JP4238088B2 - Polyimide laminated metal plate and manufacturing method thereof - Google Patents

Description

  The present invention relates to a polyimide laminate metal plate obtained by firmly bonding a metal plate and a polyimide film without using a solvent-type adhesive layer or a thermosetting liquid adhesive, and a method for producing the same.

  Because polyimide film has excellent heat resistance, mechanical strength, electrical characteristics, etc., flexible printed boards (FPC) using polyimide film are widely used in electronic devices such as cameras, personal computers, and liquid crystal displays. . Conventionally, a flexible printed board (FPC) using a polyimide film is manufactured by laminating a copper foil and a polyimide film using a liquid thermosetting adhesive such as an epoxy resin. However, since the epoxy resin is inferior in heat resistance, there is a problem that the properties of the original polyimide are impaired.

  On the other hand, US Pat. No. 4,543,295 (Patent Document 1) proposes a method of fusing by heating and pressurizing a polyimide film and a metal foil through a heat-fusible polyimide.

U.S. Pat. No. 4,543,295

  However, in the method of Patent Document 1, a polyimide adhesive (an acid anhydride and a diamine dissolved in an organic solvent) is applied to a polyimide film and then dried by heating to form a heat-fusible polyimide layer, or polyimide adhesion It is necessary to produce a heat-fusible polyimide film that is casted into a film, so that (1) there is a problem of environmental pollution due to the use of organic solvents, and (2) the number of manufacturing processes is large and the cost is high. There was also a problem that there was.

  Accordingly, a first object of the present invention is to provide a polyimide laminated metal plate and a metal composite plate obtained by firmly bonding a polyimide film to a metal plate without providing an adhesive layer containing an organic solvent.

  The second object of the present invention is to provide a method for producing such a polyimide laminated metal plate and a metal composite plate.

  As a result of diligent research in view of the above object, the present inventors have found that (a) the polyarylene sulfide film has the property of being firmly fused to both the metal plate and the polyimide film, and (2) the polyarylene sulfide film. Rather than simply fusing to a metal plate and a polyimide film, a high-quality polyimide laminate metal plate free from defects such as wrinkles due to heat shrinkage can be obtained by performing pre-thermocompression and then fusing and quenching. Discovered and came up with the present invention.

  That is, the polyimide laminated metal plate of the present invention is characterized in that a fusion layer composed of a polyarylene sulfide film is interposed between at least one surface of the metal plate and the polyimide film.

  The method for producing a polyimide laminated metal plate of the present invention is as follows: (1) A polyarylene sulfide film and a polyimide film are sequentially laminated on at least one surface of a metal plate, and the melting point of the polyarylene sulfide is −60 ° C. to the melting point of −5 ° C. Preliminary thermocompression bonding (2) By heating the obtained temporary pressure-bonded body to a temperature equal to or higher than the melting point of the polyarylene sulfide, the polyarylene sulfide film is fused to both the metal plate and the polyimide film, Next, (3) rapid cooling is characterized.

  The metal composite plate of the present invention is characterized in that a pair of metal plates are integrally joined via a fusion layer of a polyimide film and a polyarylene sulfide film provided on both sides thereof.

  The method for producing a metal composite plate of the present invention includes (1) a polyarylene sulfide film, a polyimide film and a polyarylene sulfide film interposed between a pair of metal plates, and (2) the obtained laminate is a melting point of the polyarylene sulfide. Pre-thermocompression bonding at a temperature of −60 ° C. to a melting point of −5 ° C., and (3) heating the obtained temporary pressure-bonded body to a temperature equal to or higher than the melting point of the polyarylene sulfide. It is characterized by being fused to the film and the metal plate and then (4) quenched.

  The polyarylene sulfide film is preferably a polyphenylene sulfide film. You may provide many fine through-holes in a polyarylene sulfide film.

  The polyarylene sulfide film is preferably substantially amorphous. The heat distortion rate of the fused polyarylene sulfide film is usually preferably 2% or less.

  The fusion temperature is preferably in the range of the melting point of the polyarylene sulfide to the melting point + 100 ° C., more preferably the melting point + 20 ° C. to the melting point + 80 ° C., particularly preferably the melting point + 40 ° C. to the melting point + 70 ° C.

  The quenching step is preferably carried out to a temperature below the glass transition temperature of polyarylene sulfide. The rapid cooling from the fusion temperature to a temperature lower than the glass transition temperature of the polyarylene sulfide is preferably performed within 3 seconds. The polyimide laminated metal plate and metal composite plate obtained by fusing are preferably rapidly cooled by being poured into water.

  It is preferable to preheat the metal plate to 140 to 280 ° C. before the pre-thermocompression bonding. For pre-thermocompression, (a) in the case of polyimide laminated metal plate, metal plate, polyarylene sulfide film and polyimide film, and (b) in the case of metal composite plate, metal plate, polyarylene sulfide film, polyimide It is preferable that the film, the polyarylene sulfide film, and the metal plate are passed between a pair of heat and pressure rolls to prevent air from being caught in each interface.

  The polyimide laminated metal plate of the present invention is not using an organic solvent because the polyimide film is firmly bonded to the metal plate without using an adhesive containing an organic solvent or a liquid thermosetting adhesive. In addition to the problem of environmental pollution, the number of manufacturing processes is small and the cost is low. In addition, by performing pre-thermocompression bonding, there is substantially no thermal shrinkage (thermal deformation) associated with fusion of the polyarylene sulfide film, so there is no defect such as wrinkles and the state of the polyimide film adhered to the metal plate (transparency, The surface smoothness etc.) is very good.

  By a combination of preliminary thermocompression bonding and fusion, for example, a polyarylene sulfide film as thin as 6 μm can be fused to a metal plate and a polyimide film without thermal deformation. Therefore, it is suitable when it is necessary to bond a very thin polyimide film to a metal plate.

  Since the polyarylene sulfide film itself has good heat resistance and mechanical strength, the heat resistance and mechanical strength of the polyimide laminated metal plate or metal composite plate are close to those of the polyimide film. For this reason, the polyimide laminated metal plate of this invention is suitable for uses, such as a flexible printed board (FPC).

  In addition, when the polyarylene sulfide film rapidly cooled after fusion is left after being remelted, it loses the adhesive force with the metal plate due to crystallization. Utilizing this property, the polyimide film and the polyarylene sulfide film can be easily peeled from the polyimide laminated metal plate and the metal composite plate, and recycling becomes easy.

[1] Polyimide Laminated Metal Plate The polyimide laminated metal plate of the present invention has a polyarylene sulfide film fusion layer interposed between at least one surface of the metal plate and the polyimide film.

(A) Film
(1) Polyimide film A polyimide (PI) film is basically a dehydration condensation reaction product of an aromatic tetracarboxylic dianhydride and an aromatic diamine.

  Examples of aromatic tetracarboxylic dianhydride components include pyromellitic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic acid. Dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid Dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) 1,1,1, 3,3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) 1,1,1,3,3,3-hexachloropropane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4 ′-( p-Phenylenedioxy) diphthalic dianhydride, 4,4 '-(m-phenylenedioxy) diphthalic dianhydride, 4,4'-diphenyl sulfide dioxybis 4-phthalic acid) dianhydride, 4,4'-diphenylsulfonedioxybis (4-phthalic acid) dianhydride, methylene bis- (4-phenyleneoxy-4-phthalic acid) dianhydride, ethylidene bis- (4-phenyleneoxy-4-phthalic acid) dianhydride, isopropylidenebis- (4-phenyleneoxy-4-phthalic acid) dianhydride, hexafluoroisopropylidenebis- (4-phenyleneoxy-4- Phthalic acid) dianhydride and the like.

  Examples of the aromatic diamine component include 4,4′-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- ( 3-aminophenoxy) phenyl] ketone, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenylmethane, 1,1-di (p-aminophenyl) ethane, 2,2-di (p-aminophenyl) propane, 2,2-di (p-aminophenyl) -1,1,1,3,3,3- Examples include hexafluoropropane.

  Each of the aromatic tetracarboxylic dianhydride component and the aromatic diamine component may contain only one kind or two or more kinds. PI film is, for example, “Kapton” from Toray Dubon Co., Ltd., “Apical” from Kaneka Chemical Industry Co., Ltd., “Upilex” from Ube Industries, Ltd. Etc.

（但しnは重合度を示す。）により表されるような、ピロメリット酸二無水物と4,4'-ジアミノジフェニルエーテルとの脱水縮合反応物を主成分とするものが好ましい。かかる脱水縮合反応物は、その熱膨張係数が銅の熱膨張係数とほぼ同じであるので、得られるポリイミドラミネート金属板のカールを防止することができる。さらにかかる脱水縮合反応物は、ポリアリーレンスルフィドフィルムによる熱融着性が比較的良好であり、耐ハンダ耐熱性、可撓性等にも優れている。 As a PI film, the following general formula (1):

It is preferable that the main component is a dehydration condensation reaction product of pyromellitic dianhydride and 4,4′-diaminodiphenyl ether as represented by (where n represents the degree of polymerization). Such a dehydration condensation reaction product has a thermal expansion coefficient substantially the same as the thermal expansion coefficient of copper, so that curling of the resulting polyimide laminated metal plate can be prevented. Furthermore, the dehydration condensation reaction product has relatively good heat-fusibility with a polyarylene sulfide film, and is excellent in solder heat resistance, flexibility, and the like.

（ただし式中のR₁，R₂は、水素、アルキル基、アルコキシ基及びハロゲン基からなる群から選ばれた置換基であり、R₁とR₂は同一であっても異なっていてもよい）のいずれかにより表される二価の芳香族基を示し、mは重合度を示す。］により表される繰り返し単位を主要構成単位とするホモポリマー又はコポリマーからなる。 (2) Polyarylene sulfide film Polyarylene sulfide (PAS) film has the following general formula (2):

− (Ar−S) _m − (2)

[However, -Ar- represents the following general formulas (a) to (l):

(In the formula, R ₁ and R ₂ are substituents selected from the group consisting of hydrogen, alkyl groups, alkoxy groups and halogen groups, and R ₁ and R ₂ may be the same or different. ) Represents a divalent aromatic group represented by any of the above, m represents the degree of polymerization. ] It consists of the homopolymer or copolymer which makes the repeating unit represented by a main structural unit.

（但しmは上記式(2)と同じである）により表される繰り返し単位を有するポリフェニレンスルフィド（PPS）フィルムが好ましい。 Of the PAS film, the following general formula (3):

A polyphenylene sulfide (PPS) film having a repeating unit represented by the formula (2) is preferred.

  The PPS film contains a divalent aromatic group represented by any one of the general formulas (a) to (l) as a copolymerization component in addition to the p-phenylene unit represented by the general formula (3). Can do. The PPS film preferably contains 70 mol percent or more, more preferably 90 mol percent or more of the p-phenylene unit represented by the general formula (3).

  Commercially available PPS films include, for example, “Torelina” (trade name) manufactured by Toray Industries, Inc., “DIC PPS” (trade name) manufactured by Dainippon Ink and Chemicals, and “ASAHI PPS” manufactured by Asahi Glass Co., Ltd. (Trade name), “Sustile” (trade name) manufactured by Tosoh Sastiel Co., Ltd., and the like. As the PPS film, a laminated structure in which a polyester film is sandwiched between two PPS films can be used. An example of such a laminated film is “Torelina“ TLT ”” (trade name) manufactured by Toray Industries, Inc.

  PPS films generally have a melting point of about 285 ° C and a glass transition temperature of about 88-90 ° C. The melting point can be measured by ASTM D4591, and the glass transition temperature can be measured by JIS K7121 (the same applies hereinafter).

(3) Other additive ingredients
The PI film and PAS film are not limited to those composed of a single resin component, and may be composed of a plurality of resin components. As a combination of resin components, in addition to a combination of a plurality of polyimide resins and a plurality of polyarylene sulfide resins, the effect of the present invention can be applied to one or more types of polyimide resins and one or more types of polyarylene sulfide resins. What added other thermoplastic resin in the range which does not inhibit is mentioned. Other thermoplastic resins include PAS (can be added to PI resin); PI (can be added to PAS resin); Polyamide (PA); Polyamideimide (PAI); Polyethersulfone (PES) Polyether ether ketone (PEEK); Polycarbonate; Polyurethane; Fluororesin; Polyolefin such as polyethylene and polypropylene; Polyvinyl chloride; Thermoplastic elastomer and the like.

  When other thermoplastic resins are contained, the ratio is preferably 5 to 20% by mass, more preferably 5 to 15% by mass, based on 100% by mass of the entire PI film or the entire PAS film. Particularly preferred is ˜10% by weight. Therefore, unless otherwise specified, the terms “PI film” and “PAS film” used in this specification include not only a simple substance of PI or PAS but also a composition comprising PI or PAS + other thermoplastic resin. Should be understood.

  PI film and PAS film are plasticizers, stabilizers such as antioxidants and UV absorbers, antistatic agents, surfactants, colorants such as dyes and pigments, flow, etc. Additives such as lubricants, inorganic fillers, conductivity improvers and the like may be appropriately contained.

(4) Film thickness
Although there is no restriction | limiting in particular in the thickness of a PI film and a PAS film, About 5-50 micrometers is suitable for practical use. It is technically difficult to make the thicknesses of the PI film and the PAS film less than about 5 μm, and the cost becomes high. Further, when the thickness of the PI film or PAS film exceeds about 50 μm, the film price rises, and the use of the obtained polyimide laminated metal plate is limited.

(5) Printing
Characters and / or designs may be printed on the PI film as necessary. When providing a printing layer on a PI film, characters and / or designs are provided in advance by gravure printing, ink jet printing, or the like. The printed layer may be provided on either one side or both sides of the PI film, but from the viewpoint of abrasion resistance, the printed layer is preferably provided on the side in contact with the metal plate.

  As printing ink, what mixed the pigment and various additives with base thermoplastic resins, such as an acrylic resin type, a polyester resin type, and a polyurethane resin type, can be used. Two-component polyurethane resin-based printing inks are excellent in water resistance. An ink containing a base thermoplastic resin having a melting point as close as possible to that of the PAS resin is preferred so that it melts at a time close to that of the PAS film when fused to the metal plate.

(B) Metal plate
The metal plate to which the PI film is fused is not particularly limited and can be variously selected depending on the application. For example, when producing a flexible printed board (FPC), it is preferable to use copper foil and aluminum foil as a metal plate. As the copper foil, a known rolled copper foil or special electrolytic copper foil is preferable. Moreover, when producing electrical products, such as OA equipment and household appliances, it is preferable to use a copper plate, a steel plate, an aluminum plate, or the like. Furthermore, when producing plastic laminated metal plates for vehicles such as trains and passenger cars, it is preferable to use steel plates, stainless steel plates, aluminum plates and the like. Furthermore, when producing food or beverage cans, it is preferable to use steel plates or aluminum plates. The thickness of the metal plate (foil) can be appropriately selected depending on the application.

  As the steel plate, for example, a galvanized steel plate or a chrome plated steel plate may be used. Moreover, you may form a well-known chemical conversion film on the surface of a steel plate (or plated steel plate).

[2] Method for Producing Polyimide Laminated Metal Plate FIG. 1 is a schematic side view showing an example of an apparatus for producing the polyimide laminated metal plate of the present invention. However, the present invention is not limited to this manufacturing method.

  First, the metal plate 1 unwound from the reel 10 is preheated to 180 to 240 ° C. by the heaters 40 and 40 ′. Heat the preheated metal plate 1, the PPS film 2 rewound from the reel 20, and the PI film 3 rewound from the reel 30 so that they overlap in the order of PI film 3 / PPS film 2 / metal plate 1. Pass between the pressure rolls 41 and 42, and pre-heat-press. In the example of FIG. 1, another pair of heating and pressing rolls 43 and 44 are provided downstream of the heating and pressing rolls 41 and 42. Preliminary thermocompression bonding can be reliably performed by adding the heating and pressing rolls 43 and 44, but this is not essential. The heating and pressing rolls 41 to 44 are preferably mirror-finished. For example, the heating rolls 41 to 44 are preferably set to 240 to 275 ° C. Since the metal plate 1 generally has a higher thermal conductivity than the PI film 3, the temperature of the heating and pressing rolls 41 and 43 and the heating and pressing roll 42 are adjusted as necessary so that the PPS film 2 is uniformly heated. , 44 may be set differently.

  The obtained temporary press-bonded body 11 is heated to a temperature of the melting point of PPS to the melting point + 100 ° C. by the heaters 45 and 45 ′, and the PPS film 2 is fused to the metal plate 1 and the PI film 3. The fused laminate 12 is passed through a water bath 47 through a heating guide roll 46. While passing through the water bath 47, the PPS film 2 is rapidly cooled. Even if the rapid cooling step is completed at a temperature higher than the glass transition temperature, the crystallization of the PPS film 2 may be very small, but it is preferable that the quenching step is practically performed to a temperature lower than the glass transition temperature (usually a water temperature). The obtained polyimide-laminated metal plate is dried by a dryer 49 through a guide roll 48 and wound on a reel 13 at room temperature. Hereafter, it is not limited to the apparatus of FIG. 1, Each process of the method of this invention is explained in full detail.

(A) Film pre-treatment or processing
(1) Corona discharge treatment
It is preferable to apply a corona discharge treatment to the PI film 3 and the PAS film 2 because the thermocompression bonding strength, fusion strength, and fusion strength between the films on the metal plate are improved.

(2) Micro hole processing
When the PI film 3 and the PAS film 2 are pre-thermocompression bonded to a metal plate, fine through-holes may be formed in advance on the entire surface of the PAS film 2 so that air can be discharged even if it is caught between layers . Although fine through-holes may be formed in the PI film 3, when the surface property of the PI film 3 is important, fine through-holes are not formed. The micropores preferably have an average opening diameter of 0.5 to 100 μm and a distribution density of about 500 holes / cm ² or more. If the distribution density of the micropores is less than about 500 holes / cm ² , the prevention of air accumulation is insufficient.

  In order to form micropores in the PI film 3 and the PAS film 2, for example, methods disclosed in Japanese Patent No. 2071842 and Japanese Patent Application Laid-Open No. 2002-059487 can be employed. For example, when the method disclosed in Japanese Patent No. 2071842 is used, a PI film or a second roll between a first roll in which a large number of particles having a Mohs hardness of 5 or more having sharp corners adhere to the surface and a second roll having a smooth surface is used. By passing the PAS film and adjusting the pressing force to the PI film or PAS film that passes between the rolls to be uniform over the entire film surface that is in contact with each roll, A large number of the fine holes can be formed in the PI film or PAS film at the sharp corners of the particles. As the second roll, for example, an iron-based roll, an iron-based roll having a surface plated with Ni, Cr, or the like, a stainless-based roll, a special steel roll, or the like can be used.

(B) Preheating metal plate
It is preferable to preheat the metal plate 1 to a predetermined temperature so that the pre-thermocompression bonding of the PI film 3 / PAS film 2 / metal plate 1 is facilitated. Although the preheating temperature of the metal plate 1 is adjusted according to the melting point of the PAS film, it may generally be 140 to 280 ° C. For example, when using a PPS film, the preheating temperature of the metal plate 1 is preferably 180 to 240 ° C.

(C) Pre-thermocompression The pre-thermocompression temperature is set according to the melting point of the PAS film. Specifically, in the case of a PPS film, the preliminary thermocompression bonding temperature is preferably a melting point of −60 ° C. to a melting point of −5 ° C., and more preferably a melting point of −30 ° C. to a melting point of −10 ° C. The time for maintaining the preliminary thermocompression bonding temperature is usually 2 to 10 minutes.

  When the PAS film is heated to the preliminary thermocompression bonding temperature, the PAS resin becomes sticky and thermocompression bonding is possible. When the PAS film is heated to a temperature exceeding the upper limit of the pre-thermocompression bonding temperature, the PAS film is easily cut while passing through the heat and pressure rolls 41 and 42.

  The pressure in the preliminary thermocompression bonding step is preferably 2 MPa or more, and more preferably 2.0 to 20 MPa. If the pressure is less than 2 MPa, the preliminary thermocompression bonding cannot be performed substantially, and the PAS film may be thermally deformed in the subsequent fusion process. Even if the pressure exceeds 20 MPa, the thermocompression bonding effect is saturated.

  In the pre-thermocompression process, air is not caught between the metal plate and the PAS film, and between the PAS film and the PI film, and the metal plate / PAS film / PI film is thermocompression bonded to the extent that it is not displaced in the fusion process. A temporary crimped body is obtained. Since air is not involved, not only a clean film surface with no blister on the PI film surface is obtained, but also the adhesive strength between the PAS film, the metal plate and the PI film is high.

  In addition, the PAS film of the temporary press-bonded body is substantially free from thermal shrinkage due to melting and quenching, and therefore is not substantially thermally deformed. This is considered to be because the pressure-bonding force is larger than the heat shrinkage force. Therefore, the PAS film is firmly bonded to the metal plate and the PI film without displacement without pressing the temporary pressure-bonded body in the subsequent fusion process. For this reason, when the printing layer is provided on the PAS film, the printing layer is not distorted.

(D) Fusion process In the fusion process, the temporary press-bonded body is heated to a melting point or higher of the PAS film. The fusing temperature is preferably from the melting point of the PAS resin to the melting point + 100 ° C., more preferably the melting point + 20 ° C. to the melting point + 80 ° C., and particularly preferably the melting point + 40 ° C. to the melting point + 70 ° C. At the fusing temperature, the PAS film becomes molten and fuses to the metal plate and PI film. The fusion time is usually 30 seconds to 10 minutes. It is not necessary to apply pressure during the fusing process, but it may be applied to about 1 to 10 MPa.

(E) Rapid cooling step Amorphization of the PAS film is achieved by rapidly cooling the fused laminate. In order to ensure amorphization, the rapid cooling process is preferably performed within 3 seconds from the fusion temperature to a temperature below the glass transition temperature of the PAS resin, more preferably within 1 second. The PAS film crystallizes unless it is rapidly cooled from the fusing temperature, and loses adhesion to the metal plate and the PI film. The rapid cooling can be performed by various means, but it is convenient and preferable to put it in a refrigerant such as water. In addition, a sufficiently low-temperature cold air may be blown or contacted with a cooling roll. For example, in the case of the water bath 47 shown in FIG. 1, the temperature of the water is preferably 20 ° C. or less, and more preferably an ice water bath.

  Although the method for continuously producing a polyimide laminated metal plate using a long metal plate has been described above, it can also be manufactured in a batch manner using a metal plate of a predetermined size. In the case of the batch type, a press machine can be used in the preliminary thermocompression bonding process, and a heating furnace can be used in the fusion bonding process.

  In the polyimide laminated metal plate obtained by the method of the present invention, the PAS film is firmly fused to the metal plate without substantially thermal shrinkage (thermal deformation), and the thermal deformation rate of the PAS film is 2% or less. Especially, it is as small as 1% or less. Therefore, the film surface property of the polyimide laminated metal plate is very good.

[3] Metal composite plate and manufacturing method thereof The metal composite plate of the present invention has a structure in which a pair of metal plates are integrally fused via a PI film and PAS films provided on both sides thereof. The fused state of the plate / PAS film / PI film is the same as that of the polyimide laminated metal plate. Therefore, only matters different from the polyimide laminated metal plate will be described in detail below. Unless otherwise specified, it is the same as the polyimide laminated metal plate. In addition, although the metal composite plate of this invention has a pair of metal plate, you may make it a metal composite plate which has three or more metal plates by laminating | stacking a metal composite plate.

  The pair of metal plates may be the same type or different types, and can be appropriately selected depending on the application. For example, an aluminum plate and a copper plate can be bonded by PAS film / PI film / PAS film instead of brazing.

  Since the metal composite plate of the present invention has strength, light weight and heat resistance, it is useful for, for example, elevator cab panels and doors, construction panels, vehicle panels, marine panels, aircraft panels and the like. . The metal composite plate of the present invention can also be used for a flexible printed wiring board (FPC).

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Aluminum plate: 0.3 mm x 20 mm x 180 mm.
Polyphenylene sulfide film: biaxially stretched PPS film [thickness: 25 μm, melting point: 285 ° C., glass transition temperature: 90 ° C., trade name: “Torelina” (manufactured by Toray Industries, Inc.)].
Polyimide film: biaxially stretched PI film [thickness: 12 μm, melting point: none, glass transition temperature: 280 ° C. or higher, trade name: “Kapton H” (manufactured by Toray Dubon Co., Ltd.)].

  The PI film was overlaid on the PPS film on which a lattice pattern consisting of straight lines with an interval of 1 cm was printed on one side. These were placed on an aluminum plate preheated to 200 ° C. with the PPS film facing down, and pre-press-bonded for 5 minutes at a temperature of 270 ° C. and a pressure of 5 MPa using a press.

  In the obtained temporary press-bonded body, the PPS film was in close contact with both the aluminum plate and the PI film, and no air was caught at the interface between them. This temporary press-bonded body was put in an electric oven and held at 350 ° C. (set temperature) for 8 minutes, and the PPS film was melted and fused to an aluminum plate and a PI film, respectively. The obtained laminate was taken out of the electric oven and immediately poured into 20 ° C. water, and the temperature of the laminate was set to be lower than the glass transition temperature of PPS within 3 seconds.

  The film layer of the obtained polyimide laminated aluminum plate had excellent transparency and surface smoothness. Also, the surface PI film had high hardness. The deformation rate of the lines constituting the lattice pattern on the fused PPS film was measured and found to be less than 0.5%. The deformation rate was obtained by the maximum value of the value obtained by dividing the maximum distance between a straight line connecting any two points of the line constituting the lattice pattern and the line by the length of the straight line.

  No air entrainment was observed at the PPS film / aluminum plate interface and the PPS film / PI film interface. Further, when the polyimide laminated aluminum plate was repeatedly bent, the aluminum plate was destroyed, but there was no peeling of the PPS film from the aluminum plate and the PI film.

From the above experimental results, the following was found.
(1) The PPS film becomes transparent when amorphized by rapid cooling after fusing, and firmly adheres to the aluminum plate and the PI film.
(2) Since the PPS film is fused after pre-thermocompression bonding to the aluminum plate and PI film, the PPS film hardly undergoes thermal shrinkage (thermal deformation) due to fusion or rapid cooling.
(3) Since the PPS film is fused after pre-thermocompression bonding to the aluminum plate and the PI film, there is no air entrainment at these interfaces.

  A polyimide laminated aluminum plate was produced in the same manner as in Example 1 except that an aluminum plate having a thickness of 0.1 mm was used and the holding time in the electric oven was 5 minutes.

  The film layer of the obtained polyimide laminated aluminum plate had excellent transparency and surface smoothness. Also, the surface PI film had high hardness. The deformation rate of the lines constituting the lattice pattern on the fused PPS film was measured and found to be less than 0.5%.

  No air entrainment was observed at the PPS film / aluminum plate interface and the PPS film / PI film interface. Further, when the polyimide laminated aluminum plate was repeatedly bent, the aluminum plate was destroyed, but there was no peeling of the PPS film from the aluminum plate and the PI film.

  A polyimide laminated aluminum plate was prepared in the same manner as in Example 1 except that an aluminum foil of 20 μm × 20 mm × 180 mm was used and the holding time in the electric oven was 3.5 minutes.

  The film layer of the obtained polyimide laminated aluminum plate had excellent transparency and surface smoothness. Also, the surface PI film had high hardness. The deformation rate of the lines constituting the lattice pattern on the fused PPS film was measured and found to be less than 0.5%.

  No air entrainment was observed at the PPS film / aluminum plate interface and the PPS film / PI film interface. Further, when the polyimide laminated aluminum plate was repeatedly bent, the aluminum plate was destroyed, but there was no peeling of the PPS film from the aluminum plate and the PI film.

Comparative Example 1
A polyimide-laminated aluminum plate was produced in the same manner as in Example 1 except that the fused laminate was taken out from the electric oven at almost the same fusion temperature and allowed to cool to room temperature. It can be seen that the PPS film is slightly cloudy and not amorphous. Moreover, when the same polyimide laminate aluminum plate as in Example 1 was subjected to a destructive test, peeling of the PPS film layer from the aluminum plate occurred in the destructive portion. From this, it can be seen that the PPS film does not adhere firmly to the aluminum plate unless it is rapidly cooled after fusing.

Comparative Example 2
A polyimide laminated aluminum plate was produced in the same manner as in Example 1 except that the fused laminate was taken out from the electric oven at almost the same fusion temperature and then immersed in hot water at 100 ° C. When the obtained polyimide laminated aluminum plate was broken in the same manner as in Example 1, peeling of the PPS film layer from the aluminum plate occurred in the broken portion. From this, it can be seen that if the cooling rate after fusion is slow, the PPS film does not sufficiently fuse to the aluminum plate.

Comparative Example 3
A polyimide-laminated aluminum plate was produced in the same manner as in Example 1 except that the set temperature of the electric oven was 250 ° C. When the obtained polyimide laminated aluminum plate was broken in the same manner as in Example 1, peeling of the PPS film layer from the aluminum plate occurred in the broken portion. From this, it can be seen that the PPS film does not fuse to the aluminum plate unless heated above the melting point of the PPS film.

Comparative Example 4
A polyimide-laminated aluminum plate was produced in the same manner as in Example 1 except that the fusion treatment was carried out in a state where the PPS film and the PI film were directly placed on the aluminum plate without performing preliminary thermocompression bonding. The PPS film layer of the obtained polyimide laminated aluminum plate was significantly heat-shrinked, and the lattice pattern on the PPS film was also significantly deformed. In addition, the PPS film was not partially fused to the aluminum plate. From this, it can be seen that the PPS film cannot be uniformly fused to the aluminum plate without thermal deformation unless preliminary thermocompression bonding is performed before the fusion process.

It is a schematic side view which shows an example of the apparatus for manufacturing a polyimide laminated metal plate.

Explanation of symbols

1 ... Metal plate
11 ... Temporary crimping body
12 ... Fused laminate
13 ・ ・ ・ Reel wound with polyimide laminated metal plate 2 ・ ・ ・ PAS (PPS) film
20 ・ ・ ・ Reel with PAS (PPS) film 3 ・ ・ ・ PI film
30 ・ ・ ・ Reel wrapped with PI film
40, 40 ', 45, 45' ・ ・ ・ Heater
41, 42, 43, 44 ・ ・ ・ Heating roll
46, 48 ・ ・ ・ Guide roll
47 ... bathing
49 ... Dryer

Claims (24)

A polyimide-laminated metal plate, wherein a fusion layer composed of a polyarylene sulfide film is interposed between at least one surface of the metal plate and the polyimide film. The polyimide laminated metal plate according to claim 1, wherein the polyarylene sulfide film is a polyphenylene sulfide film. 3. The polyimide laminated metal plate according to claim 1, wherein the polyarylene sulfide film is substantially amorphous. The polyimide laminated metal plate according to any one of claims 1 to 3, wherein a thermal deformation rate of the fused polyarylene sulfide film is 2% or less. A method for producing a polyimide laminated metal plate, wherein (1) a polyarylene sulfide film and a polyimide film are sequentially stacked on at least one surface of a metal plate, and the polyarylene sulfide has a melting point of −60 ° C. to a melting point of −5 ° C. Preliminary thermocompression bonding (2) By heating the obtained temporary pressure-bonded body to a temperature equal to or higher than the melting point of the polyarylene sulfide, the polyarylene sulfide film is fused to both the metal plate and the polyimide film, Next, (3) a method characterized by quenching. 6. The method for producing a polyimide-laminated metal sheet according to claim 5, wherein the quenching step is performed to a temperature lower than the glass transition temperature of the polyarylene sulfide. The method for producing a polyimide laminated metal plate according to claim 5 or 6, wherein a polyphenylene sulfide film is used as the polyarylene sulfide film. The method for producing a polyimide-laminated metal sheet according to any one of claims 5 to 7, wherein the fusion temperature is in the range of the melting point of the polyarylene sulfide to the melting point + 100 ° C. The method for producing a polyimide-laminated metal sheet according to any one of claims 5 to 8, wherein the rapid cooling is performed within 3 seconds from the fusion temperature to a temperature lower than the glass transition temperature of the polyarylene sulfide. 10. The method for producing a polyimide laminated metal plate according to claim 9, wherein the polyimide laminated metal plate obtained by fusion bonding is rapidly cooled by being poured into water. The method for producing a polyimide-laminated metal plate according to any one of claims 5 to 10, wherein the metal plate is preheated to 140 to 280 ° C before the preliminary thermocompression bonding step. The method for producing a polyimide-laminated metal plate according to any one of claims 5 to 11, wherein each interface is formed by passing the metal plate, the polyarylene sulfide film, and the polyimide film between a pair of heat and pressure rolls. A method of carrying out preliminary thermocompression bonding while preventing air from being caught in the air. 13. The method for producing a polyimide-laminated metal plate according to claim 5, wherein a polyarylene sulfide film having a large number of fine through holes is used as the polyarylene sulfide film. A metal composite plate, wherein a pair of metal plates are integrally joined via a fusion layer of a polyimide film and a polyarylene sulfide film provided on both sides thereof. 15. The metal composite plate according to claim 14, wherein the polyarylene sulfide film is a polyphenylene sulfide film. 16. The metal composite plate according to claim 14 or 15, wherein the polyarylene sulfide film is substantially amorphous. The metal composite plate according to any one of claims 14 to 16, wherein the thermal deformation rate of the fused polyarylene sulfide film is 2% or less. The method for producing a metal composite plate according to any one of claims 14 to 17, wherein (1) a polyarylene sulfide film, a polyimide film and a polyarylene sulfide film are interposed between a pair of metal plates, and (2) obtained. The laminate is pre-thermocompression bonded at a temperature of the melting point of the polyarylene sulfide of −60 ° C. to the melting point of −5 ° C., and (3) by heating the obtained temporary pressing body to a temperature equal to or higher than the melting point of the polyarylene sulfide. Each of the polyarylene sulfides is fused to the polyimide film and the metal plate, and then (4) quenched. 19. The method for producing a metal composite plate according to claim 18, wherein the quenching step is performed to a temperature lower than a glass transition temperature of the polyarylene sulfide. 20. The method for producing a metal composite sheet according to claim 18 or 19, wherein the fusion temperature is in the range of the melting point of the polyarylene sulfide to the melting point + 100 ° C. 21. The method for producing a metal composite sheet according to any one of claims 18 to 20, wherein the rapid cooling is performed within 3 seconds from the fusion temperature to a temperature lower than the glass transition temperature of the polyarylene sulfide. 22. The method for producing a metal composite plate according to claim 21, wherein the composite plate obtained by fusing is rapidly cooled by being poured into water. 23. The method for producing a metal composite plate according to any one of claims 18 to 22, wherein the metal plate is preheated to 140 to 280 [deg.] C. before the preliminary thermocompression bonding step. 24. The method for producing a metal composite plate according to claim 18, wherein the metal plate, the polyarylene sulfide film, the polyimide film, the polyarylene sulfide film and the metal plate are passed between a pair of heat and pressure rolls. A method of performing preliminary thermocompression bonding while preventing air from being caught in each interface.

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