JP5040451B2 - Manufacturing method of laminate of release material and single-sided metal foil laminated resin film, single-sided metal foil laminated film - Google Patents

Description

The present invention relates to a method for producing a laminate of a release material and a single-sided metal foil laminated resin film, and a roll-like laminate obtained by these production methods and a single-sided metal foil laminated film .

  Aromatic polyimide films are widely used as applications for electronic devices such as cameras, personal computers, and liquid crystal displays. In order to use an aromatic polyimide film as a substrate material such as a flexible printed board (FPC) or tape-automated bonding (TAB), a copper foil is bonded using an adhesive such as an epoxy resin. The method is adopted.

Conventionally, when a single-area layer substrate is laminated, wrinkles may occur due to the difference between expansion and contraction of each constituent base material before and after heating and pressurization, resulting in poor appearance. As a method for suppressing the generation of wrinkles, a method of sticking a release material to the other surface has been proposed. For example, Patent Document 1 proposes a heat-resistant film or metal foil having an Rz of less than 3 μm.
Patent Document 2 includes an adhesive film in which an adhesive layer is laminated on both surfaces of a heat-resistant core layer containing a heat-resistant resin, and a heat-resistant resin backing layer containing a metal layer and a heat-resistant resin. There has been proposed a single-sided metal-clad laminate in which the metal layer is laminated only on one surface and a heat-resistant resin backing layer is laminated on the other surface.
Patent Document 3 discloses a single-sided metal-clad laminate in which a conductive layer is formed on one side of a heat-resistant adhesive sheet having an adhesive layer containing thermoplastic polyimide on both sides of a non-thermoplastic polyimide layer, and a heat-resistant resin backing layer is formed on the other side. A single-sided metal-clad laminate that satisfies the following conditions has been proposed.
80 ≦ (Linear expansion coefficient of conductive layer / Linear expansion coefficient of backing layer) × 100 ≦ 120
80 ≦ (Linear expansion coefficient of heat-resistant adhesive sheet / Linear expansion coefficient of backing layer) × 100 ≦ 120
JP 2001-162719 A JP 2007-055039 A JP 2007-098672 A

When manufacturing a roll of a laminate in which a reinforcing material and a single-sided metal foil laminated resin film are laminated by laminating using a metal foil, a resin film having thermocompression bonding on both sides, and a release material, occasionally Curling may occur in the TD direction in the laminated body after lamination, and as a result, wrinkles may enter the roll. In particular, when a resin film having both sides having thermocompression bonding and a thin total thickness is used, the frequency of occurrence of curling in the TD direction increases in the laminated body after lamination. For this reason, there is a demand for a method in which even if a resin film having thin thermocompression bonding layers on both sides is used, the frequency of occurrence of curling is low or not generated at all in the laminated body after lamination.
In this invention, the roll of the laminated body which laminated | stacked the reinforcing material and the single-sided metal foil laminated resin film is manufactured by laminate molding using a metal foil, a resin film having both sides thermocompression bonding, and a release material. In the case where the laminate obtained after lamination does not curl in the TD direction, or a production method capable of obtaining a roll having a very low frequency of occurrence, particularly when a thin film is used as a resin film having thermocompression bonding on both sides However, it is an object of the present invention to provide a method for producing a roll having no wrinkles by producing a laminate in which curling does not occur in the TD direction or the occurrence frequency is extremely low.

In the present invention, for the purpose of preventing curling in the TD direction of the laminate obtained after lamination, attention was paid to the linear expansion coefficient in the TD direction in a temperature range lower than the lamination temperature.
The first of the present invention is to supply a metal foil, a resin film having thermocompression bonding on both surfaces, and a heat pressurizing thermocompression bonding apparatus while sequentially stacking a release material, and the metal foil and the resin film by thermocompression bonding. Is a method of manufacturing a laminated body of a laminated single-sided metal foil laminated resin film and a release material,
The linear expansion coefficient (TD-P) (50 to 200 ° C.) in the TD direction of the release material is in the range of 0.7 to 0.9 times the linear expansion coefficient (TD-M) in the TD direction of the metal foil. It is related with the manufacturing method of the laminated body characterized by the above-mentioned.
By the first method for producing a laminate of the present invention, a laminate having a small curl in the TD direction can be obtained, and as a result, a laminate having a small curl in the TD direction can be obtained after the release material is peeled off. Furthermore, a roll-shaped laminated body without wrinkles can be produced, and a single-sided metal foil laminated film having excellent productivity, excellent workability, and good appearance can be obtained.

In the first production method of the present invention, the linear expansion coefficient (TD-B) (50 to 200 ° C.) in the TD direction of the resin film having thermocompression bonding on both surfaces is the linear expansion coefficient (TD) in the TD direction of the metal foil. The effect is particularly excellent by being in the range [(TD-B) / (TD-M)] of 0.8 times to 1.2 times of -M).
In the first manufacturing method of the present invention, the linear expansion coefficient (MD-P) (50 to 200 ° C.) in the MD direction of the release material is 0.7 of the linear expansion coefficient (MD-M) in the MD direction of the metal foil. Times to 0.9 times [(MD-P) / (MD-M)],
The linear expansion coefficient (MD-B) (50 to 200 ° C.) in the MD direction of the resin film having thermocompression bonding on both sides is 0.8 to 1 times the linear expansion coefficient (MD-M) in the MD direction of the metal foil. .3 times the range [(MD-B) / (MD-M)]
Furthermore, the linear expansion coefficient (MD-P) (50 to 200 ° C.) in the MD direction of the release material is in the range of 0.7 to 0.9 times the linear expansion coefficient (MD-M) in the MD direction of the metal foil [ (MD-P) / (MD-M)],
The linear expansion coefficient (MD-B) (50 to 200 ° C.) in the MD direction of the resin film having thermocompression bonding on both sides is 0.8 to 1 times the linear expansion coefficient (MD-M) in the MD direction of the metal foil. .3 times the range [(MD-B) / (MD-M)], and the linear expansion coefficient (MD-P) (50 to 200 ° C.) in the MD direction of the release material is a line in the TD direction of the release material. By the expansion coefficient (TD-P) (50 to 200 ° C.) in the range of 0.9 to 1.1 [(MD-P) / (TD-P)],
The effect is particularly excellent.

In the second aspect of the present invention, the metal foil, the resin film having thermocompression bonding on both sides, and the release material are supplied to the heat and pressure thermocompression bonding apparatus while being stacked in order, and the metal foil and the resin film are bonded by thermocompression bonding. Is a method of manufacturing a laminated body of a laminated single-sided copper foil laminated resin film and a release material,
The linear expansion coefficient (50 to 200 ° C.) in the TD direction of the release material should be (−6 to −2 ppm / ° C.) relative to the linear expansion coefficient (50 to 200 ° C.) of the metal foil in the TD direction. It is related with the manufacturing method of the laminated body characterized.
By the method for producing a second laminate of the present invention, a laminate having a small curl in the TD direction can be obtained, and as a result, a laminate having a small curl in the TD direction can be obtained after the release material is peeled off. Furthermore, a roll-shaped laminated body without wrinkles can be produced, and a single-sided metal foil laminated film having excellent productivity, excellent workability, and good appearance can be obtained.
In the second of the present invention, the linear expansion coefficient (50 to 200 ° C.) in the MD direction of the release material is (−9 to −2 ppm / ° C.) with respect to the linear expansion coefficient (50 to 200 ° C.) in the MD direction of the metal foil. ) Is particularly effective.
In the second aspect of the present invention, particularly by using a release material having a linear expansion coefficient ratio (MD / TD ratio) (50 to 200 ° C.) of 0.8 to 1.1 in the MD direction and the TD direction, Excellent effect.
In the second aspect of the present invention, the linear expansion coefficient (50 to 200 ° C.) in the TD direction of the resin film having both sides thermocompression bonding is (with respect to the linear expansion coefficient (50 to 200 ° C.) in the TD direction of the metal foil ( The effect is particularly excellent by using a material of −5 to 5 ppm / ° C.).
In the second aspect of the present invention, the linear expansion coefficient (50 to 200 ° C.) in the MD direction of the resin film having both sides thermocompression bonding is (with respect to the linear expansion coefficient (50 to 200 ° C.) in the MD direction of the metal foil ( The effect is particularly excellent by using a material of −3 to 6 ppm / ° C.).

The first and second preferred embodiments of the present invention will be described below. A plurality of preferred embodiments can be combined.
1) It can be applied when manufacturing a roll in which a release material is wound inside with respect to a single-sided metal foil laminated resin film.
2) The metal foil is a copper foil, and a resin film having a thermocompression bonding property on both sides and a release material can use a polyimide film.
3) The thickness of the metal foil is in the range of 5 to 30 μm,
The thickness of the resin film having both sides thermocompression bonding is in the range of 8 to 40 μm,
This is particularly applicable when the thickness of the release film is in the range of 15 to 50 μm.
4) Use a multilayer polyimide film in which the thermocompression bonding polyimide layer is laminated on both surfaces of the polyimide layer as the resin film having both surfaces thermocompression bonding.
5) Use a double belt press for the heat and pressure thermocompression bonding equipment.

From the first and second aspects of the present invention, a single-sided metal foil laminated resin film or a roll-shaped laminate can be produced.
The single-sided metal foil laminated resin film of the present invention is a laminate having excellent appearance and small curl in the TD direction.

According to the present invention, it is possible to produce a laminate in which a single-sided metal foil laminated resin film and a release material that do not curl in the TD direction overlap with each other, and as a result, easily produce a roll-like long laminate without wrinkles. It can be done and has excellent productivity.
The laminate or roll-like laminate produced by the production method of the present invention can obtain a single-sided metal foil laminate that is not curled in the TD direction, has a good appearance, and has excellent workability by removing the release material. I can do it.

As the resin film having both sides thermocompression bonding, any resin film having both sides thermocompression bonding can be used, for example,
1) Thermocompression bonding such as an adhesive layer, a heat-fusible resin layer (thermocompression resin layer), or a thermosetting resin layer on both sides of a resin film used for a substrate material such as an electronic / electric wiring board. A multilayer resin film having a layer having,
2) The thermocompression bonding resin film in which the resin film itself has thermocompression bonding,
3) The resin film itself has thermocompression bonding such as an adhesive layer, a heat-fusible resin layer (thermocompression bonding resin layer), or a thermosetting resin layer on one surface of the thermocompression bonding resin film having thermocompression bonding. A multilayer resin film having a layer,
And so on.

Adhesive layer, heat-fusible resin layer (thermo-compressible resin layer) on both sides of the central base resin film used for circuit board materials such as electronic / electric wiring boards for resin films with both sides thermo-compression bonding, Or in a multilayer resin film having a layer having a thermocompression bonding property such as a thermosetting resin layer,
As the resin film for the central substrate, known thermoplastics such as polyimides such as wholly aromatic polyimides, polyamides such as polyamideimide and aramid, liquid crystal polymers, polyesters, polyphenylene sulfide, polycarbonate, polyvinyl chloride, and polyvinylidene chloride Alternatively, a non-thermoplastic resin film can be used, and a film made of a high melting point or non-melting polymer such as polyimide such as wholly aromatic polyimide, polyamide such as polyamide imide, and aramid is preferable. Two or more layers may be used in combination, and a multilayer or single-layer film having a thermocompression-bonding resin layer such as polyimide or an adhesive layer on both surfaces of these films can be used.
As the thermocompression-bonding resin film having a thermocompression bonding property, the resin film itself having thermocompression bonding can be a resin that can be directly thermocompression bonded to a metal foil under a known heat and pressure. Examples include polyimides such as group polyimide, polyamideimide, polyamide, liquid crystal polymer, polyester, polycarbonate and the like, and these films may be used in combination of two or more layers.

In the first manufacturing method of the present invention, it is preferable that the resin film and the release material having both surfaces having thermocompression bonding have at least one of the following characteristics. (These features can be combined with any number of features.)
1) The linear expansion coefficient (TD-P) (50 to 200 ° C.) of the release material in the TD direction is 0.7 to 0.9 times the linear expansion coefficient (TD-M) of the metal foil in the TD direction. , Preferably in the range of 0.7 times to 0.8 times,
2) The linear expansion coefficient (TD-B) (50-200 ° C.) in the TD direction of the resin film having thermocompression bonding on both surfaces is 0.8 times the linear expansion coefficient (TD-M) in the TD direction of the metal foil. Is in the range of -1.2 times, preferably in the range of 0.9-1.1 times, more preferably in the range of 0.9-1.0 times,
3) The linear expansion coefficient (MD-P) (50 to 200 ° C) in the MD direction of the release material is 0.8 times the linear expansion coefficient (TD-P) (50 to 200 ° C) in the TD direction of the release material. Those in the range of 1.2 times, preferably in the range of 0.9 times to 1.1 times, more preferably in the range of 0.9 times to 1.0 times,
4) The linear expansion coefficient (MD-B) (50 to 200 ° C.) in the MD direction of the resin film having thermocompression bonding on both surfaces is 0.8 times the linear expansion coefficient (MD-M) in the MD direction of the metal foil. Those in the range of -1.3 times, preferably in the range of 0.9-1.2 times, more preferably in the range of 0.9-1.1 times,
5) The linear expansion coefficient (MD-P) (50 to 200 ° C.) in the MD direction of the release material is in the range of 0.7 to 1.0 times the linear expansion coefficient (MD-M) in the MD direction of the metal foil. More preferably in the range of 0.7 times to 0.9 times, particularly preferably in the range of 0.7 times to 0.8 times,
6) Tensile elastic modulus (MD, ASTM-D882) is 3000 MPa or more, further 4000 MPa or more, particularly 5000 MPa or more.
In the method for producing a roll-shaped laminate of the present invention, by selecting the above 1), preferably 1) and 2) above, it is possible to obtain a curled product in the TD direction, and at least the above-mentioned By selecting 3), 4) or 5), it is possible to obtain one in which curling is suppressed in the MD direction.

In the second manufacturing method of the present invention, it is preferable that the resin film and the release material having both surfaces having thermocompression bonding have at least one of the following characteristics. (These features can be combined with any number of features.)
In the second aspect of the present invention, the optimum linear expansion coefficient (50 to 200 ° C.) of the release film and the resin film having both surfaces thermocompression bonding is in the following range, and these ranges can be selected and combined. .
a) Optimum linear expansion coefficient of the release material (50 to 200 ° C.)
-TD direction: (-6 to -2 ppm / ° C), preferably (-5 to -2 ppm / ° C), more preferably (-4 to -2 ppm / ° C) with respect to the linear expansion coefficient of the metal foil in the TD direction. ), Particularly preferably in the range of (−4 to −3 ppm / ° C.).
MD direction: (−9 to −1 ppm / ° C.), preferably (−7 to −2 ppm / ° C.), more preferably (−6 to −2 ppm / ° C.) with respect to the linear expansion coefficient in the MD direction of the metal foil. ), More preferably (−5 to −2 ppm / ° C.), and particularly preferably (−4 to −3 ppm / ° C.).
-Ratio of the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction of the release material (MD / TD ratio): 0.8 to 1.1, preferably 0.9 to 1.1, more preferably 0.8. A range of 9 to 1.0.
b) Optimum linear expansion coefficient (50 to 200 ° C.) of a resin film having thermocompression bonding on both sides
-TD direction: (-5-5 ppm / ° C), preferably (-4-4 ppm / ° C), more preferably (-3-3 ppm / ° C), relative to the linear expansion coefficient in the TD direction of the metal foil, The range is preferably (-2 to 2 ppm / ° C), particularly preferably (-1 to 1 ppm / ° C).
MD direction: (−4 to 6 ppm / ° C.), preferably (−3 to 5 ppm / ° C.), more preferably (−2 to 4 ppm / ° C.) with respect to the linear expansion coefficient in the MD direction of the metal foil The range is preferably (−1 to 3 ppm / ° C.), particularly preferably (0 to 2 ppm / ° C.).
-Ratio of the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction (MD / TD ratio) of the resin film having thermocompression bonding on both surfaces: 0.8 to 1.1, preferably 0.9 to 1. A range of 1.
In the method for producing a roll-shaped laminate of the present invention, by selecting the linear expansion coefficient in the TD direction of the above-mentioned a), preferably a) and b) above, a product in which curling is suppressed in the TD direction is obtained. Further, by selecting at least the linear expansion coefficient in the MD direction of the above-mentioned a), a) and b), it is possible to obtain a curl suppressed in the MD direction.

In the second aspect of the present invention, when the metal foil is a copper foil such as a rolled copper foil or an electrolytic copper foil, the optimal linear expansion coefficient (50 to 200 ° C.) of the release film and the resin film having both sides thermocompression bonding is It is the following ranges, and these ranges can be selected and combined. (However, when the coefficient of linear expansion in the TD and MD directions of the copper foil is 18 ppm / ° C)
a) Optimum linear expansion coefficient of the release material (50 to 200 ° C.)
TD direction: 12 to 16 ppm / ° C., preferably 13 to 16 ppm / ° C., more preferably 14 to 16 ppm / ° C., particularly preferably 14 to 15 ppm / ° C.
MD direction: 9 to 16 ppm / ° C, preferably 11 to 16 ppm / ° C, more preferably 12 to 16 ppm / ° C, still more preferably 13 to 16 ppm / ° C, and particularly preferably 14 to 15 ppm / ° C.
MD / TD ratio: 0.8 to 1.1, preferably 0.9 to 1.1, more preferably 0.9 to 1.0.
b) Optimum linear expansion coefficient (50 to 200 ° C.) of a resin film having thermocompression bonding on both sides
TD direction: 13 to 23 ppm / ° C., preferably 14 to 22 ppm / ° C., more preferably 15 to 21 ppm / ° C., further preferably 16 to 20 ppm / ° C., particularly preferably 17 to 19 ppm / ° C.
MD direction: 15 to 24 ppm / ° C., preferably 16 to 23 ppm / ° C., more preferably 17 to 22 ppm / ° C., further preferably 18 to 21 ppm / ° C., particularly preferably 18 to 20 ppm / ° C.
MD / TD ratio: 0.8 to 1.1, preferably 0.9 to 1.1.

  Hereinafter, the manufacturing method of the 1st and 2nd laminated body of this invention is demonstrated in detail.

In the method for producing a roll laminate,
Metal foil, resin film having thermocompression bonding on both sides, and the thickness of the release material can be appropriately selected depending on the pressure device used, and any one can be used.
1) The thickness of the metal foil is preferably in the range of 5 to 35 μm, more preferably in the range of 7 to 30 μm, still more preferably in the range of 9 to 25 μm, particularly preferably in the range of 10 to 20 μm.
2) The thickness of the resin film having thermocompression bonding on both sides is preferably in the range of 8 to 125 μm, more preferably 9 to 75 μm, still more preferably 10 to 40 μm, and particularly preferably in the range of 12 to 28 μm.
3) The thickness of the release agent film is preferably in the range of 5 to 75 μm, more preferably 8 to 60 μm, still more preferably 15 to 50 μm, and particularly preferably 22 to 40 μm.
These thicknesses can be selected as appropriate.
Especially in the manufacturing method of the roll-shaped laminate,
The thickness of the metal foil is in the range of 5 to 30 μm,
The thickness of the resin film having both sides thermocompression bonding is in the range of 8 to 40 μm,
The thickness of the release film is in the range of 15-50 μm,
Applicable when combining

  The adhesive is not particularly limited as long as it is a heat-resistant adhesive used in the electric and electronic fields. For example, polyimide adhesive, epoxy-modified polyimide adhesive, phenol resin-modified epoxy resin adhesive, epoxy Examples thereof include a modified acrylic resin adhesive, an epoxy-modified polyamide adhesive, a polyamidephenol adhesive, and an NBR epoxy adhesive. This adhesive can itself be provided by any method implemented in the electronic field. For example, an adhesive solution may be applied to a resin film such as a polyimide film and dried. You may paste together with an agent.

A resin film containing inorganic fine particles can be used for the resin film having both surfaces having thermocompression bonding.
Inorganic fine particles include fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, inorganic oxide powder such as zinc oxide powder, fine particle silicon nitride powder, and titanium nitride powder. Inorganic nitride powder such as silicon carbide powder, inorganic carbide powder such as silicon carbide powder, and inorganic salt powder such as particulate calcium carbonate powder, calcium sulfate powder, and barium sulfate powder. These inorganic fine particles may be used in combination of two or more. In order to uniformly disperse these inorganic fine particles, a means known per se can be applied.

As an example of a resin film having thermocompression bonding on both sides, a film in which a polyimide serving as a central substrate having known heat resistance and strength and a polyimide having thermocompression bonding are laminated on both sides of the polyimide of the central substrate Alternatively, a polyimide film having a known thermocompression bonding property can be used.
The polyimide used as the central substrate is preferably a resin film such as a heat-resistant polyimide that constitutes a base film that can be used as a material for electronic components such as a printed wiring board, a flexible printed circuit board, and a TAB tape.
It is preferable to use a polyimide having at least one of the following characteristics as the polyimide serving as the central substrate. (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) Non-thermoplastic polyimide can be used.

As polyimide as the central substrate,
(1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride and 1,4-hydroquinone dibenzoate-3,3 ′, 4,4′-tetracarboxylic acid bis An acid component containing at least one component selected from anhydrides, preferably an acid component containing at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more of these acid components;
(2) A diamine containing at least one component selected from p-phenylenediamine, 4,4-diaminodiphenyl ether, m-tolidine, and 4,4′-diaminobenzanilide as the diamine component, preferably at least 70 of these diamine components. A polyimide obtained from a diamine component containing at least mol%, more preferably at least 80 mol%, more preferably at least 90 mol% can be used.
In particular, as an example of a combination of an acid component and a diamine component that constitutes the polyimide serving as the central substrate,
1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, p-phenylenediamine or p-phenylenediamine and 4,4-diaminodiphenyl ether,
2) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride, p-phenylenediamine or p-phenylenediamine and 4,4-diaminodiphenyl ether,
3) pyromellitic dianhydride, p-phenylenediamine and 4,4-diaminodiphenyl ether,
4) What is obtained by using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine as main components (50 mol% or more in a total of 100 mol%) is a printed wiring board, Used as a material for electronic components such as flexible printed circuit boards and TAB tapes, has excellent mechanical properties over a wide temperature range, has long-term heat resistance, excellent hydrolysis resistance, and high thermal decomposition starting temperature, It is preferable because the heat shrinkage rate and the linear expansion coefficient are small and the flame retardancy is excellent.

As an acid component that can obtain a polyimide as a central substrate, in addition to the acid component shown above, the characteristics of the present invention are not impaired.
2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2 Acid dianhydride components such as 2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride can be used.

As a diamine component that can obtain a polyimide as a central substrate, in addition to the diamine component shown above, the characteristics of the present invention are not impaired.
m-phenylenediamine, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4, , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, and the like can be used. .

The polyimide used as the thermocompression-bonding polyimide substrate can be a known heat-bondable or thermocompression-bondable polyimide that can be used as a material for electronic components such as printed wiring boards, flexible printed boards, and TAB tapes. .
As a polyimide used as a thermocompression bonding (heat-bonding) polyimide substrate, a polyimide that can be heat-bonded (thermocompression bonding) with a metal foil can be used, preferably 150 to 400 ° C, more preferably. A polyimide such as a thermoplastic polyimide that can be heat-sealed (thermocompression bonded) at a temperature of 200 to 400 ° C., more preferably 250 to 400 ° C., can be used.
The polyimide used as the thermocompression bonding substrate is preferably one having a glass transition temperature of 170 to 320 ° C, more preferably 180 to 300 ° C, still more preferably 190 to 280 ° C, and particularly preferably 200 to 275 ° C. Can do.

The polyimide used as the thermocompression bonding polyimide substrate is
(1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′ , 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4- Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and 1,4-hydroquinone dibenzoate An acid component containing at least one component selected from acid dianhydrides such as −3,3 ′, 4,4′-tetracarboxylic dianhydride, preferably at least 70 mol% of these acid components; Preferably 80 mol% or more, more preferably an acid component comprising 90 mol% or more,
(2) As the diamine component, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-Diaminobenzophenone, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4 -(4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] Ter, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] It is obtained from a diamine containing at least one component selected from diamines such as propane, preferably a diamine component containing these diamine components at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more. Polyimide or the like can be used.

As an example of a combination of an acid component and a diamine component that can obtain a polyimide to be a thermocompression bonding polyimide substrate,
(1) At least one component selected from acid dianhydrides of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride An acid component containing seeds, preferably an acid component containing at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more of these acid components;
(2) As the diamine component, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene 4,4′-bis (3-aminophenoxy) biphenyl, bis [4 -(3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4 A diamine containing at least one component selected from diamines such as-(4-aminophenoxy) phenyl] propane, preferably at least 70 mol%, more preferably 80 mol% or more, more preferably 90 mol, of these diamine components. The polyimide etc. which are obtained from the diamine component which contains% or more can be used.

As a diamine component that can obtain a polyimide that becomes a thermocompression bonding polyimide substrate, in addition to the diamine component shown above, the characteristics of the present invention are not impaired.
m-phenylenediamine, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4, , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, and the like can be used. .

  Other tetracarboxylic dianhydrides, such as 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3, as long as the physical properties of the polyimide used as the thermocompression bonding substrate are not impaired. , 4-dicarboxyphenyl) propane dianhydride or 2,3,6,7-naphthalenetetracarboxylic dianhydride, preferably 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride It may be replaced. Further, other diamines such as 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylmethane, 2,2-bis, as long as the physical properties of the thermocompression bonding polyimide are not impaired. (4-aminophenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenyl) diphenyl ether, 4,4′-bis (4-aminophenyl) Diphenylmethane, 4,4′-bis (4-aminophenoxy) diphenyl ether, 4,4′-bis (4-aminophenoxy) diphenylmethane, 2,2-bis [4- (aminophenoxy) phenyl] propane, 2, Flexible aromatic di- having a plurality of benzene rings, such as 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane Mine, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane and other aliphatic diamines, bis (3-aminopropyl) tetra It may be replaced by a diaminodisiloxane such as methyldisiloxane. The proportion of other aromatic diamine used is preferably 20 mol% or less, particularly preferably 10 mol% or less, based on the total diamine. Moreover, it is preferable that the usage-amount of aliphatic diamine and diaminodisiloxane is 20 mol% or less with respect to all the diamine. If this ratio is exceeded, the heat resistance of the thermocompression bonding polyimide decreases. Dicarboxylic anhydrides, such as phthalic anhydride and its substitutes, hexahydrophthalic anhydride and its substitutes, succinic anhydride and its substitutes, etc., for sealing the amine ends of the thermocompression bonding polyimides, Phthalic anhydride may be used.

  The synthesis of the polyimide that will be the central substrate and / or the polyimide that will be the thermocompression bonding substrate will ultimately be random polymerization, block polymerization, or two types of polyamic acid if the proportion of each component is within the above range. In addition, it can be achieved by any method in which both polyamic acid solutions are mixed and then mixed under reaction conditions to obtain a uniform solution.

  Using each of the above-mentioned components, a substantially equimolar amount of a diamine component and a tetracarboxylic dianhydride are reacted in an organic solvent to give a polyamic acid solution (partly imidized if a uniform solution state is maintained) May be used).

The synthesis of the polyimide as the central base material and / or the polyimide as the thermocompression bonding base material is carried out by using an approximately equimolar amount of the diamine component and the tetracarboxylic dianhydride component (in some cases, the acid content is excessive or the diamine component). Is allowed to react in an organic solvent at a temperature of about 100 ° C. or less, particularly 20 to 60 ° C., to form a polyamic acid solution, and this polyamic acid solution is used as a dope solution. It can be produced by evaporating and removing the solvent from the thin film and cyclizing the polyamic acid with an imide. In addition, the polyamic acid solution produced as described above 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. Thereafter, the solvent is evaporated or precipitated in a poor solvent to form a powder, and then the powder is dissolved in an organic solution to obtain an organic solvent solution of a thermocompression bonding polyimide.
The solution viscosity of the polyamic acid solution may be appropriately selected according to the production method, and the polyamic (polyimide precursor) acid solution has a rotational viscosity measured at 30 ° C. of about 0.1 to 5000 poises, particularly 0.8. From the viewpoint of workability in handling this polyamic acid solution, it is preferably about 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.

  In order to obtain a polyimide as a central substrate and / or a polyimide as a thermocompression bonding substrate, 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 (tetraacid (As the total moles of dianhydride and dicarboxylic anhydride as acid anhydride groups), preferably 0.92 to 1.1, in particular 0.98 to 1.1, in particular 0.99 to 1.1, and the ratio of the amount of the dicarboxylic acid anhydride used to react the tetracarboxylic dianhydride with respect to the molar amount of the acid anhydride group is preferably 0.05 or less. it can.

  When the ratio of the diamine and dicarboxylic acid anhydride is out of the above range, the resulting polyamic acid, and thus the molecular weight of the thermocompression bonding polyimide, is small, which may result in a decrease in the adhesive strength of the laminate with the metal foil. is there. Further, for the purpose of limiting the gelation of polyamic acid, phosphorus stabilizers such as triphenyl phosphite and triphenyl phosphate are 0.01 to 1% based on the solid content (polymer) concentration during polyamic acid polymerization. It can be added in the range of. For the purpose of promoting imidization, a basic organic compound can be added to the dope solution. For example, 0.05-10 mass of imidazole, 2-imidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline, substituted pyridine, etc. with respect to the polyamic acid. %, In particular 0.1 to 2% by weight. Since these form a polyimide film at a relatively low temperature, they can be used to avoid insufficient imidization. For the purpose of stabilizing the adhesive strength, an organoaluminum compound, an inorganic aluminum compound, or an organotin compound may be added to the thermocompression bonding polyimide raw material dope. 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.

  The organic solvent used for the production of polyamic acid is N-methyl-2-pyrrolidone, N, N-dimethylformamide, N for any of polyimide as a central substrate and / or polyimide as a thermocompression bonding substrate. , N-dimethylacetamide, N, N-diethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, N-methylcaprolactam, cresols and the like. These organic solvents may be used alone or in combination of two or more.

また、上記の自己支持性フィルムのイミド化率は、ＩＲ（ＡＴＲ）で測定し、フィルムとフルキュア品との振動帯ピーク面積の比を利用して、イミド化率を算出することができる。振動帯ピークとしては、イミドカルボニル基の対称伸縮振動帯やベンゼン環骨格伸縮振動帯などを利用する。またイミド化率測定に関し、特開平９−３１６１９９号公報に記載のカールフィッシャー水分計を用いる手法もある。 In the production of a multilayer polyimide film, for example, a polyamic acid solution of polyimide as a central base material and a polyamic acid solution for a thermocompression bonding layer are coextruded on a support and cast to the extent that it becomes self-supporting. (It means the stage before the normal curing process), for example, it can be peeled from the support, and is heated at a temperature of 100 to 180 ° C. for about 2 to 60 minutes to produce a self-supporting film. Examples of the self-supporting film include a solidified film in which the solvent and generated water are preferably about 25 to 60% by weight, particularly preferably 30 to 50% by weight.
A self-supporting film is heat-treated to obtain a polyimide film. As the heat treatment of the self-supporting film, a known method can be used. For example, at least a pair of both edges of the self-supporting film can be moved with the film continuously or intermittently. In a state of being fixed by a fixing device or the like, the temperature is higher than the drying temperature, preferably in the range of 200 to 550 ° C, more preferably in the range of 300 to 500 ° C, and particularly preferably in the range of 320 to 500 ° C. The self-supporting film is dried and heat-treated at a temperature, preferably for 1 to 100 minutes, particularly for 1 to 10 minutes, and preferably a volatile substance composed of an organic solvent and product water in the finally obtained polyimide film. The solvent is sufficiently removed from the self-supporting film and the film is constituted so that the content is 1% by weight or less. The imidization of Rimmer performed sufficiently to form a multi-layer polyimide film having thermal adhesiveness.
Further, in the continuous heat treatment at 200 ° C. or higher, it is preferable to carry out the heat treatment with pin tenters, clips, frames, etc., at least fixing both end edges in the direction perpendicular to the longitudinal direction of the long self-supporting film. In particular, when a thin film is manufactured, the heat treatment time may be short.
As the support, for example, a stainless steel substrate or a stainless steel belt is used.
As the polyimide polyamic acid solution, a solution obtained by further adding an imidization catalyst, an organic phosphorus-containing compound, inorganic fine particles and the like can be used.
The loss on heating of the self-supporting film is a value calculated according to Equation 1 from the weight W1 before drying and the weight W2 after drying after drying the film to be measured at 420 ° C. for 20 minutes.

Moreover, the imidation rate of said self-supporting film can be measured by IR (ATR), and an imidation rate can be calculated using the ratio of the vibration band peak area of a film and a full cure product. As the vibration band peak, a symmetric stretching vibration band of an imidecarbonyl group, a benzene ring skeleton stretching vibration band, or the like is used. Further, regarding the imidization rate measurement, there is also a method using a Karl Fischer moisture meter described in JP-A-9-316199.

The thickness of the resin film having thermocompression bonding on both sides is preferably in the range of 8 to 125 μm, more preferably 9 to 75 μm, still more preferably 10 to 40 μm, still more preferably 12 to 28 μm, and particularly preferably 12 to 18 μm. Range.
In the resin film having both surfaces having thermocompression bonding, layers having thermocompression bonding are formed on both surfaces of the resin film, and preferably, layers having thermocompression bonding having substantially the same thickness are formed on both surfaces of the resin film.
As the resin film having both surfaces having thermocompression bonding, a resin film formed so that the layers having thermocompression bonding are integrated on both surfaces of the resin film can be used.
A resin film having thermocompression bonding on both sides has a thermocompression bonding layer having substantially the same thickness on both surfaces, and the total of the thickness of the thermocompression bonding layer on one side and the thickness of the thermocompression bonding layer on the other surface is 3 to 10 μm. The laminate preferably has a thickness of 3 to 9 μm, more preferably 3 to 8 μm, and can provide a laminate that is excellent in pressure-bonding property to the metal foil and does not curl or hardly curl.

  Examples of the metal foil include various metal foils such as copper, aluminum, gold, and alloy foils, and preferred examples include rolled copper foil, electrolytic copper foil, and aluminum foil. A metal foil having a surface roughness Rz of 0.5 μm or more can be used. Further, it is preferable that the surface roughness Rz of the metal foil is 10 μm or less, particularly 7 μm or less.

The release material may be any material that can be easily peeled off from a laminate in which a metal foil and a resin film having thermocompression bonding on both sides are bonded together by a heat and pressure type thermocompression bonding apparatus. In the case where the resin film having the properties is bonded with a heat-pressure type thermocompression bonding apparatus, it is preferable that the resin film does not deform greatly due to the bonding temperature and pressure.
Examples of the release material include resin films and metal foils having an Rz of less than 3 μm.
Examples of release materials include fluororesin films such as PTFE, polyimide films such as Upilex S (manufactured by Ube Industries), resin films such as aramid films, metal foils such as rolled copper foil, rolled aluminum foil, and electrolytic copper foil. Can be mentioned.

An example of the manufacturing method of a roll-shaped laminated body is shown.
Resin film with thermocompression bonding on both sides, metal foil on one side, and reinforcing material on the other side, and continuously supplied to at least a pair of heat and pressure thermocompression bonding equipment Is a long roll-shaped laminate, preferably a release material, which is thermocompressed under heating in a temperature range where the thermocompression bonding layer can be thermocompressed, and a release material is stacked on the opposite side of the metal foil of the resin film. A long roll-shaped laminated body on the inside can be manufactured.
The heat and pressure type thermocompression bonding device is a device having a pressure member, and includes a pair of pressure bonding metal rolls (the pressure bonding portion may be made of metal or ceramic sprayed metal), a double belt press, In particular, it can be thermocompression-bonded and cooled under pressure, and among them, a double belt press can be particularly preferred.

  In the present invention, the resin film and the metal foil having thermocompression bonding on both sides are placed along an inlet drum that leads to a double belt press, preferably at a temperature higher than 100 ° C. and lower than 250 ° C. for about 2 to 120 seconds. A single-sided metal foil laminated resin film can be obtained by preheating, thermocompression-bonding under pressure, cooling and bonding.

  In the present invention, by preheating the resin film in advance, appearance defects due to foaming may occur in the laminated body after lamination due to moisture contained in the resin film such as polyimide, or immersion in a solder bath when forming an electronic circuit Occasional foaming can be prevented and the product yield can be prevented from deteriorating. As a method for preheating the resin film in advance, any method can be used as long as it can be preheated before being supplied to the heating and pressurizing apparatus.

  In the method for producing a single-sided metal foil laminated resin film of the present invention, the temperature of the thermocompression bonding zone of the double belt press is preferably 20 ° C. or more higher than the glass transition temperature of the thermocompression bonding polyimide and 400 ° C. or less, particularly glass. Thermocompression bonding under pressure at a temperature of 30 ° C. or higher and 400 ° C. or lower than the transition temperature, followed by cooling under pressure with a cooling zone, preferably 20 ° C. or more lower than the glass transition temperature of the thermocompression bonding polyimide It can be manufactured by cooling and laminating to a temperature, especially a temperature lower by 30 ° C. or more.

  In the method for producing a single-sided metal foil laminated resin film of the present invention, a highly heat-resistant film that can be easily peeled, such as a high heat-resistant film or metal foil having a Rz of less than 2 μm, preferably a polyimide film (manufactured by Ube Industries, Ltd. -A protective material such as a heat-resistant film such as Pyrex S), a fluororesin film, or a copper foil may be interposed between the metal foil and the belt of the double belt press. This protective material is preferably removed from the laminate after being laminated and wound up.

  In the present invention, it is possible to preferably achieve a take-up speed of 1 m / min or more by laminating by thermocompression-cooling under pressure using a double belt press, and the resulting flexible metal foil laminate is long. Adhesive strength with a width of about 400 mm or more, especially about 500 mm or more, and high adhesion strength (90 ° peel strength: 0.7 kN / m or more, further 0.8 kN / m or more, further 0.9 kN / m or more In particular, it is possible to obtain a flexible metal foil laminate having a good appearance so that wrinkles are not substantially observed on the surface of the metal foil.

  In the present invention, the single-sided metal foil laminated resin film is a single-sided metal foil laminated resin film that is supplied to a double belt press in a state in which the resin film having both sides thermocompression bonding, the metal foil, and the release material are rolled. And a mold release material can be obtained in a rolled state.

Single-sided metal foil laminated resin film is used as a substrate material for flexible printed boards (FPC), tape-automated bonding (TAB), COF, etc. for electronic devices such as cameras, personal computers and liquid crystal displays. Can be used.
The single-sided metal foil laminated resin film has a small curl and can be suitably used as a substrate material for forming a fine pitch circuit.

A sample cut into a length of 540 mm × width of 700 mm (or length of 540 mm × width of 400 mm) of a laminate of a single-sided metal foil laminated resin film and a release material obtained from the method for producing a roll-shaped laminate of the present invention,
1) The curl amount is preferably 25 mm or less, more preferably 20 mm or less, further preferably 15 mm or less, particularly preferably 10 mm or less at both ends on the TD side on the release film side.
And / or
2) The curl amount is preferably 25 mm or less, more preferably 20 mm or less, still more preferably 15 mm or less, particularly preferably 10 mm or less at both ends on the TD side on the metal foil side.
It has the characteristics of.
Furthermore, the sample cut into a length of 540 mm × width of 700 mm (or length of 540 mm × width of 400 mm) of the laminate of the single-sided metal foil laminated resin film and the release material obtained from the method for producing a roll-shaped laminate of the present invention,
The curl amount is preferably 25 mm or less, more preferably 15 mm or less, still more preferably 8 mm or less, and particularly preferably 5 mm or less at both ends on the MD side on the release film side or metal foil side.

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

(Evaluation method)
In each of the following examples, “part” means “part by mass”. In each of the following examples, the physical property evaluation was measured according to the following method.
1) Measuring method of linear expansion coefficient: TMA was measured (MD or TD) at a heating rate of 20 to 200 ° C. and 5 ° C./min.
2) Measuring method of glass transition temperature: Measured from viscoelasticity.
3) Measuring method of tensile modulus: Using a sample having a length of 200 mm and a width of 10 mm, it was performed at a speed of 10 mm / min in accordance with ASTM D882.
4) Measuring method of curl amount: A sample cut into a predetermined size (length 540 mm × width 700 mm or length 540 mm × width 400 mm) is placed on a flat surface as shown in FIG. Measure the amount.
In FIG. 1, the release material film is indicated by symbol 1, the single-sided metal foil laminated resin film is indicated by symbol 2, and the laminate in which the single-sided metal foil laminated resin film and the release material film are overlapped is indicated by symbol 3.
FIG. 1A is a schematic diagram in which both end portions on the TD side of a laminate 3 in which a single-sided metal foil laminated resin film and a release material film overlap are curled on the release material film side 1. X1 indicates the curl amount on the release material film side at both ends of the TD side.
FIG. 1B is a schematic diagram in which both end portions on the TD side of the laminate 3 in which the single-sided metal foil laminated resin film and the release material film overlap are curled to the single-sided metal foil laminated resin film side (metal foil side) 2. It is a figure. X2 indicates the amount of curl on the single-sided metal foil laminated resin film side (metal foil side) at both ends of the TD side.
5) Product appearance: The appearance of the product after lamination was evaluated by visual observation for the presence of wrinkles.
(○: No wrinkles, △: Some wrinkles, ×: Many wrinkles)
6) Adhesive strength (90 ° peel strength): The 90 ° peel strength between the resin film of the single-sided metal foil laminated resin film and the metal foil was measured at a rate of 50 mm / min for a 10 mm wide sample.

(Reference Example 1: Synthesis Example 1 of Dope for Manufacturing Central Substrate Layer Polyimide)
N-methyl-2-pyrrolidone is added to a reaction vessel equipped with a stirrer and a nitrogen introducing tube, and further, paraphenylenediamine (PPD) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ( s-BPDA) at a molar ratio of 1000: 998 so that the monomer concentration was 18% (mass%, the same applies hereinafter). After completion of the addition, the reaction was continued for 3 hours while maintaining 50 ° C. The obtained polyamic acid solution was a brown viscous liquid, and the solution viscosity at 25 ° C. was about 1500 poise. This solution was used as a dope.

(Reference Example 2: Synthesis of dope for producing thermocompression bonding polyimide-1)
N-methyl-2-pyrrolidone is added to a reaction vessel equipped with a stirrer and a nitrogen introducing tube, and 1,3-bis (4-aminophenoxy) benzene (TPE-R) and 2,3,3 ′, 4'-biphenyltetracarboxylic dianhydride (a-BPDA) was added at a molar ratio of 1000: 1000 to a monomer concentration of 22%, and triphenyl phosphate was reduced to 0% of the monomer mass. Added 1%. After completion of the addition, the reaction was continued for 1 hour while maintaining 25 ° C. The solution viscosity at 25 ° C. was about 2000 poise. This solution was used as a dope.

(Reference Example 3: Production of multilayer polyimide film A)
A three-layer extrusion die using a film forming apparatus provided with a three-layer extrusion die (multi-manifold die) for the central substrate layer polyimide manufacturing dope and the thermocompression bonding polyimide manufacturing dope. Then, it was cast on a metal support and continuously dried with hot air at 140 ° C. to form a solidified film. After the solidified film is peeled off from the support, the temperature is gradually raised from 200 ° C. to 320 ° C. in a heating furnace to remove the solvent and imidize, and wind a long three-layer extruded polyimide film on a winding roll. I took it.

The resulting three-layer extruded polyimide film (A1)
The thickness of each layer is 4 μm / 17 μm / 4 μm (total thickness 25 μm), the linear expansion coefficient (50-200 ° C.) is MD: 20 ppm / ° C., TD: 19 ppm / ° C., and the glass transition temperature of the base layer polyimide Is not clearly confirmed at a temperature of 340 ° C. or lower, and the thermocompression-bonding layer polyimide has a glass transition temperature of 250 ° C.

The resulting three-layer extruded polyimide film (A2)
The thickness of each layer is 3 μm / 9 μm / 3 μm (total thickness 15 μm), the linear expansion coefficient (50-200 ° C.) is MD: 19 ppm / ° C., TD: 18 ppm / ° C., and the glass transition temperature of the base layer polyimide Is not clearly confirmed at a temperature of 340 ° C. or lower, and the thermocompression-bonding layer polyimide has a glass transition temperature of 250 ° C.

(Reference Example 4: Production of polyimide film as release material)
The above-mentioned center substrate layer polyimide production dope is cast on a metal support from a single layer extrusion die using a single layer extrusion die and is continuously dried with hot air. A solidified film was formed. After peeling this solidified film from the support, the temperature is gradually raised in a heating furnace to remove the solvent and imidize, and roll several kinds of long polyimide films having the thickness and linear expansion coefficient shown in Table 1 into rolls. Rolled up.

(Example 1, Comparative Examples 1-3)
Rolled rolled copper foil (manufactured by Microhardware, VSBK, thickness 18 μm), three-layer extruded polyimide film (A1), and a rolled release polyimide film shown in Table 1 from each roll The film is pulled out and the three films are stacked and continuously supplied to the double belt press. The heating zone temperature (maximum heating temperature) is 380 ° C., the cooling zone temperature (minimum cooling temperature) is 117 ° C., and continuously. Thermocompression-bonding-cooling was continuously performed under pressure, and a single-sided copper foil laminated polyimide film having a copper foil laminated on one side and a releaser polyimide film were wound into a roll with the releaser polyimide film inside. . The three-layer extruded polyimide film (A1) was preheated to 150 ° C. and supplied to a double belt press.
From the wound roll, a sample having a width of 540 mm and a length of 700 mm was cut out in a state where the polyimide film of the release material and the single-sided copper foil laminated polyimide film were stacked, and the curl amount of the cut sample was evaluated. Show.

(Example 2, Comparative Example 4)
Rolled rolled copper foil (manufactured by Hitachi Cable, HPF-ST12-X, thickness 12 μm), a three-layer extruded polyimide film (A2), and a rolled release polyimide film shown in Table 1, respectively, Pull out the film from the roll of the three layers, superimpose three films, continuously supply to the double belt press, heating zone temperature (maximum heating temperature) 380 ℃, cooling zone temperature (minimum cooling temperature) 117 ℃, Continuously pressurizing and cooling under pressure, and continuously performing cooling. Rolled with a single-sided copper foil laminated polyimide film with a copper foil laminated on one side and a polyimide film as a release material, with the polyimide film as a release material inside. Winded up. The three-layer extruded polyimide film (A2) was preheated to 150 ° C. and supplied to a double belt press.
From the wound roll, a sample having a width of 540 mm and a length of 400 mm was cut out in a state where the polyimide film of the release material and the single-sided copper foil laminated polyimide film were overlapped, and the curl amount of the cut sample was evaluated. Show.

(Example 3)
From each roll using a rolled electrolytic copper foil (manufactured by Nippon Electrolytic Co., Ltd., HLB, thickness 9 μm), a three-layer extruded polyimide film (A2), and a rolled release polyimide film shown in Table 1 The film is pulled out and the three films are stacked and continuously supplied to the double belt press. The heating zone temperature (maximum heating temperature) is 380 ° C., the cooling zone temperature (minimum cooling temperature) is 117 ° C., and continuously. Thermocompression-bonding-cooling was continuously performed under pressure, and a single-sided copper foil laminated polyimide film having a copper foil laminated on one side and a releaser polyimide film were wound into a roll with the releaser polyimide film inside. . The three-layer extruded polyimide film (A1) was preheated to 150 ° C. and supplied to a double belt press.
From the wound roll, a sample having a width of 540 mm and a length of 700 mm was cut out in a state where the polyimide film of the release material and the single-sided copper foil laminated polyimide film were stacked, and the curl amount of the cut sample was evaluated. Show.

Example 4
Rolled rolled copper foil (manufactured by Nikko Metals, BHY22BHA, thickness 18 μm), a three-layer extruded polyimide film (A2), and a roll-released polyimide film shown in Table 1 were used. The film is pulled out and the three films are stacked and continuously supplied to the double belt press. The heating zone temperature (maximum heating temperature) is 380 ° C., the cooling zone temperature (minimum cooling temperature) is 117 ° C., and continuously. Thermocompression-bonding-cooling was continuously performed under pressure, and a single-sided copper foil laminated polyimide film having a copper foil laminated on one side and a releaser polyimide film were wound into a roll with the releaser polyimide film inside. . The three-layer extruded polyimide film (A1) was preheated to 150 ° C. and supplied to a double belt press.
From the wound roll, a sample having a width of 540 mm and a length of 700 mm was cut out in a state where the polyimide film of the release material and the single-sided copper foil laminated polyimide film were stacked, and the curl amount of the cut sample was evaluated. Show.

(Examples 5 and 6)
Rolled rolled copper foil (manufactured by Nikko Metals, BHY13HHA, thickness 12 μm), a three-layer extruded polyimide film (A2), and a roll-released polyimide film shown in Table 1 were used. The film is pulled out and the three films are stacked and continuously supplied to the double belt press. The heating zone temperature (maximum heating temperature) is 380 ° C., the cooling zone temperature (minimum cooling temperature) is 117 ° C., and continuously. Thermocompression-bonding-cooling was continuously performed under pressure, and a single-sided copper foil laminated polyimide film having a copper foil laminated on one side and a releaser polyimide film were wound into a roll with the releaser polyimide film inside. . The three-layer extruded polyimide film (A1) was preheated to 150 ° C. and supplied to a double belt press.
From the wound roll, a sample having a width of 540 mm and a length of 700 mm was cut out in a state where the polyimide film of the release material and the single-sided copper foil laminated polyimide film were stacked, and the curl amount of the cut sample was evaluated. Show.

In Table 1, the linear expansion coefficient ratio between the copper foil and the release film is
It means (linear expansion coefficient of release film) / (linear expansion coefficient of copper foil), and the linear expansion coefficient of copper foil was 18 ppm in both the MD direction and the MD direction.
In Example 6, when the one having a small linear expansion coefficient ratio between the copper foil in the MD direction and the release film was used, a product curled in the MD direction was obtained.
The appearances of the single-sided copper foil laminated polyimide films wound out from the roll-shaped laminates of Examples 1 to 6 and Comparative Examples 1 to 4 were good without any wrinkles.
The 90 ° peel strengths of the single-sided copper foil laminated polyimide films wound out from the roll-like laminates of Examples 1 to 6 and Comparative Examples 1 to 4 were all 1 kN / m or more.

FIG. 1 is a schematic diagram for explaining the curl amount of a sample in which a single-sided metal foil laminated resin film and a release material film are overlapped in the curl amount measurement method.

Explanation of symbols

1: release material film,
2: Single-sided metal foil laminated resin film,
3: A laminate in which a single-sided metal foil laminated resin film and a release material film overlap.

Claims (10)

A single-sided metal foil in which the metal foil and the resin film are bonded together by thermocompression bonding while supplying the metal foil, a resin film having thermocompression bonding on both sides, and a release material in order. It is a method for producing a laminated body in which a laminated resin film and a release material are overlapped,
The linear expansion coefficient (TD-P) (50 to 200 ° C.) of the release material in the TD direction is 0.7 times to the linear expansion coefficient (TD-M) (50 to 200 ° C.) of the metal foil in the TD direction. A method for producing a laminate, wherein a range of 9 times is used.   The linear expansion coefficient (TD-B) (50 to 200 ° C.) in the TD direction of the resin film having thermocompression bonding on both surfaces is the linear expansion coefficient (TD-M) (50 to 200 ° C.) in the TD direction of the metal foil. The method for producing a laminate according to claim 1, wherein the range is 0.8 to 1.2 times. The linear expansion coefficient (MD-P) (50 to 200 ° C.) in the MD direction of the release material is in the range of 0.7 to 0.9 times the linear expansion coefficient (MD-M) in the MD direction of the metal foil. ,
The linear expansion coefficient in the MD direction (MD-B) (50 to 200 ° C.) of the resin film having thermocompression bonding on both surfaces is the linear expansion coefficient (MD-M) (50 to 200 ° C.) in the MD direction of the metal foil. It is the range of 0.8 times-1.3 times, The manufacturing method of the laminated body of Claim 1 or Claim 2 characterized by the above-mentioned. A single-sided copper foil in which the metal foil and the resin film are bonded to each other by thermocompression bonding while supplying the metal foil, the resin film having thermocompression bonding on both sides, and the release material in order. It is a method for producing a laminated body in which a laminated resin film and a release material are overlapped,
The linear expansion coefficient (50 to 200 ° C.) in the TD direction of the release material should be (−6 to −2 ppm / ° C.) relative to the linear expansion coefficient (50 to 200 ° C.) of the metal foil in the TD direction. The manufacturing method of the laminated body characterized. The linear expansion coefficient (50 to 200 ° C.) in the MD direction of the release material is (−9 to −1 ppm / ° C.) relative to the linear expansion coefficient (50 to 200 ° C.) in the MD direction of the metal foil.
The linear expansion coefficient ratio (MD / TD ratio) (50 to 200 ° C.) in the MD direction and TD direction of the release material is in the range of 0.8 to 1.1,
The linear expansion coefficient (50 to 200 ° C.) in the TD direction of the resin film having thermocompression bonding on both sides is (−5 to 5 ppm / ° C.) with respect to the linear expansion coefficient (50 to 200 ° C.) in the TD direction of the metal foil. Use
The linear expansion coefficient (50 to 200 ° C.) in the MD direction of the resin film having thermocompression bonding on both sides is (−3 to 6 ppm / ° C.) with respect to the linear expansion coefficient (50 to 200 ° C.) in the MD direction of the metal foil. The manufacturing method of the laminated body of Claim 4 characterized by the above-mentioned. The thickness of the metal foil is in the range of 5 to 30 μm,
The thickness of the resin film having both sides thermocompression bonding is in the range of 8 to 40 μm,
The thickness of a release film is the range of 15-50 micrometers, The manufacturing method of the laminated body of any one of Claims 1-5 characterized by the above-mentioned.   The laminate is a roll-like laminate in which the release material is wound inward with respect to the single-sided metal foil laminated resin film. The laminate according to any one of claims 1 to 6, Production method.   The method for producing a laminate according to any one of claims 1 to 7, wherein the metal foil is a copper foil, and the resin film having a thermocompression bonding property on both sides and the release material are polyimide films.   The method for producing a laminate according to any one of claims 1 to 7, wherein the metal foil is a rolled copper foil, and both the resin film having thermocompression bonding and the release material are polyimide films.   The resin film having thermocompression bonding on both sides is a film in which polyimide having thermocompression bonding is laminated on both surfaces of polyimide as a central base material, and the polyimide having thermocompression bonding is a temperature of 150 ° C. to 400 ° C. The method for producing a laminate according to any one of claims 1 to 9, wherein the polyimide is a thermoplastic polyimide that can be heat-sealed with a glass.

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