization as necessary.

  As a method of applying and applying a solution of a thermoplastic polyimide copolymer or a precursor thereof, a known method can be used, for example, a gravure coating method, a spin coating method, a silk screen method, a dip coating method, Known coating methods such as spray coating method, bar coating method, knife coating method, roll coating method, blade coating method and die coating method can be exemplified.

  The thermoplastic polyimide copolymer can be synthesized by a known method. Random polymerization, block polymerization, or a plurality of polyimide precursor solutions or polyimide solutions are synthesized in advance, and the plurality of solutions are mixed and then subjected to reaction conditions. It can be achieved by any method of mixing under a homogeneous solution.

The thermoplastic polyimide copolymer contains an acid component and a diamine component in an organic solvent at a temperature of about 100 ° C. or lower, further 80 ° C. or lower, further 0 to 60 ° C., particularly 20 to 60 ° C. Reaction for 2 to 60 hours to form a polyimide precursor solution, using this polyimide precursor solution as a dope solution, forming a thin film of the dope solution, evaporating and removing the solvent from the thin film and removing the polyimide precursor It can be produced by imidization. It is also preferable to add various basic compounds as an imidization reaction catalyst to the polyimide precursor solution.
Moreover, in the polyimide which is excellent in solubility, the polyimide precursor solution is heated to 150 to 250 ° C., or an imidizing agent is added and reacted at a temperature of 150 ° C. or less, particularly 15 to 50 ° C., to imide cyclization. After the solvent is evaporated or precipitated into a poor solvent to form a powder, the powder can be dissolved in an organic solution to obtain an organic solvent solution of polyimide.

  In carrying out the polymerization reaction of the polyimide solution or the polyimide precursor solution, the concentration of all monomers in the organic polar solvent may be appropriately selected according to the purpose of use and the purpose of production. For example, in the organic polar solvent It is preferable that the concentration of the total monomer is 1 to 15% by mass, particularly 2 to 8% by mass.

When carrying out the polymerization reaction of the polyimide solution or the polyimide precursor solution, the solution viscosity may be appropriately selected according to the purpose of use (coating, casting, etc.) and the purpose of production. Polyamic (polyimide precursor) acid solution It is preferable from the viewpoint of workability that the rotational viscosity measured at 30 ° C. is about 0.1 to 5000 poise, particularly 0.5 to 2000 poise, more preferably about 1 to 2000 poise. Therefore, it is desirable to carry out the polymerization reaction to such an extent that the produced polyamic acid exhibits the above viscosity.
A polyimide solution or a polyimide precursor solution is produced by the above method, and an organic solvent is newly added to the solution to dilute it.

The thermoplastic polyimide copolymer is a polyimide precursor obtained by reacting an approximately equimolar amount of a diamine component and a tetracarboxylic dianhydride, a slight excess amount of a diamine component or a slight excess amount of an acid component in an organic solvent. (A part of the solution may be imidized as long as a uniform solution state is maintained).
Thermoplastic polyimide copolymers are used for diamine anhydrides, such as phthalic anhydride and its substitution, hexahydrophthalic anhydride and its substitution, succinic anhydride and its substitution, etc. It can be synthesized by adding phthalic anhydride.

  In the thermoplastic polyimide copolymer, the amount of diamine (as the number of moles of amino group) used in the organic solvent is the total number of moles of acid anhydride (as the acid anhydride group of tetraacid dianhydride and dicarboxylic acid anhydride). The ratio to the total mole) is preferably 0.95 to 1.05, particularly 0.98 to 1.02, and particularly preferably 0.99 to 1.01. When the dicarboxylic acid anhydride is used, each component can be reacted at a ratio of 0.05 or less as a ratio of the tetracarboxylic dianhydride to the molar amount of the acid anhydride group.

For the purpose of limiting the gelation of the polyimide precursor, a phosphorus stabilizer such as triphenyl phosphite, triphenyl phosphate, etc. is in the range of 0.01 to 1% with respect to the solid content (polymer) concentration during polyamic acid polymerization. Can be added.
For the purpose of promoting imidization, a basic organic compound can be added to the dope solution. For example, imidazole, 2-imidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline, substituted pyridine and the like are 0.05 to 10% by weight, particularly 0.1 to 2% by weight, based on the polyamic acid. Can be used in proportions. Since these form a polyimide film at a relatively low temperature, they can be used to avoid insufficient imidization.
Further, for the purpose of stabilizing the adhesive strength, an organoaluminum compound, an inorganic aluminum compound or an organotin compound may be added to the polyamic acid solution for heat-fusible polyimide. For example, aluminum hydroxide, aluminum triacetylacetonate or the like can be added in an amount of 1 ppm or more, particularly 1 to 1000 ppm as an aluminum metal with respect to the polyamic acid.

  As the organic solvent used for the production of the polyimide or the polyimide precursor, a known organic solvent capable of synthesizing these can be used. N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, N-methylcaprolactam, phenols, cresols and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

The heat-resistant polyimide metal laminate of the present invention comprises a multilayered polyimide film having a heat-fusible property and a metal foil, preferably laminated with a 90 ° peel strength of 1.0 kgf / cm or more. It does not adhere to other base materials such as films and metals not only at room temperature but also when heated at about 300 ° C., for example, even if laminated with other heat resistant polyimide film under pressure at a temperature of about 300 ° C. ° Peel strength is 20 gf / cm or less.
The single-sided metal foil laminate of the present invention has good moldability, and can be directly subjected to drilling, bending, drawing, metal wiring formation, electronic circuit thermocompression bonding on the wiring, and the like.

  The heat-resistant polyimide metal laminate of the present invention can be used as a wiring board material for electronic components such as printed wiring boards, flexible printed boards, TAB, COF, and COB and electronic devices.

  The glass transition temperature of the thermoplastic polyimide copolymer can be determined by measurement of dynamic viscoelasticity.

  Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited by the examples.

In each of the following examples, “part” means “part by mass”.
In each of the following examples, the physical property evaluation and the peel strength of the copper foil laminated film were measured according to the following methods.
1) Glass transition temperature (° C.) of film: Rheometric Scientific, Inc. Using a Rheometrics Solid Analyzer II manufactured by the company, dynamic viscoelasticity measurement (temperature increase rate: 10 ° C./min, frequency: 6.28 rad / sec) was evaluated based on the peak temperature of tan δ.
2) Dynamic viscoelasticity measurement: Rheometric Scientific, Inc. Using a manufactured Rheometrics Solid Analyzer II, the heating rate was 10 ° C./min and the frequency was 6.28 rad / sec.
The presence or absence of crystallization of the film was evaluated by the retention tendency of the storage elastic modulus above the glass transition temperature.
FIGS. 1A and 1B show measurement examples of dynamic viscoelasticity measurement (E ′) of a polyimide film, and FIG. 1B shows an example of non-crystalline determination.
In the crystallinity example of FIG. 1 (a), E ′ decreases slowly without decreasing rapidly after Tg, or E ′ decreases rapidly, gradually decreases, and further decreases as the temperature increases after Tg. In contrast, in the non-crystalline example of FIG. 1B, E ′ rapidly decreases after Tg. The crystallinity and non-crystallinity can be judged from the decreasing tendency of E ′ after Tg.
3) Crystallinity of film: X-ray diffraction intensity was measured by a transmission method using a rotating counter-cathode X-ray diffractometer RINT2500 manufactured by Rigaku Corporation, and a crystallinity was calculated using a Ruland method.
4) Moisture-absorbing solder heat resistance: Polyimide metal laminates conditioned at 23 ° C-60% RH for 24 hours are floated for 10 seconds in solder baths at various temperatures (270 ° C, 300 ° C, 310 ° C, 340 ° C), and foamed. The presence or absence of blistering was confirmed visually.
It was judged that there was no problem when foaming and swelling were not observed.

(Reference Example 1: Production of polyimide for heat-resistant polyimide film)
Monomer concentration of paraphenylenediamine (PPD) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) in N-methyl-2-pyrrolidone at a molar ratio of 1000: 998 Was 18% (weight%, the same applies hereinafter), and reacted at 50 ° C. for 3 hours. The solution viscosity at 25 ° C. of the obtained polyamic acid solution was about 1680 poise.

(Reference Example 2: Production of thermoplastic polyimide copolymer)
1,3-bis (4-aminophenoxy) benzene (TPE-R) and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) in N-methyl-2-pyrrolidone and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) is added at a molar ratio of 1000: 200: 800 to give a monomer concentration of 18% and triphenylphosphine. The fat was added at 0.5% by weight with respect to the monomer weight, and reacted at 40 ° C. for 3 hours. The solution viscosity at 25 ° C. of the obtained polyamic acid solution was about 1680 poise.
The polyimide obtained from TPE-R and a-BPDA is non-crystalline as a result of measurement of viscoelasticity, and the polyimide obtained from TPE-R and s-BPDA is crystalline as a result of measurement of viscoelasticity. It was.

(Reference Example 3: Production of thermocompression bonding polyimide film)
Using a film forming apparatus provided with a three-layer extrusion die (multi-manifold type die), the polyamic acid solution obtained in Reference Example 1 and Reference Example 2 was used to change the thickness of the three-layer extrusion die and to make a metal support. The film was cast on the substrate, dried continuously with hot air at 140 ° C., and then peeled to form a self-supporting film. After peeling this self-supporting film from the support, the temperature is gradually raised from 150 ° C. to 450 ° C. in a heating furnace to remove the solvent and imidize, and thermocompression bonding of a long three-layer structure with a thickness of 25 μm The conductive polyimide film was wound up on a roll.
The thickness structure (thermoplastic / heat resistance / thermoplasticity) of the thermocompression bonding polyimide film having a three-layer structure is 4 μm / 17 μm / 4 μm.

(Reference Example 4: Production of thermoplastic film A)
Since the viscoelasticity of the thermoplastic polyimide copolymer of the long thermocompression-bondable polyimide film obtained in Reference Example 3 cannot be directly measured, a thermoplastic film is produced from the polyamic acid solution of Reference Example 2, and this thermoplasticity The viscoelasticity of the film was measured to judge non-crystalline or crystalline.
The thermoplastic polyimide copolymer precursor obtained in Reference Example 2 was cast on a glass plate so that the thickness after drying was 50 μm, dried with hot air at 140 ° C., and then peeled and self-supported. An adhesive film was formed. This self-supporting film was attached to a four-way tenter, and the temperature was gradually raised from 150 ° C. to 350 ° C. to remove the solvent and imidize to obtain a thermoplastic film A.
The glass transition temperature of the thermoplastic film A was 240 (° C.).

(Reference Example 5: Production of thermoplastic polyimide)
1,3-bis (4-aminophenoxy) benzene (TPE-R) and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) in N-methyl-2-pyrrolidone Was added at a molar ratio of 1000: 1000 so that the monomer concentration was 18%, and triphenyl phosphate was added at 0.5% by weight based on the monomer weight, and the mixture was reacted at 40 ° C. for 3 hours. . The obtained polyamic acid solution was obtained.

Example 1
(Manufacture of single-sided copper foil polyimide laminates)
Rolled electrolytic copper foil (manufactured by Nikko Materials, BHY-22B-T, thickness 12 μm) and heat produced in Reference Example 3 preheated by heating with hot air at 200 ° C. for 30 seconds in-line immediately before double belt press A pressure-sensitive polyimide film and Upilex 25S are laminated, and the heating zone temperature (maximum heating temperature: 330 ° C., cooling zone temperature (minimum cooling temperature: 180 ° C.), continuously crimping pressure: 3.9 MPa, crimping time In 2 minutes, it was continuously laminated by thermocompression-cooling and cooling, and a single-sided copper foil polyimide laminate (width: 540 mm, length: 1000 m) was wound on a take-up roll.

(Manufacture of heat-resistant polyimide metal laminates)
The roll-rolled single-sided copper foil polyimide laminate thus obtained was heated from room temperature to 300 ° C. over 1 hour in a nitrogen atmosphere and held at 300 ° C. for 16 hours to obtain a heat-resistant polyimide metal laminate. At the same time, the thermoplastic film A obtained in Reference Example 4 was attached to a tenter and the same treatment was performed to obtain a heat-treated film A. It was 310 degreeC as a result of evaluating the solder heat resistance of the heat-resistant polyimide metal laminated board processed after 23 degreeC-60% RH-24Hr humidity control. Moreover, the X-ray diffraction of the heat processing film A was measured, and a result is shown in FIG. The peak accompanying crystallization was seen from FIG. 2, and the crystallinity was calculated as 7%. Furthermore, the dynamic viscoelasticity of the heat-treated film A was measured, and the results are shown in FIG. From FIG. 3, a change in elastic modulus due to crystallization was observed at a temperature higher than the glass transition temperature.

(Example 2)
The roll-rolled single-sided copper foil polyimide laminate obtained in Example 1 was heated from room temperature to 300 ° C. in 1 hour in a nitrogen atmosphere and held at 300 ° C. for 2 hours to obtain a heat-resistant polyimide metal laminate. Obtained. At the same time, the thermoplastic film A obtained in Reference Example 4 was attached to a tenter and subjected to the same treatment to obtain a heat-treated film B. It was 310 degreeC as a result of evaluating the solder heat resistance of the processed heat resistant polyimide metal laminated board. Moreover, the dynamic viscoelasticity of the heat processing film B was measured, and a result is shown in FIG. From FIG. 4, a change in elastic modulus due to crystallization was observed at a temperature higher than the glass transition temperature.

(Example 3)
The roll-rolled single-sided copper foil polyimide laminate obtained in Example 1 was heated from room temperature to 350 ° C. in a nitrogen atmosphere over 1 hour and held at 350 ° C. for 4 hours to obtain a heat-resistant polyimide metal laminate. Obtained. At the same time, the thermoplastic film A obtained in Reference Example 4 was attached to a tenter and subjected to the same treatment to obtain a heat-treated film C. As a result of evaluating the solder heat resistance of the treated heat-resistant polyimide metal laminate after humidity adjustment at 23 ° C.-60% RH-24Hr, there is no problem even at 340 ° C. Moreover, the dynamic viscoelasticity of the heat processing film C was measured, and a result is shown in FIG. From FIG. 5, a change in elastic modulus due to crystallization was observed at a temperature higher than the glass transition temperature.

(Comparative Example 1)
A thermoplastic film B was obtained in the same manner as in Reference Example 4 using the polyamic acid solution of Reference Example 5. The thermoplastic film B was heated in the same manner as in the production of the heat-resistant polyimide metal laminate of Example 1 to obtain a heat-treated film D.
The dynamic viscoelasticity of the heat-treated film D was measured, and the result is shown in FIG. From FIG. 6, it was non-crystalline and no change in elastic modulus due to crystallization was observed.

(Comparative Example 2)
(Manufacture of single-sided copper foil polyimide laminates)
Rolled electrolytic copper foil (manufactured by Nikko Materials, BHY-22B-T, thickness 12 μm) and heat produced in Reference Example 3 preheated by heating with hot air at 200 ° C. for 30 seconds in-line immediately before double belt press A pressure-sensitive polyimide film and Upilex 25S are laminated, and the heating zone temperature (maximum heating temperature: 330 ° C., cooling zone temperature (minimum cooling temperature: 180 ° C.), continuously crimping pressure: 3.9 MPa, crimping time In 2 minutes, it was continuously laminated by thermocompression-cooling and cooling, and a single-sided copper foil polyimide laminate (width: 540 mm, length: 1000 m) was wound on a take-up roll.
It was 270 degreeC as a result of evaluating the solder heat resistance after 23 degreeC-60% RH-24Hr humidity control of the obtained single-sided copper foil polyimide laminated board (heat-unprocessed).
Further, the X-ray diffraction of the thermoplastic film A was measured, and the results are shown in FIG. From FIG. 7, no peak associated with crystallization was observed. Furthermore, the dynamic viscoelasticity of the thermoplastic film A was measured, and the result is shown in FIG. From FIG. 8, no change in elastic modulus due to crystallization was observed at a temperature higher than the glass transition temperature.

(Comparative Example 3)
The roll-rolled single-sided copper foil polyimide laminate obtained in Example 1 was heated from room temperature to 250 ° C. in 1 hour in a nitrogen atmosphere and held at 250 ° C. for 4 hours to obtain a heat-resistant polyimide metal laminate. Obtained. At the same time, the thermoplastic film A obtained in Reference Example 4 was attached to a tenter and subjected to the same treatment to obtain a heat-treated film B. It was 270 degreeC as a result of evaluating the solder heat resistance of the processed heat resistant polyimide metal laminated board. Moreover, the dynamic viscoelasticity of the heat processing film B was measured, and a result is shown in FIG. From FIG. 9, no change in elastic modulus due to crystallization was observed at a temperature higher than the glass transition temperature.

It is a reference measurement figure of the measurement of dynamic viscoelasticity which shows the crystallinity (a) and non-crystallinity (b) of a polyimide film. 2 is a spectrum diagram of X-ray diffraction of the heat-treated film A of Example 1. FIG. 3 is a measurement diagram of dynamic viscoelasticity of the heat-treated film A of Example 1. FIG. 3 is a measurement diagram of dynamic viscoelasticity of the heat-treated film B of Example 2. FIG. 6 is a measurement diagram of dynamic viscoelasticity of the heat-treated film C of Example 3. FIG. 6 is a measurement diagram of dynamic viscoelasticity of a heat-treated film D of Comparative Example 1. FIG. 5 is a spectrum diagram of X-ray diffraction of a thermoplastic film A of Comparative Example 2. FIG. 5 is a measurement diagram of dynamic viscoelasticity of a thermoplastic film A of Comparative Example 2. FIG. 6 is a measurement diagram of dynamic viscoelasticity of a thermoplastic film A of Comparative Example 3. FIG.

Claims (5)

Using the amorphous thermoplastic polyimide copolymer obtained by copolymerizing the component from which the crystalline polyimide is obtained from the measurement of dynamic viscoelasticity and the component from which the amorphous polyimide is obtained,
A polyimide metal laminate is manufactured by laminating a heat-resistant polyimide film and a metal foil with a laminating device through an amorphous thermoplastic polyimide copolymer layer,
Furthermore, the polyimide metal laminate is heated in an inert gas atmosphere, and the amorphous thermoplastic polyimide copolymer is measured from the dynamic viscoelasticity measurement. A method for producing a heat-resistant polyimide metal laminate, characterized by being combined. Using the amorphous thermoplastic polyimide copolymer obtained by copolymerizing the component from which the crystalline polyimide is obtained from the measurement of dynamic viscoelasticity and the component from which the amorphous polyimide is obtained,
Lamination of polyimide metal by bonding heat-resistant polyimide film and metal foil to the glass transition temperature of amorphous thermoplastic polyimide copolymer or higher using laminating device via amorphous thermoplastic polyimide copolymer layer Manufacturing the board,
Furthermore, the polyimide metal laminate is heated to a temperature higher than the glass transition temperature of the amorphous thermoplastic polyimide copolymer in an inert gas atmosphere, and the amorphous thermoplastic polyimide copolymer is obtained by measuring dynamic viscoelasticity. A method for producing a heat-resistant polyimide metal laminate, characterized in that a thermoplastic polyimide copolymer exhibiting crystallinity is obtained from measurement of dynamic viscoelasticity. Using the amorphous thermoplastic polyimide copolymer obtained by copolymerizing the component from which the crystalline polyimide is obtained from the measurement of dynamic viscoelasticity and the component from which the amorphous polyimide is obtained,
A polyimide metal laminate is manufactured by laminating a heat-resistant polyimide film and a metal foil with a laminating device through an amorphous thermoplastic polyimide copolymer layer,
Furthermore, when the polyimide metal laminate is heated in an inert gas atmosphere, the crystallinity calculated by the Randland method from the X-ray diffraction intensity of the thermoplastic polyimide copolymer alone is 3% or less. Heat-resistant polyimide metal laminate characterized in that the thermoplastic polyimide copolymer is a thermoplastic polyimide copolymer having a crystallinity of more than 3% calculated from the X-ray diffraction intensity by the Ruland method. A manufacturing method of a board. Using the amorphous thermoplastic polyimide copolymer obtained by copolymerizing the component from which the crystalline polyimide is obtained from the measurement of dynamic viscoelasticity and the component from which the amorphous polyimide is obtained,
Lamination of polyimide metal by bonding heat-resistant polyimide film and metal foil to the glass transition temperature of amorphous thermoplastic polyimide copolymer or higher using laminating device via amorphous thermoplastic polyimide copolymer layer Manufacturing the board,
Further, the polyimide metal laminate is heated to a temperature higher than the glass transition temperature of the amorphous thermoplastic polyimide copolymer in an inert gas atmosphere. From the X-ray diffraction intensity in the transmission method of the thermoplastic polyimide copolymer alone, the Rand A non-crystalline thermoplastic polyimide copolymer having a crystallinity calculated by the method of 3% or less, and a crystallinity calculated from the X-ray diffraction intensity by the Ruland method to a crystallinity exceeding 3%. A method for producing a heat-resistant polyimide metal laminate, characterized by comprising a plastic polyimide copolymer. The thermoplastic polyimide copolymer is
A component containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene, from which a crystalline polyimide can be obtained by measuring dynamic viscoelasticity; Copolymerizing a component containing 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 1,3-bis (4-aminophenoxy) benzene to obtain an amorphous polyimide from the measurement of viscoelasticity The method for producing a heat-resistant polyimide metal laminate according to any one of claims 1 to 4, wherein the thermoplastic polyimide copolymer is obtained by heating.

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