JP4911296B2 - Manufacturing method of metal wiring heat-resistant resin substrate - Google Patents

Description

  The present invention is a metal wiring heat-resistant resin substrate having excellent metal plating properties such as tin plating and excellent adhesion to an anisotropic conductive film (hereinafter referred to as ACF) or an adhesive such as an epoxy resin for bonding an IC chip to the film. The present invention relates to a manufacturing method and a metal wiring heat-resistant resin substrate obtained by this method. In particular, a method for producing a metal wiring heat-resistant resin substrate that can be used for high-performance electronic devices, particularly flexible wiring boards, built-up circuit boards, IC carrier tapes, and the like suitable for miniaturization and weight reduction. The present invention relates to a metal wiring heat-resistant resin substrate obtained by the method.

  Conventionally, metal foil laminated heat-resistant resin film, in which metal foil such as copper foil is laminated on heat-resistant resin film such as polyimide, makes use of the features of thin and lightweight, high-performance electronic equipment, especially small and lightweight It has been used for flexible wiring boards and IC carrier tapes, which are suitable for high-density wiring.

  In metal foil laminated heat-resistant resin film in which metal foil such as copper foil is laminated on resin film such as polyimide by laminating method, adhesion with adhesive that bonds ACF and IC chip to film as metal wiring becomes finer In order to improve the heat resistance, as a heat-resistant resin film, Patent Document 1 discloses that a thermoplastic polyimide having DA3EG in 0 to 50% of the diamine component and BPDA, ODPA or BTDA as the main acid component. Using a resin, a flexible metal foil laminate in which a heat-resistant bond ply having the thermoplastic polyimide layer on at least one side of a heat-resistant base film and a foil layer metal are heat-laminated, and the adhesion with ACF is 5 N / cm or more, After absorbing moisture at 40 ° C and 90RH% for 96 hours, heat was measured at 260 ° C for 10 seconds with a solder dip test. A copper-clad laminate using a thermoplastic polyimide resin characterized in that the plastic polyimide layer has no cloudiness and the thermoplastic polyimide layer does not peel off from the metal foil, and Patent Document 2 discloses a diamine component. A flexible metal obtained by thermally laminating a heat-resistant bond ply having a thermoplastic polyimide layer on at least one surface of a heat-resistant base film and a foil layer metal using a thermoplastic polyimide resin having a hydroxyl group or a carboxyl group in 5 to 50% as an adhesive. A foil laminate is disclosed.

  Furthermore, as an improvement of the adhesive that bonds the resin film and the copper foil, Patent Document 3 discloses a composite material having a conductor layer on one side or both sides of a composite of A: viscoelastic resin composition and B: polyimide film. It is a thin-leaf wiring board material having a total thickness of 100 μm or less, the storage elastic modulus of the viscoelastic resin composition is 300 to 1700 MPa at 20 ° C., and the viscoelastic resin composition is 2 to 10 parts of glycidyl in the polymer. A thin-leaf wiring board material containing an acrylic polymer having an acrylate, an epoxy value of 2 to 18, and a weight average molecular weight (Mw) of 50,000 or more is disclosed.

For the purpose of improving the surface roughness of the resin film, Patent Document 4 discloses that the value Ra1 measured with a cutoff value of 0.002 mm of arithmetic average roughness is 0.05 μm or more and 1 μm or less, and the cutoff value is 0. A resin film having at least one surface shape having a ratio Ra1 / Ra2 of 0.4 to 1 with respect to a value Ra2 measured at 1 mm is disclosed.
JP 2002-322276 A JP 11-354901 A JP-A-11-68271 JP 2004-276401 A

In a metal foil laminated heat resistant resin film in which a metal foil such as copper foil is laminated on a heat resistant resin film such as polyimide by a laminating method, etc., when the metal foil is etched to form fine wiring, the metal foil between the wirings Adhesion between the surface of the removed heat-resistant resin film and an adhesive that bonds the ACF or IC chip to the film is required.
In addition, when manufacturing metal foil laminated heat-resistant resin film with metalizing type, it is difficult to increase the thickness of the copper foil due to the cost of forming the copper layer, the adhesion between copper and heat-resistant resin film is small, and the adhesion is reliable. It is known to be inferior.

The present invention relates to a metal foil laminated heat resistant resin film obtained by laminating a heat resistant resin substrate such as polyimide and a metal foil such as copper foil by a laminating method, etc., to form fine wiring by etching the metal foil, between the wirings, etc. The object of the present invention is to provide a method for producing a metal foil laminated heat-resistant resin substrate in which the surface of the heat-resistant resin film from which the metal foil is removed is excellent in adhesiveness with an adhesive that bonds an ACF or IC chip to the film.
Furthermore, the present invention provides a method for producing a metal foil laminated heat-resistant resin substrate that is excellent in insulation reliability between metal wirings when at least a part of the metal wiring formed by etching the metal foil is plated with tin or the like. The purpose was to provide.

A first aspect of the present invention is a metal whose surface is treated with at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo or an alloy containing at least one of these metals on at least one surface of a heat resistant resin substrate. A metal wiring heat-resistant resin substrate having a metal wiring on a heat-resistant resin substrate using a metal foil heat-resistant resin substrate laminated with a surface-treated surface of a foil (hereinafter referred to as a surface-treated metal). In a method for producing a conductive resin substrate,
Forming a metal wiring on the heat resistant resin substrate from the metal foil laminated on the heat resistant resin substrate;
A cleaning step of improving the adhesion of the heat resistant resin substrate by cleaning the surface of the heat resistant resin substrate on the side having the metal wiring with an etching solution capable of removing at least one kind of the surface treated metal. The present invention relates to a method for manufacturing a metal wiring heat-resistant resin substrate.

  2nd of this invention is related with the metal wiring heat resistant resin substrate manufactured by the manufacturing method of the 1st metal wiring heat resistant resin substrate of this invention.

The first and / or second preferred embodiments of the present invention are shown below, and a plurality of these embodiments can be combined.
1) At least selected from Ni, Cr, Co, Zn, Sn and Mo resulting from the surface treatment of the metal foil present on the surface of the heat resistant resin substrate obtained by removing the metal of the metal laminated heat resistant resin substrate by etching Metals present on the surface of a heat resistant resin substrate obtained by removing one kind of metal and an alloy containing at least one of these metals by etching, more preferably by removing the metal of the metal laminated heat resistant resin substrate by etching Removing at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo resulting from the surface treatment of the foil and an alloy containing at least one of these metals with an acidic etchant;
2) The etching solution can remove at least one kind of the surface-treated metal at a faster rate than the material of the metal wiring, is an acidic etching solution, and the etching solution is an etching agent for Ni—Cr alloy (Ni -Cr seed layer removing agent).
3) The metal foil is surface-treated with at least one metal selected from Ni and Cr on at least one side or an alloy containing at least one of these metals,
The etching solution is an etching solution that can mainly remove at least one metal selected from Ni and Cr used for the surface treatment of the metal foil and an alloy containing at least one of these metals.
4) The metal wiring heat resistant resin substrate is formed by partially removing the metal foil laminated on at least one surface of the heat resistant resin substrate by etching to form a metal wiring on the surface of the heat resistant resin substrate.
5) The metal foil is a copper foil.
6) The metal foil is a metal foil having a roughened surface Ra of 0.27 μm or less.
7) The metal wiring heat resistant resin substrate is formed by partially etching a metal foil laminated on at least one surface of the heat resistant resin substrate to form a metal wiring having a pitch of 80 μm or less on the surface of the heat resistant resin substrate. .
8) The heat-resistant resin substrate is a polyimide film, and is a laminate in which a thermocompression-bonding polyimide layer is laminated on at least one surface of a highly heat-resistant polyimide layer.
9) The heat resistant resin substrate is obtained by laminating a thermocompression bonding polyimide layer on at least one surface of a high heat resistant polyimide layer,
The metal laminated heat-resistant resin substrate is obtained by laminating the surface treated surface of the metal foil on the thermocompression-bondable polyimide layer of the heat-resistant resin substrate, and further on the thermocompression-bondable polyimide layer of the heat-resistant resin substrate. The surface of the metal foil that has been surface-treated is laminated by heating and pressing.
10) The use of the metal wiring heat-resistant resin substrate that has been etched and cleaned is a flexible wiring circuit substrate, a built-up circuit substrate, or an IC carrier tape substrate.
11) In the laminated surface of the heat resistant resin substrate and the metal foil, at least one of the surface of the heat resistant resin substrate or the surface of the metal foil is treated with a silane coupling agent,
The cleaning process should be performed so that the silicon atom concentration on the surface after processing is higher than that before processing.
12) The step of forming the metal wiring is as follows:
It is a step of forming metal wiring on the surface of the heat resistant resin substrate by patterning the metal foil by etching.
13) The metal wiring heat-resistant resin substrate is used for an application in which a layer of an adhesive organic material is provided on at least a part of the exposed surface of the heat-resistant resin substrate on which the metal wiring is formed.
14) The layer of the adhesive organic material is a layer having at least one function of a conductive layer, an insulating layer, a protective layer, an adhesive layer, a sealing layer, and a sealing layer.
15) The method further includes a metal plating step after the cleaning step.

The method for producing a metal wiring heat resistant resin substrate according to the present invention is such that the surface of the heat resistant resin film obtained by etching away the metal foil between the metal wirings obtained by etching the metal foil is bonded to the ACF or IC chip as a film. A metal wiring heat-resistant resin substrate having excellent adhesiveness with an adhesive such as an epoxy resin to be combined can be obtained.
The metal wiring heat resistant resin substrate manufactured by the manufacturing method of the present invention has a metal foil between the wirings when metal plating such as tin plating is performed on at least a part of the metal wiring obtained by etching the metal foil. It can prevent or suppress the abnormal deposition due to the plated metal on the surface of the removed heat-resistant resin film, improve the insulation reliability between metal wiring, etc., and the appearance of the wiring board obtained after plating is good, especially at high density It can be used for wired flexible wiring boards, built-up circuit boards, and IC carrier tapes.
The metal wiring heat-resistant resin substrate manufactured by the manufacturing method of the present invention can form a fine wiring having a pitch of 40 μm or less or 50 μm or less by etching a metal foil, and a high-density flexible wiring substrate or built-up circuit A substrate and an IC carrier tape can be obtained.

  From the production method of the present invention, metal foil is etched to form metal wiring, metal plating such as tin plating is performed on at least a part of the metal wiring, and a flexible wiring board, built-up circuit board, A plated metal wiring heat-resistant resin substrate that can be used for an IC carrier tape can be obtained, in particular, a metal foil is etched to a pitch of 40 μm or less or 50 μm or less to form a fine wiring, and at least a part of the metal wiring A plated metal wiring heat-resistant resin substrate that can be used for a flexible wiring board, a built-up circuit board, and an IC carrier tape wired with high density can be obtained.

The metal foil is at least one surface selected from Ni, Cr, Co, Zn, Sn and Mo or an alloy containing at least one of these metals, roughening treatment, rust prevention treatment, heat resistance treatment, Those that have been subjected to surface treatment such as chemical treatment, and further subjected to silane coupling treatment can be used.
Although it does not specifically limit as metal foil, 100 micrometers or less, such as copper and copper alloys, such as electrolytic copper foil and rolled copper foil, aluminum and aluminum alloy, stainless steel and its alloy, nickel and nickel alloy (42 alloy is also included), etc. Preferably, a metal having a thickness of 0.1 to 100 μm, particularly 1 to 100 μm can be used.
The roughness of the surface of the metal foil that is bonded to the heat resistant resin substrate is not particularly limited, but the roughened surface Ra of the metal foil on the side to be bonded to the heat resistant resin substrate is preferably 2.0 μm or less, and more preferably Can be a smooth one of 1.5 μm or less, more preferably 1.0 μm or less, and particularly preferably 0.27 μm or less.
A metal surface-treated with at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo or an alloy containing at least one of these metals is referred to as a surface-treated metal.

When a thin metal foil is used (for example, one having a thickness of 0.1 to 8 μm), a laminate of protective foils (for example, carrier foils) that serve to reinforce and protect the metal foil can be used.
The protective foil (carrier foil) is not particularly limited in material, but can be bonded to a metal foil such as an ultrathin copper foil, and has a role of reinforcing and protecting the metal foil such as an ultrathin copper foil. For example, an aluminum foil, a copper foil, a resin foil whose surface is metal-coated, or the like can be used.
The thickness of the protective foil (carrier foil) is not particularly limited as long as it can reinforce a thin metal foil, and is generally 10 to 200 μm thick, further 12 to 100 μm thick, particularly 15 to 75 μm thick. It is preferable to use one.
The protective foil (carrier foil) may be used as long as it is planarly bonded to an ultrathin metal foil such as an ultrathin copper foil.

Use a protective foil (carrier foil) that flows through a continuous manufacturing process and maintains the state of being bonded to the metal foil layer and facilitating handling at least until the end of the production of the metal laminated heat-resistant resin substrate. Can do.
As a method of removing the protective foil (carrier foil) from the metal foil such as copper foil, the protective foil (carrier foil) is peeled off after the metal foil with the protective foil (carrier foil) is laminated on the heat-resistant resin substrate. What removes protective foil (carrier foil) by an etching method before or after lamination | stacking metal foil with protective foil (carrier foil) on a heat resistant resin board | substrate can be used.
In the electrolytic copper foil with carrier foil, since the copper component that becomes the electrolytic copper foil is electrodeposited on the surface of the carrier foil, the carrier foil needs to have at least conductivity.

  As an ultrathin copper foil with a carrier, Nippon Electrolytic Co., Ltd. (YSNAP-3B: carrier thickness 18 μm / thin copper foil 3 μm), ultra thin copper foil (XTF: copper foil thickness 5 μm / carrier thickness 35 μm), copper Foil thickness 3 μm / carrier thickness 35 μm, etc.), Furukawa Electric Co., Ltd. ultra-thin copper foil (F-CP: thickness 5 μm / 35 μm, thickness 3 μm / 35 μm, both ultra-thin copper foil / carrier copper foil) Can be mentioned.

The metal foil can be treated with a silane coupling agent in order to chemically improve the adhesion to the heat-resistant resin substrate or the adhesive layer after the roughening treatment, the rust prevention treatment, and the like are finished.
The silane coupling agent is not particularly limited, and an epoxy silane coupling agent, an amino silane coupling agent, a mercapto silane coupling is considered in consideration of the heat-resistant resin substrate and the adhesive layer to be used. It can be arbitrarily selected and used from agents. For example, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, Vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ- Aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane, etc. It is possible. These silane coupling agents are usually made into 0.001 to 5% aqueous solution, applied to the surface of a metal foil such as copper foil, and then dried by heating as it is. In addition, it can replace with a silane coupling agent, and the same effect can be acquired even if it uses coupling agents, such as a titanate type | system | group and a zirconate type | system | group.

The physical properties of the heat-resistant resin substrate are not particularly limited, but can be laminated with metal foil without problems, easy to manufacture and handle, and can etch metal foil such as copper foil, and has excellent heat resistance and electrical insulation. As long as it is necessary, the metal foil can be sufficiently supported if necessary, and it is not greatly affected by the developer or stripper that removes the photoresist layer used when forming the metal wiring if necessary. It ’s fine.
In particular, the physical properties of the heat-resistant resin substrate are that the thermal shrinkage rate is 0.05% or less and the linear expansion coefficient (50 to 200 ° C.) is close to the linear expansion coefficient of a metal foil such as a copper foil laminated on the heat-resistant resin substrate. When a copper foil is used as the metal foil, the coefficient of linear expansion (50 to 200 ° C.) of the heat resistant resin substrate is 0.5 × 10 ^{−5 to} 2.8 × 10 ⁻⁵ cm / cm / ° C. preferable.

As the heat-resistant resin substrate, polyimide, polyamide, aramid, liquid crystal polymer, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyetherketone, polyetheretherketone, polybenzazole, BT (bismaleimide-triazine) resin, An epoxy resin, a thermosetting polyimide, etc. are mentioned, The board | substrate which made these resin into a film form, a sheet form, and plate shape can be used.
In particular, as a heat-resistant resin substrate, polyimide can be preferably used because it is excellent in heat resistance and flame retardancy, has high rigidity, and is excellent in electrical insulation.
As the heat-resistant resin substrate, “UPILEX (S, R)” (product name) manufactured by Ube Industries, Ltd. “Kapton (H, EN, K)” (product name) manufactured by Toray DuPont, manufactured by Kaneka Chemical Industry Co., Ltd. Biphenyltetracarboxylic such as “Apical (AH, NPI, HP)” (trade name), “Espanex (S, M)” (trade name) manufactured by Nippon Steel Chemical Co., Ltd., “Miktron” (trade name) manufactured by Toray Industries, Inc. Commercially available polyimide film mainly composed of an acid component selected from an acid skeleton and a pyromellitic acid skeleton, and a diamine component selected from a phenylenediamine skeleton, a diaminodiphenyl ether skeleton and a biphenyl skeleton. Examples include, but are not limited to, commercially available liquid crystal polymers such as “Espanex (L)” (trade name) manufactured by Nippon Steel Chemical Co., Ltd.

The heat-resistant resin substrate is formed with fillers such as inorganic fillers and organic fillers, fiber materials such as glass fibers, aramid fibers and polyimide fibers, and the fibers are short fibers, woven, knitted and assembled fibers. Or it can use as a shape of a nonwoven fabric.
As a heat resistant resin substrate, it can be used as the shape of a single layer, a multilayer film in which two or more layers are laminated, a sheet, and a plate.

  The thickness of the heat-resistant resin substrate is not particularly limited, but may be any thickness as long as it can be laminated with a metal foil without problems, can be manufactured and handled, and can sufficiently support the metal foil, preferably 1 to 500 μm, more preferably Is preferably 2 to 300 μm, more preferably 5 to 200 μm, more preferably 7 to 175 μm, and particularly preferably 8 to 100 μm.

As the heat resistant resin substrate, a substrate on which at least one surface of the substrate is subjected to surface treatment such as corona discharge treatment, plasma treatment, chemical roughening treatment, physical roughening treatment, or the like can be used.
As the heat-resistant resin substrate, when handling is difficult due to low rigidity of the substrate, a rigid film or substrate that can be peeled off in a later process can be attached to the back surface of the substrate.
It is extremely preferable that the surface of the heat resistant resin substrate is treated with a surface treatment agent such as a silane coupling agent.

The surface treatment agent is not particularly limited, and in consideration of the heat-resistant resin substrate, the adhesive layer, the metal foil, etc. used, a silane coupling agent such as an aminosilane type or an epoxy silane type, or a titanate type. A surface treating agent can be used.
As the aminosilane-based surface treatment agent, γ-aminopropyl-triethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-triethoxysilane, N- (aminocarbonyl) -γ-aminopropyl-triethoxysilane, Compounds such as N- [β- (phenylamino) -ethyl] -γ-aminopropyl-triethoxysilane, N-phenyl-γ-aminopropyl-triethoxysilane, γ-phenylaminopropyltrimethoxysilane, epoxy silane The surface treatment agent is a compound such as β- (3,4-epoxycyclohexyl) -ethyl-trimethoxylane, γ-glycidyloxypropyl-trimethoxysilane, and the titanate surface treatment agent is isopropyl-tricumylphenyl-titanate. , Dicumylphenyl-oxyacetate-tita Compounds such as chromatography bets and the like.
As the surface treatment agent, a silane coupling agent such as aminosilane or epoxysilane can be preferably used.
The surface treatment agent may be present as it is, or may be present in a state where it has been subjected to a change such as a heat change or a chemical change due to heating.

As the heat resistant resin substrate, a polyimide film excellent in heat resistance, electrical insulation and the like can be suitably used.
The polyimide film preferably has a thermal shrinkage ratio of 0.05% or less and a linear expansion coefficient (50 to 200 ° C.) close to the linear expansion coefficient of a metal foil such as a copper foil laminated on a heat resistant resin substrate. When the copper foil is used, the linear expansion coefficient (50 to 200 ° C.) of the heat resistant resin substrate can be 0.5 × 10 ^{−5 to} 2.8 × 10 ⁻⁵ cm / cm / ° C.
As the polyimide film, a single polyimide film, a laminated polyimide film of two or more layers in which two or more layers of polyimide are laminated, and the kind of polyimide are not particularly limited.

The polyimide film can be produced by a known method. For example, in a single-layer polyimide film,
(1) A method in which a polyamic acid solution, which is a polyimide precursor, is cast or applied to a support and imidized;
(2) The polyimide solution can be cast on a support, applied, and heated as necessary, etc.
In polyimide film of two or more layers,
(3) A polyamic acid solution in which a polyamic acid solution, which is a polyimide precursor, is cast or applied to a support, and a polyamic acid solution, which is a polyimide precursor in the second layer or more, is cast or applied to the support in advance. Casting or coating on the upper surface of the acid layer, imidizing,
(4) A method in which a polyamic acid solution, which is a precursor of two or more layers of polyimide, is simultaneously cast or applied to a support and imidized;
(5) The polyimide solution is cast or coated on the support, and further, the polyimide solution of the second layer or more is cast or coated on the upper surface of the polyimide layer cast or coated on the support before sequentially. How to heat,
(6) A method in which two or more layers of polyimide solution are simultaneously cast or coated on a support and heated as necessary.
(5) It can be obtained by a method of laminating two or more polyimide films obtained in (1) to (6) directly or via an adhesive.

As the heat resistant resin substrate, a polyimide film having two or more layers having a thermocompression bonding polyimide layer (S2) on at least one surface of the heat resistant polyimide layer (S1) can be used.
Examples of the layer structure of the multilayer polyimide film include S2 / S1, S2 / S1 / S2, S2 / S1 / S2 / S1, S2 / S1 / S2 / S1 / S2,
In the polyimide film having thermocompression bonding, the thickness of the heat-resistant polyimide layer (S1) and the thermocompression bonding polyimide layer (S2) can be appropriately selected and used.
The thickness of the outermost thermocompression bonding polyimide layer (S2) of the polyimide film having thermocompression bonding is in the range of 0.5 to 10 μm, preferably 1 to 7 μm, more preferably 2 to 5 μm. Curling can be suppressed by providing thermocompression-bondable polyimide layers (S2) having substantially the same thickness on both sides of (S1).

In the polyimide film having thermocompression bonding, as the heat-resistant polyimide of the heat-resistant polyimide layer (S1 layer), those having at least one of the following features, those having at least two of the following features [1] and 2), Combinations of 1), 3), 2) and 3)], particularly those having all the following characteristics can be used.
1) In the case of a single polyimide film, the glass transition temperature is 300 ° C. or higher, preferably the glass transition temperature is 330 ° C. or higher, and more preferably cannot be confirmed.
2) In the case of a single polyimide film, the linear expansion coefficient (50 to 200 ° C.) (MD) is preferably close to the thermal expansion coefficient of a metal foil such as a copper foil laminated on a heat resistant resin substrate. When copper foil is used, the thermal expansion coefficient of the heat resistant resin substrate is preferably 5 × 10 ^{−6 to} 28 × 10 ⁻⁶ cm / cm / ° C., and 9 × 10 ^{−6 to} 20 × 10 ⁻⁶ cm / cm. it is preferably / ° C., is preferably further ^{12 × 10 -6 ~18 × 10 -6} cm / cm / ℃.
3) In the case of a single polyimide film, the tensile elastic modulus (MD, ASTM-D882) is 300 kg / mm ² or more, preferably 500 kg / mm ² or more, and further 700 kg / mm ² or more.
4) Preferably the thermal shrinkage is 0.05% or less.

The heat-resistant polyimide layer (S1) of the polyimide film having thermocompression bonding is composed of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) as a main acid component, paraphenylenediamine (PPD) and 4,4′-diaminodiphenyl ether (DADE) ) And a polyimide synthesized from the main diamine component.
Preferably (1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and paraphenylenediamine (PPD) and optionally further 4,4′-diaminodiphenyl ether ( In this case, the PPD / DADE (molar ratio) is preferably 100/0 to 85/15,
(2) manufactured from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, paraphenylenediamine and 4,4′-diaminodiphenyl ether, in this case BPDA / PMDA is preferably 15/85 to 85/15, and PPD / DADE is preferably 90/10 to 10/90,
(3) produced from pyromellitic dianhydride, paraphenylenediamine and 4,4′-diaminodiphenyl ether, in which case DADE / PPD is preferably 90/10 to 10/90,
(4) Manufactured from 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride, paraphenylenediamine and 4,4′-diaminodiphenyl ether . In this case, it is preferable that BTDA / PMDA in the acid dianhydride is 20/80 to 90/10, and PPD / DADE in the diamine is 30/70 to 90/10.

The synthesis of the heat-resistant polyimide of the heat-resistant polyimide layer (S1 layer) is as follows. If the ratio of each component is finally within the above range, random polymerization, block polymerization, or two types of polyamic acids are synthesized in advance and both polyamics are synthesized. This can be achieved by any method in which the acid solution is mixed and then mixed under reaction conditions to obtain a homogeneous solution.
In the synthesis of the heat-resistant polyimide of the heat-resistant polyimide layer (S1 layer), each of the above components is used, and an approximately equimolar amount of a diamine component and tetracarboxylic dianhydride is reacted in an organic solvent to form a polyamic acid. A solution (a part may be imidized as long as a uniform solution state is maintained).
Other types and amounts of other tetracarboxylic dianhydrides and diamines that do not impair the physical properties of the heat-resistant polyimide of the heat-resistant polyimide layer (S1 layer) may be used.

The thermocompression bonding polyimide of the thermocompression bonding polyimide layer (S2) of the polyimide film having thermocompression bonding,
1) Polyimide having thermocompression bonding with metal foil, preferably polyimide having thermocompression bonding by laminating with metal foil at a temperature of not less than the glass transition temperature of thermocompression bonding polyimide (S2) to 400 ° C. or less.
It is preferable that the thermocompression bonding polyimide of the thermocompression bonding polyimide layer (S2) of the polyimide film having thermocompression bonding further has at least one of the following characteristics.
2) The thermocompression bonding polyimide (S2) has a peel strength of 0.7 N / mm or more between the metal foil and the polyimide (S2), and a peel strength retention of 90% or more even after heat treatment at 150 ° C. for 168 hours, Further, the polyimide should be 95% or more, particularly 100% or more.
2) The glass transition temperature is 130 to 330 ° C.
3) The tensile elastic modulus is 100 to 700 kg / mm 2.
4) The linear expansion coefficient (50 to 200 ° C.) (MD) is 13 to 30 × 10 ⁻⁶ cm / cm / ° C.

The thermocompression bonding polyimide of the thermocompression bonding polyimide layer (S2) of the polyimide film having thermocompression bonding can be selected from various known thermoplastic polyimides, for example,
2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), pyromellitic acid dianhydride Anhydride (PMDA), 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 4,4 ′ -Acid component selected from oxydiphthalic dianhydride (ODPA), p-phenylenebis (trimellitic acid monoester anhydride), 3,3 ', 4,4'-ethylene glycol dibenzoate tetracarboxylic dianhydride An acid component, preferably as a main component,
1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl A diamine component having three benzene rings in at least the main chain selected from sulfone and the like, preferably including as a main component, and further including a diamine component having one or two benzene rings in the main chain as necessary. Polyimide synthesized from a diamine component can be used.

The thermocompression bonding polyimide of the thermocompression bonding polyimide layer (S2) of the polyimide film having thermocompression bonding is preferably,
1) 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), pyromerit An acid component selected from acid dianhydride (PMDA) and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA);
2) 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene and 2,2-bis [4- ( Polyimide synthesized from a diamine component selected from 4-aminophenoxy) phenyl] propane can be used, and if necessary, a diamine component having one or two benzene rings in the main chain, a diamine other than the above, an acid Can contain ingredients,
In particular, it contains 80 mol% or more of 1,3-bis (4-aminophenoxybenzene) as a diamine component (hereinafter sometimes abbreviated as TPER) and 3,3 ′, 4,4′-biphenyltetracarboxylic acid dicarboxylic acid. It is produced from an anhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as a-BPDA). In this case, s-BPDA / a-BPDA is preferably 100/0 to 5/95, and other tetracarboxylic dianhydrides such as 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride or 2,3,6,7-naphthalenetetracarboxylic dianhydride may be substituted.

The thermocompression bonding polyimide of the thermocompression bonding polyimide layer (S2) of the polyimide film having thermocompression bonding, each of the above components, and optionally other tetracarboxylic dianhydrides and other diamines in an organic solvent, Reaction is performed at a temperature of about 100 ° C. or less, particularly 20 to 60 ° C. to form a polyamic acid solution. The polyamic acid solution is used as a dope solution to form a thin film of the dope solution, and the solvent is evaporated from the thin film. It can be produced by removing and cyclizing the polyamic acid with 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.

  In order to obtain the thermocompression bonding polyimide of the thermocompression bonding polyimide layer (S2) of the polyimide film having thermocompression bonding, the amount of diamine (as the number of moles of amino group) used in the organic solvent is an acid anhydride. As a ratio to the total number of moles (as the total moles of tetraacid dianhydride and dicarboxylic anhydride as acid anhydride groups), 0.95 to 1.0, especially 0.98 to 1.0, of which It is preferable that it is 0.99-1.0. When the dicarboxylic acid anhydride is used, each component can be reacted at a ratio of 0.05 or less as a ratio of the tetracarboxylic dianhydride to the molar amount of the acid anhydride group.

In the thermocompression bonding polyimide of the thermocompression bonding polyimide layer (S2) of the polyimide film having thermocompression bonding, when the molecular weight of the resulting polyamic acid is small, the adhesive strength of the laminate with the metal foil may be lowered.
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, imidazole, 2-imidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline, substituted pyridine and the like are 0.05 to 10% by weight, particularly 0.1 to 2% by weight, based on the polyamic acid. Can be used in proportions. Since these form a polyimide film at a relatively low temperature, they can be used to avoid insufficient imidization.
For the purpose of stabilizing the adhesive strength, an organoaluminum compound, an inorganic aluminum compound, or an organotin compound may be added to the polyamic acid solution for thermocompression bonding polyimide. For example, aluminum hydroxide, aluminum triacetylacetonate or the like can be added in an amount of 1 ppm or more, particularly 1 to 1000 ppm as an aluminum metal with respect to the polyamic acid.

  The organic solvent used for the production of polyamic acid from the acid component and the diamine component is N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N- for any of heat-resistant polyimide and thermocompression bonding polyimide. Examples thereof include 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.

  Heat-resistant polyimide and thermocompression-bonding polyimide are dicarboxylic anhydrides, such as phthalic anhydride and its substitutes, hexahydrophthalic anhydride and its substitutes, succinic anhydride and its substitutes, etc. In particular, phthalic anhydride can be used.

The polyimide film having thermocompression bonding property is preferably formed by a coextrusion-casting film forming method (also simply referred to as a multilayer extrusion method) and a heat-resistant polyimide (S1) dope solution and a thermocompression bonding polyimide (S2) solution. A method of obtaining a multilayer polyimide film by laminating a dope solution, drying, imidization,
Alternatively, a dope solution of heat-resistant polyimide (S1) is cast-coated on a support, and a dope solution of thermocompression bonding polyimide (S2) is applied to one or both sides of a dried self-supporting film (gel film) and dried. It can be obtained by a method of imidizing to obtain a multilayer polyimide film.
As the coextrusion method, a method described in JP-A-3-180343 (Japanese Patent Publication No. 7-102661) can be used.

An example of the production of a three-layer polyimide film having thermocompression bonding on both sides is shown.
A polyamic acid solution of polyimide (S1) and a polyamic acid solution of polyimide (S2) are subjected to a three-layer coextrusion method to form a heat-resistant polyimide layer (S1 layer) having a thickness of 4 to 45 μm and thermocompression-bonding polyimide layers on both sides (S2 Layer) is supplied to a three-layer extrusion die so that the total thickness becomes 3 to 10 μm, cast on a support, and cast on a support surface such as a stainless steel mirror surface or a belt surface. A polyimide film A that is a self-supporting film that is semi-cured or dried before ˜200 ° C. can be obtained.
When the cast film is processed at a high temperature exceeding 200 ° C., the self-supporting polyimide film A tends to cause defects such as a decrease in adhesiveness in the production of a polyimide film having thermocompression bonding. This semi-cured state or an earlier state means that it is in a self-supporting state by heating and / or chemical imidization.

  The polyimide film A of the obtained self-supporting film was measured at a temperature not higher than the temperature at which deterioration occurs at a temperature higher than the glass transition temperature (Tg) of the polyimide (S2), preferably 250 to 420 ° C. (measured with a surface thermometer). Heat to surface temperature (preferably heated for 0.1 to 60 minutes at this temperature), dried and imidized, and thermocompression-bondable polyimide layer (S2 layer on both sides of heat-resistant polyimide layer (S1 layer)) ) Can be produced.

The polyimide film A of the obtained self-supporting film preferably has about 25 to 60% by mass, particularly preferably 30 to 50% by mass of the solvent and generated water, and the self-supporting film is heated to the drying temperature. When heating, it is preferable to raise the temperature within a relatively short time, for example, a temperature increase rate of 10 ° C./min or more is suitable. By increasing the tension applied to the self-supporting film at the time of drying, the linear expansion coefficient of the finally obtained polyimide film A can be reduced.
Then, following the above-described drying step, at least a pair of both end edges of the self-supporting film is continuously or intermittently fixed with a fixing device or the like that can be moved together with the self-supporting film. Higher than the above drying temperature, and preferably at a high temperature in the range of 200 to 550 ° C., particularly preferably in the range of 300 to 500 ° C., preferably 1 to 100 minutes, in particular 1 to 10 minutes. The support film is dried and heat-treated, and the solvent is preferably removed from the self-support film so that the content of volatile substances composed of an organic solvent and product water in the finally obtained polyimide film is 1% by weight or less. The polyimide film which has the thermocompression bonding on both sides by sufficiently imidizing the polymer constituting the film It can be formed.

  Examples of the fixing device for the self-supporting film include, for example, a belt-like or chain-like one provided with a large number of pins or gripping tools at equal intervals, and the length of the solidified film supplied continuously or intermittently. A device that can be installed in a pair along both side edges in the direction and can fix the film while moving the film continuously or intermittently with the movement of the film is suitable. The solidified film fixing device can stretch or shrink the film being heat-treated in the width direction or the longitudinal direction at an appropriate elongation or contraction rate (particularly preferably about 0.5 to 5%). It may be a device.

  The polyimide film having thermocompression bonding on both sides produced in the above step is preferably at a temperature of 100 to 400 ° C. under a low tension or no tension of preferably 4N or less, particularly preferably 3N or less. Can be made into a polyimide film having thermocompression bonding on both surfaces particularly excellent in dimensional stability when heat-treated for 0.1 to 30 minutes. Moreover, the manufactured polyimide film which has thermocompression bonding on both sides can be wound up in a roll shape by an appropriate known method.

The metal-laminated heat-resistant resin substrate is obtained by laminating a surface treated with a metal foil on one surface or both surfaces of a heat-resistant resin substrate, and is not limited by the manufacturing method.
Metal laminated heat-resistant resin substrate
1) One or both surfaces of a heat-resistant resin substrate laminated with a surface-treated surface of a metal foil directly or via an adhesive,
2) One or both sides of a heat-resistant resin substrate laminated with a surface treated surface of a metal foil directly or via an adhesive,
3) One or both surfaces of a heat-resistant resin substrate laminated by pressing the surface treated with metal foil directly or via an adhesive,
4) One or both surfaces of the heat-resistant resin substrate, which are obtained by laminating the surface-treated surface of the metal foil directly or by heating and pressing through an adhesive, can be used.
In particular, the heat-resistant resin substrate is preferably laminated via an adhesive if the surface of the substrate and the metal foil are pressed, heated or heated under pressure, but the pressure-bonding property is low.
The adhesive can be applied by a commonly used method such as a roll coater, a slit coater, or a comma coater.
When laminating a metal foil with an adhesive layer and a heat resistant resin substrate, or a metal foil and a heat resistant resin substrate with an adhesive layer, a heating device, a pressure device or a pressure device can be used, and heating conditions The pressure condition is preferably selected as appropriate depending on the material used, and is not particularly limited as long as it can be laminated continuously or batchwise, but it is preferably carried out continuously using a roll laminate or a double belt press.

As the metal laminated heat-resistant resin substrate, a laminate obtained by laminating at least one surface of the heat-resistant polyimide (S1) with a surface treated with a metal foil via an adhesive can be used.
In the metal laminated heat-resistant resin substrate, the adhesive for laminating the heat-resistant polyimide (S1) and the metal layer via an adhesive may be thermosetting or thermoplastic, for example, epoxy resin, NBR-phenolic resin. , Phenol-butyral resin, epoxy-NBR resin, epoxy-phenolic resin, epoxy-nylon resin, epoxy-polyester resin, epoxy-acrylic resin, acrylic resin, polyamide-epoxy-phenolic resin And thermosetting adhesives such as polyimide resins and polyimide siloxane-epoxy resins, or thermoplastic adhesives such as polyamide resins, polyester resins, polyimide adhesives, and polyimide siloxane adhesives. In particular, a polyimide adhesive, a polyimide siloxane-epoxy adhesive, and an epoxy resin adhesive can be suitably used.

The metal laminated heat-resistant resin substrate can be obtained by using the polyimide film having thermocompression bonding on both surfaces and laminating the surface-treated surface of the metal foil on both surfaces of the thermocompression bonding polyimide film. ,
As an example of a method for producing a metal laminated heat-resistant resin substrate,
1) Three sheets of a long metal foil, a polyimide film having a long thermocompression bonding property, and a long metal foil are stacked in this order.
Preferably, preheating using a preheater such as a hot air supply device or an infrared heater so that it can be preheated at about 150 to 250 ° C., particularly at a temperature higher than 150 ° C. and lower than 250 ° C. for about 2 to 120 seconds, just before introduction. And
Using a pair of crimping rolls or a double belt press, the temperature of the thermocompression bonding zone of the pair of crimping rolls or double belt press is in a temperature range from a temperature 20 ° C. higher than the glass transition temperature of polyimide (S2) to 400 ° C., particularly Thermocompression bonding under pressure in a temperature range of 30 ° C or higher than the glass transition temperature to 400 ° C, especially in the case of a double belt press, it is subsequently cooled under pressure with a cooling zone, preferably polyimide. A roll-like single-sided or double-sided metal foil laminated polyimide film is produced by cooling to a temperature lower than the glass transition temperature of (S2) by 20 ° C. or more, particularly 30 ° C. or lower, and laminating and winding up into a roll shape. be able to.

The metal laminated heat-resistant resin substrate can be obtained by using a polyimide film having thermocompression bonding on both sides and laminating a surface treated with a metal foil on one surface of the polyimide film having thermocompression bonding. ,
As an example of a method for producing a single-sided metal foil laminated polyimide substrate,
1) A long metal foil, a long polyimide film having thermocompression bonding, a thermocompression bonding polyimide and a long film having no thermocompression bonding (Upex Corporation, Upilex S) , Toray DuPont Kapton H etc.)
Preferably, preheating using a preheater such as a hot air supply device or an infrared heater so that it can be preheated at about 150 to 250 ° C., particularly at a temperature higher than 150 ° C. and lower than 250 ° C. for about 2 to 120 seconds, just before introduction. And
Using a pair of crimping rolls or a double belt press, the temperature of the thermocompression bonding zone of the pair of crimping rolls or double belt press is in a temperature range from a temperature 20 ° C. higher than the glass transition temperature of polyimide (S2) to 400 ° C., particularly Thermocompression bonding under pressure in a temperature range of 30 ° C or higher than the glass transition temperature to 400 ° C, especially in the case of a double belt press, it is subsequently cooled under pressure with a cooling zone, preferably polyimide. It is possible to produce a roll-shaped single-sided metal foil-laminated polyimide film by cooling to a temperature lower than the glass transition temperature of (S2) by 20 ° C. or more, particularly 30 ° C. or lower, and laminating and winding it into a roll. it can.

  In the manufacturing method of the present invention, by preheating before thermocompression bonding, it is possible to prevent occurrence of poor appearance due to foaming of the laminate after thermocompression bonding due to moisture contained in the polyimide, or solder at the time of electronic circuit formation By preventing foaming during bath immersion, deterioration of product yield can be prevented. In addition, although a method of installing the entire thermocompression bonding apparatus in the furnace is also conceivable, the thermocompression bonding apparatus is substantially limited to a compact one, and is not practical due to limitations on the shape of the double-sided metal foil laminated polyimide film, or Even if the pre-heat treatment is performed in the outline, it absorbs moisture again before lamination, and it is difficult to avoid the appearance defect and the decrease in solder heat resistance due to the foaming.

The double belt press can perform high temperature heating and cooling under pressure, and is preferably a hydraulic type using a heat medium.
The double-sided metal foil laminated polyimide film is preferably formed by laminating a polyimide film having thermocompression bonding on both sides and a metal foil by thermocompression-cooling under pressure using a double belt press, and laminating. The obtained double-sided metal foil laminated polyimide film has a long and wide width of about 400 mm or more, particularly about 500 mm or more, and has a high adhesive strength (the peel strength between the metal foil and the polyimide layer is high). A double-sided metal foil having a good appearance so that no wrinkles are substantially observed on the surface of the metal foil, even after heat treatment at 150 ° C. for 168 hours at 0.7 N / mm or more) A laminated polyimide film can be obtained.

  In the present invention, in order to mass-produce a double-sided metal foil laminated polyimide film having a good product appearance, at least one combination of a thermocompression bonding polyimide film and a metal foil is supplied and between the both sides of the outermost layer and the belt. A protective material (that is, two protective materials) is interposed, and thermocompression-bonded and cooled under pressure to be laminated. As the protective material, any material can be used as long as it is non-thermocompressible and has good surface smoothness. For example, metal foil, particularly copper foil, stainless steel foil, aluminum foil, high heat resistant polyimide film (Ube) Suitable examples include those having a thickness of about 5 to 125 μm such as Kupton H) manufactured by Kosan Co., Ltd., Upilex S, and Toray DuPont.

The metal wiring heat resistant resin substrate is formed on the surface of the heat resistant resin substrate by partially removing the metal foil laminated on at least one surface of the heat resistant resin substrate using an etching solution or using a laser or the like. A metal wiring is provided.
As the metal wiring heat-resistant resin substrate, it is possible to use a metal wiring having a metal wiring having a pitch of 80 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less.

The metal wiring heat resistant resin substrate can be manufactured from the metal laminated heat resistant resin substrate.
1) Provided by applying a photoresist layer on the metal surface of the metal laminated heat-resistant resin substrate or bonding the film together,
2) Expose through a photomask of wiring pattern,
3) The unexposed portion of the photoresist is developed and removed with a dedicated developer, washed with water as necessary, and dried to form an exposed photoresist layer of the wiring pattern on the metal foil.
4) The exposed metal foil is removed using an etching solution or a laser, washed with water if necessary, and dried. 6) The exposed photoresist layer on the metal foil is removed by peeling or the like, and if necessary. Wash with water and dry,
The method can be used.

Using copper foil laminated polyimide film, showing an example of producing a copper wiring polyimide film by subtractive method,
1) If necessary, perform copper plating on the copper foil,
3) A photoresist layer is provided on the upper surface of the copper foil,
4) Expose the wiring pattern using a photomask, etc.
5) Remove portions other than the wiring pattern portion of the photoresist layer by development,
6) Remove the copper foil other than the part that becomes the wiring pattern by etching,
7) Remove the photoresist layer on the copper foil by peeling,
8) An etching solution capable of mainly removing at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo and an alloy containing at least one of these metals used for the surface treatment of the copper foil. Wash with.
In each of the above steps 1) to 8), it is washed and dried as necessary.

Using copper foil laminated polyimide film, showing an example of producing a copper wiring polyimide film by a semi-additive method,
1) If necessary, thin the copper foil by etching, etc.
2) A photoresist layer is provided on the upper surface of the copper foil,
4) Expose the wiring pattern using a photomask, etc.
5) Development and removal of the portion of the photoresist layer that becomes the wiring pattern,
6) Copper plating the exposed copper foil part,
7) Remove the photoresist layer on the copper foil by peeling,
8) The copper foil from which the photoresist layer has been removed is removed by flash etching or the like to expose the polyimide,
9) Etching solution capable of mainly removing at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo and an alloy containing at least one of these metals used for the surface treatment of the copper foil Wash with.
In each of the above steps 1) to 9), washing and drying are performed as necessary.

When another production example of a metal wiring heat resistant resin substrate is shown,
1) A method of forming a wiring by partially removing a metal foil of a metal laminated heat-resistant resin substrate using a laser can be used.

When another production example of a metal wiring heat resistant resin substrate is shown, for example,
1) Surface treatment of a thermocompression bonding polyimide layer and a copper foil using a copper foil as a metal foil and using a thermocompression bonding polyimide layer laminated on at least one surface of a high heat resistance polyimide layer as a heat resistant resin substrate. A copper foil laminated polyimide is manufactured using a press roll capable of pressurizing and heating, such as a laminating roll that can heat and press the applied surface, or a double belt press,
2) A photoresist layer is applied to the copper foil surface of the copper foil laminated polyimide by coating or film lamination,
3) Expose through a photomask of wiring pattern,
4) The unexposed portion of the photoresist is developed and removed with a dedicated developer, washed with water as necessary, dried, and a photoresist layer exposed to a wiring pattern is formed on the copper foil.
5) Remove the exposed copper using an iron chloride, copper chloride, or hydrogen peroxide-based copper etchant or laser, etc., wash with water if necessary, and dry.
6) A copper wiring polyimide can be produced by a method in which the exposed photoresist layer on the copper wiring is peeled and removed with a dedicated stripping solution, washed with water if necessary, and dried.

When manufacturing a metal wiring heat resistant resin substrate from a metal laminated heat resistant resin substrate, the photoresist layer used for forming the metal wiring can be a positive type or a negative type, and is selected and used as appropriate according to the manufacturing method. be able to.
When a metal wiring heat resistant resin substrate is manufactured from a metal laminated heat resistant resin substrate, the metal wiring can be formed by a subtractive method or a semi-additive method.

  As an etching solution for the metal foil of the metal laminated heat-resistant resin substrate, a known etching solution can be used. For example, an aqueous solution of potassium ferricyanide, an aqueous solution of iron chloride, an aqueous solution of copper chloride, an aqueous solution of ammonium persulfate, an aqueous solution of sodium persulfate, Hydrogen oxide water, hydrofluoric acid aqueous solution, a combination thereof, or the like can be used.

The etched metal wiring heat-resistant resin substrate is obtained by removing the metal of the metal wiring heat-resistant resin substrate from the surface of the substrate, and the Ni, Cr, Co, Zn, Sn and Mo used for the surface treatment of the metal foil. An etching solution that can remove at least one metal selected from the group consisting of at least one metal and an alloy containing at least one of these metals at a faster rate than the main metal component of the metal foil, such as an etchant for Ni—Cr alloy (Ni— It is obtained by washing with a Cr seed layer removing agent), washing with water if necessary, and drying.
The metal wiring heat-resistant resin substrate that has been etched and cleaned is cleaned with an etching solution, whereby the surface of the substrate obtained by removing the metal foil has improved ACF adhesion such as epoxy resin, and at least a part of the metal wiring. When plating such as tin plating is performed on the substrate, abnormal plating of the plating metal does not occur on the surface of the substrate obtained by removing the metal foil and the portion where the substrate surface obtained by removing the metal foil contacts the metal wiring. Or electrical insulation can be improved.
In particular, when copper foil is used as the metal foil, when plating such as tin plating is performed on the copper wiring, the substrate surface obtained by removing the copper foil, and the substrate surface obtained by removing the copper foil and the copper wiring In the portion that contacts, abnormal deposition of plating metal such as tin plating does not occur or can be suppressed, and electrical insulation is improved.

As an etching solution that can mainly remove at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo used in the surface treatment of metal foil and an alloy containing at least one of these metals. Etching capable of mainly removing at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo and an alloy containing at least one of these metals used for surface treatment of known metal foils As long as it is a solution, a known Ni etching solution, Cr etching solution, Co etching solution, Zn etching solution, Sn etching solution, Mo etching solution, Ni-Cr alloy etching solution, or an acidic etching solution can be used. However, it is not limited to these.
As an etching solution that can mainly remove at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo used in the surface treatment of metal foil and an alloy containing at least one of these metals. The removal rate of at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo and an alloy containing at least one of these metals, rather than the main metal component of the metal wiring of the metal wiring heat-resistant resin substrate It is preferable to use a fast etching solution.
As the etchant, an etchant for Ni—Cr alloy (Ni—Cr seed layer remover) can be used, for example, Melstrip NC-3901 from Meltex, Adekari remover NR-135 from Asahi Denka Kogyo, etc. A known etching solution such as FLICKER-MH manufactured by Nippon Chemical Industry Co., Ltd. can be used.

  At least one metal selected from Ni, Cr, Co, Zn, Sn and Mo used for surface treatment of metal foil of a metal wiring heat-resistant resin substrate and an alloy containing at least one of these metals are mainly removed. The cleaning conditions with the etching solution that can be selected can be appropriately selected depending on the etching solution to be used, but are preferably 30 to 60 ° C., more preferably 40 to 60 ° C., preferably 0.3 to 20 minutes, The immersion (dip) or spray treatment is preferably performed for 0.5 to 10 minutes, particularly preferably for 1 to 7 minutes.

In order to perform the elemental analysis of the surface of the heat resistant resin substrate that appears by removing the metal of the metal wiring heat resistant resin substrate, and to have the effect of the present invention, Ni, Cr, Co, At least one metal selected from Zn, Sn and Mo and an alloy containing at least one of these metals can be used to remove mainly the metal removal rate before and after cleaning (after cleaning / before cleaning). X100) is preferably at least one range selected from the following 1) to 4), and the removal rate of Cr is particularly preferably in the following range.
1) The Cr removal rate is 15% to 100%, 20% to 100%, 25% to 100%, 30% to 100%, 40% to 100%, 50% It is preferably ˜100%.
2) Co removal rate is 20% to 100%, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100%, 70% ~ 100%, preferably 80% ~ 100%.
3) Zn removal rate is 20% to 100%, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100%, 70% ~ 100%, preferably 80% ~ 100%.
4) Mo removal rate is 20% to 100%, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100%, 70% ~ 100%, preferably 80% ~ 100%.
The measurement method of elemental analysis of the surface of the heat-resistant resin substrate that appears after removing the metal of the metal wiring heat-resistant resin substrate uses a Quantum-2000 scanning X-ray photoelectron spectrometer manufactured by PHI, and the measurement conditions are X-ray source Use Al · Kα (monochrome), analysis area 100 μmφ, electron neutralizing gun.

  In order to perform the elemental analysis of the surface of the heat resistant resin substrate that appears by removing the metal of the metal wiring heat resistant resin substrate, and to have the effect of the present invention, Ni, Cr, Co, At least one metal selected from Zn, Sn and Mo and an Cr atom concentration after cleaning with an etching solution capable of mainly removing at least one metal containing these metals and an alloy containing 7.5 or less, and further 7 or less Further, it is preferably 6.5 or less. It is preferably 7.5 atomic% or less, more preferably 7 atomic% or less, and even more preferably 6.5 atomic% or less.

  In order to perform the elemental analysis of the surface of the heat resistant resin substrate that appears by removing the metal of the metal wiring heat resistant resin substrate, and to have the effect of the present invention, Ni, Cr, Co, Used for surface treatment of heat-resistant resin substrates or metal foils after cleaning with an etchant that can mainly remove at least one metal selected from Zn, Sn and Mo and an alloy containing at least one of these metals. The Si atom concentration by the silane coupling agent is preferably increased.

The etched metal wiring heat-resistant resin substrate can be further subjected to metal plating on at least a part of the metal wiring, and a plated metal wiring heat-resistant resin substrate can be manufactured.
As an example of metal plating of the etched metal wiring heat resistant resin substrate, in the case of copper wiring, it is possible to manufacture a plated metal wiring heat resistant resin substrate by performing tin plating, gold plating, silver plating, etc. on the copper wiring. it can.

  Etched cleaned metal wiring heat resistant resin substrate and plated metal wiring heat resistant resin substrate are used as flexible wiring circuit substrates, built-up circuit substrates, or IC carrier tape substrates as electronic computers, terminal devices, telephones, It can be utilized in all fields of electronics such as communication equipment, measurement control equipment, cameras, watches, automobiles, office equipment, home appliances, aircraft instruments, medical equipment, etc.

  In the present invention, the polyimide surface that appears by laminating polyimide and copper foil and removing a part of the copper foil is at least selected from Ni, Cr, Co, Zn, Sn and Mo used for the surface treatment of the copper foil. Ni used for the surface treatment of the copper foil existing on the polyimide surface or the surface of the polyimide layer by washing with an etching solution capable of mainly removing one kind of metal and an alloy containing at least one kind of these metals By removing mainly at least one metal selected from Cr, Co, Zn, Sn and Mo and an alloy containing at least one of these metals, it is possible to suppress plating precipitation abnormality, such as epoxy adhesive and ACF. It is considered that the adhesiveness with the adhesive improves.

  In the production method of the present invention, when a polyimide film is used as the heat-resistant resin substrate, the metal foil and the laminated surface of the polyimide film have an acid content of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or Or it is effective for polyimide using pyromellitic dianhydride.

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

The physical properties were evaluated according to the following methods.
1) Glass transition temperature (Tg) of polyimide film: determined from a peak value of tan δ by a dynamic viscoelasticity method (tensile method, frequency 6.28 rad / sec, temperature rising rate 10 ° C./min).
2) Linear expansion coefficient of polyimide film (50 to 200 ° C.): An average linear expansion coefficient of 20 to 200 ° C. was measured by a TMA method (tensile method, heating rate 5 ° C./min).
3) Peel strength (normal state) of metal foil laminated polyimide film, Peel strength of polyimide film and adhesive film: 3 mm wide leads specified in the same test method are prepared in accordance with JIS C6471, and the inside and outside of the winding The 90 ° peel strength was measured at a crosshead speed of 50 mm / min for each of the nine test pieces. The polyimide film and the copper foil laminated polyimide film have an average value of 9 points as peel strength. The laminate of the polyimide film and the adhesive sheet has an average value of three points as the peel strength. When the thickness of the metal foil is less than 5 μm, the plating is performed by electroplating to a thickness of 20 μm.
(However, “inside winding” means the peel strength inside the wound metal foil laminated polyimide film and “outside winding” means the peel strength outside the wound metal foil laminated polyimide film.)
4) Peel strength of the metal foil laminated polyimide film (after heating at 150 ° C. × 168 hours): A 3 mm-wide lead defined by the same test method was prepared in accordance with JIS C6471, and 150 ° C. was used for three test pieces. After being placed in an air circulating thermostat for 168 hours, 90 ° peel strength was measured at a crosshead speed of 50 mm / min. The average value of the three points was taken as the peel strength. When the thickness of the metal foil is less than 5 μm, the plating is performed by electroplating to a thickness of 20 μm.
The peel strength retention after heat treatment at 150 ° C. for 168 hours was calculated according to the following formula (1).
(However, “inside winding” means the peel strength inside the wound metal foil laminated polyimide film and “outside winding” means the peel strength outside the wound metal foil laminated polyimide film.)

5) Dielectric breakdown voltage of polyimide film: compliant with ASTM D149 (voltage was increased at a rate of 1000 V / second, and the voltage at which dielectric breakdown occurred was measured). The polyimide was measured in the air up to 50 μm, and in the oil when it was thicker than 50 μm.
6) Interline insulation resistance / volume resistance of metal foil laminated polyimide film: measured in accordance with JIS C6471.
7) Mechanical properties and tensile strength of polyimide film: Measured in accordance with ASTM D882 (crosshead speed 50 mm / min).
Elongation rate: Measured according to ASTM D882 (crosshead speed 50 mm / min).
-Tensile elastic modulus: Measured according to ASTM D882 (crosshead speed 5 mm / min).

(Reference Example 1: Production of polyimide S1)
Monomer concentration of paraphenylenediamine (PPD) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) in N-methyl-2-pyrrolidone at a molar ratio of 1000: 998 Was 18% (weight%, the same applies hereinafter), and reacted at 50 ° C. for 3 hours. The solution viscosity at 25 ° C. of the obtained polyamic acid solution was about 1680 poise.

(Reference Example 2: Production of polyimide S2)
1,3-bis (4-aminophenoxy) benzene (TPE-R) and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) in N-methyl-2-pyrrolidone and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) is added at a molar ratio of 1000: 200: 800 to give a monomer concentration of 18% and triphenylphosphine. The fat was added at 0.5% by weight with respect to the monomer weight, and reacted at 40 ° C. for 3 hours. The solution viscosity at 25 ° C. of the obtained polyamic acid solution was about 1680 poise.

(Reference Example 3: Production of polyimide film A1)
Using a film forming apparatus provided with a three-layer extrusion die (multi-manifold type die), the polyamic acid solution obtained in Reference Example 1 and Reference Example 2 was used to change the thickness of the three-layer extrusion die and to make a metal support. The film was cast on the substrate, dried continuously with hot air at 140 ° C., and then peeled to form a self-supporting film. After peeling this self-supporting film from the support, the temperature is gradually raised from 150 ° C. to 450 ° C. in a heating furnace to remove the solvent and imidize, and roll the long three-layer polyimide film into a roll. Winded up.
The characteristics of the obtained three-layer polyimide film (layer structure: S2 / S1 / S2) were evaluated.
Thickness configuration: 4 μm / 17 μm / 4 μm (total 25 μm)
-Glass transition temperature of S2 layer: 240 ° C
-Glass transition temperature of S1 layer: It was 340 degreeC or more, and clear temperature was not able to be confirmed.
・ Linear expansion coefficient (50 to 200 ° C.): MD 19 ppm / ° C., TD 17 ppm / ° C.
Mechanical properties 1) Tensile strength: MD, TD 520 MPa
2) Elongation: MD, TD 100%
3) Tensile modulus: MD, TD 7100 MPa
Electrical characteristics 1) Dielectric breakdown voltage: 7.2 kV
2) Dielectric constant (1 GHz): 3.20
3) Dissipation factor (1 GHz): 0.0047

Example 1
Rolled electrolytic copper foil (manufactured by Nippon Electrolytic Co., Ltd., USLP-R2, thickness 12 μm) and polyimide film produced in Reference Example 3 preheated by heating with hot air at 200 ° C. for 30 seconds in-line immediately before double belt press A1 (three-layer structure of S2 / S1 / S2) and a rolled electrolytic copper foil (manufactured by Nippon Electrolytic Co., Ltd., USLP-R2, thickness 12 μm) are laminated, and the temperature of the heating zone (maximum heating temperature) : 330 ° C., cooling zone temperature (minimum cooling temperature: 180 ° C.), continuous pressure bonding pressure: 3.9 MPa, pressure bonding time 2 minutes, continuous thermocompression-cooling and laminating A copper-clad polyimide film (width: 540 mm, length: 1000 m) of a double-sided copper foil was wound around a winding roll.
The characteristics of the copper-clad polyimide film of the obtained roll-wound double-sided copper foil were evaluated.
Thickness configuration (copper foil / polyimide / copper foil): 12 μm / 25 μm / 12 μm.
・ Peel strength (normal state): 1.5N / mm inside the winding, 2.1N / mm outside the winding
・ Peel strength (after heating at 150 ° C. × 168 hours): 1.6 N / mm in winding (retention rate of peel strength 107%), 2.1 N / mm outside winding (retention rate of peel strength 100%)
-Solder heat resistance: No abnormality.
Dimensional change rate: (MD direction: -0.03%, TD direction: 0.00%).
-Dielectric breakdown voltage: 12.0 kV.
Line insulation resistance: 3.3 × 10 ¹³ Ω · cm.
Volume resistance: 3.6 × 10 ¹⁶ Ω · cm.

(Cleaning with Ni-Cr seed layer remover)
A sample having a size of 10 × 10 cm was cut out from the roll-wound double-sided copper foil laminated polyimide film, and the cut sample was immersed in a ferric chloride solution (room temperature), which is a copper etching solution, for 20 minutes. The foil is completely removed by etching and then washed with water, and then immersed in a FLICKER-MH (manufactured by Nippon Chemical Industry Co., Ltd.) (temperature 30 ° C.) solution that is a Ni-Cr seed layer remover for 20 minutes. Further, the copper etching was immersed in a 5 wt% NaOH aqueous solution (temperature: 50 ° C.) for 1 minute, immersed in a 3 vol% hydrochloric acid aqueous solution (room temperature: about 20 ° C.) for 30 seconds, and washed with a Ni—Cr seed layer remover. A removed polyimide film was obtained.

(Preparation of adhesive sheet)
25 g of Epicoat 1009 (manufactured by Japan Epoxy Resin Co., Ltd.) is dissolved in 25 g of a mixed solvent of toluene / methyl ethyl ketone (1 part by volume / one part by volume), and 25 g of latent curing agent HX3942HP (manufactured by Asahi Kasei) and silane coupling agent KBM-403 A raw material dope was prepared by adding 0.5 g (manufactured by Shin-Etsu Chemical Co., Ltd.). The produced dope was applied to a release film and dried at 80 ° C. for 5 minutes to produce an epoxy-based bonding sheet (thickness: about 30 μm).

(Adhesive evaluation)
The polyimide film removed by copper etching washed with the Ni—Cr seed layer remover and the epoxy bonding sheet are directly superposed, and a heat press machine (manufactured by TOYO SEIKI, MP, under the conditions of temperature 170 ° C. and pressure 30 kgf / cm ² ) -WNH) was used for 5 minutes to produce a laminated sheet. With respect to the obtained laminated sheet and two samples after wet heat treatment (temperature: 105 ° C., humidity: 100% RH, treatment time: 12 hours), the strength by 90 ° peel was measured, and the results are shown in Table 1. Shown in

(Example 2)
Except for producing a copper-clad polyimide film of roll-wound double-sided copper foil using a roll-wound electrolytic copper foil (manufactured by Nippon Electrolytic Co., Ltd., HLS, thickness 9 μm) as the copper foil in Example 1. In the same manner as in Example 1 (cleaning with a Ni—Cr seed layer remover), (preparation of adhesive sheet) and (evaluation of adhesiveness), the evaluation result of 90 ° peel is shown in Table 1.

Example 3
In Example 1, a copper-clad polyimide film of a roll-wound double-sided copper foil was produced using a roll-wound electrolytic copper foil (F2-WS, thickness 12 μm, manufactured by Furukawa Circuit Foil Co., Ltd.) as the copper foil. Except for the above, (cleaning with a Ni—Cr seed layer remover), (preparation of adhesive sheet) and (evaluation of adhesiveness) are carried out in the same manner as in Example 1, and the evaluation results of 90 ° peel are shown in Table 1.

(Comparative Example 1)
In Example 1, a copper-clad polyimide film of roll-wound double-sided copper foil was produced in the same manner as in Example 1 except that the polyimide film removed by copper etching was not washed with the Ni-Cr seed layer remover. Then, a polyimide film removed by copper etching was prepared, an adhesive sheet was prepared, the adhesiveness was evaluated, and the obtained 90 ° peel evaluation results are shown in Table 1.

(Comparative Example 2)
In Example 2, a copper-clad polyimide film of roll-wound double-sided copper foil was produced in the same manner as in Example 1 except that the polyimide film removed by copper etching was not washed with the Ni-Cr seed layer remover. Then, a polyimide film removed by copper etching was prepared, an adhesive sheet was prepared, the adhesiveness was evaluated, and the obtained 90 ° peel evaluation results are shown in Table 1.

(Comparative Example 3)
In Example 3, a copper-clad polyimide film of roll-wound double-sided copper foil was produced in the same manner as in Example 1 except that the polyimide film removed by copper etching was not washed with the Ni-Cr seed layer remover. Then, a polyimide film removed by copper etching was prepared, an adhesive sheet was prepared, the adhesiveness was evaluated, and the obtained 90 ° peel evaluation results are shown in Table 1.

The elemental analysis of the surface of the polyimide film from which copper was removed by etching in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 was performed using a scanning X-ray photoelectron spectrometer, and the measurement results are shown in Table 2.
The measurement method of the elemental analysis of the surface of the polyimide film is a Quantum-2000 scanning X-ray photoelectron spectrometer manufactured by PHI, and the measurement conditions are an X-ray source, Al · Kα (monochrome), an analysis region of 100 μmφ, and electron neutralization. A gun was used.
When comparing the atomic concentration of the polyimide film surface,
1) In Example 1, Example 2, Comparative Example 1, and Comparative Example 2, the atomic concentrations of chromium, cobalt, zinc, and molybdenum were decreased in Examples 1 and 2.
2) In all of Example 1, Example 2, Comparative Example 1 and Comparative Example 2, silicon atoms are present, and it is considered that a silane coupling agent is present on the surface of the polyimide. In addition, the Si atom concentration before and after cleaning with the etching solution is increased after cleaning as compared with that before cleaning.

Example 4
Rolled electrolytic copper foil (manufactured by Nippon Electrolytic Co., Ltd., HLS, thickness 9 μm) and polyimide film A1 manufactured in Reference Example 3 preheated by heating with hot air at 200 ° C. for 30 seconds in-line immediately before double belt press ( 3 layers of S2 / S1 / S2) and Upilex S (manufactured by Ube Industries, thickness 25 μm) are laminated, and the temperature of the heating zone (maximum heating temperature: 330 ° C., the temperature of the cooling zone (minimum) (Cooling temperature: 180 ° C.), continuous pressure bonding pressure: 3.9 MPa, pressure bonding time 2 minutes, continuous thermocompression-cooling and laminating, roll-rolled single-sided copper-clad polyimide film ( (Width: 540 mm, length: 1000 m) was wound on a winding roll.

The copper-clad polyimide film of roll-wound single-sided copper foil was cut out, and a dry film type negative photoresist (UFG-072 manufactured by Asahi Kasei) was laminated on the copper foil of the copper-clad polyimide film with a hot roll at 110 ° C. Then, the circuit formation site was exposed, spray-developed with 1% sodium carbonate aqueous solution at 30 ° C. for 20 seconds to remove the unexposed resist, and the exposed portion of the copper foil was removed with ferric chloride solution at 50 ° C. for 15 seconds. Spray etching was performed to form a copper wiring having a pitch of 44 μm. Subsequently, the resist was removed by spraying a 2% aqueous solution of sodium hydroxide at 42 ° C. for 15 seconds, and then immersed in FLICKER-MH made by Nihon Chemical Industry Co., Ltd., which is a Ni—Cr etching solution at 45 ° C. for 5 minutes. The copper circuit part was tin-plated using Pogit LT-34H at 80 ° C. for 4 minutes.
The tin-plated copper wiring of the obtained tin-plated copper wiring polyimide film and the polyimide film surface from which the copper foil between the wirings was removed were photographed with a metal microscope (lens magnification: 1000 times, reflected light), An image is shown in FIG. From FIG. 1, the surface of the polyimide film from which the copper foil between the wirings is removed is clean, the junction between the copper wiring and the polyimide film from which the copper foil between the wirings has been removed, and the surface of the polyimide film from which the copper foil between the wirings has been removed. Thus, the occurrence of abnormal metal precipitation due to tin plating could not be confirmed.

(Comparative Example 4)
Using the copper-clad polyimide film of roll-rolled single-sided copper foil produced in Example 4, the copper-clad polyimide film was cut out, and a dry film type negative photoresist (Asahi Kasei) was formed on the copper foil of the copper-clad polyimide film. After laminating UFG-072) with a hot roll at 110 ° C., the circuit formation site was exposed, and developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 20 seconds to remove the unexposed resist and remove the copper foil. The exposed part was spray-etched with a ferric chloride solution at 50 ° C. for 15 seconds to form a 44 μm pitch copper wiring. Subsequently, a 2% caustic soda aqueous solution was sprayed at 42 ° C. for 15 seconds to remove the resist, and then tin plating was performed on the copper circuit portion at 80 ° C. for 4 minutes using SHIPLEY Tinposit LT-34H. The obtained tin-plated copper wiring polyimide film was photographed using a metal microscope in the same manner as in Example 4, and the image is shown in FIG.
From FIG. 2, many occurrences of abnormal metal deposition due to tin plating were confirmed at the junction between the copper wiring and the polyimide film from which the copper foil between the wirings was removed, and at the surface of the polyimide film from which the copper foil was removed between the wirings. .

It is the image obtained by the metallurgical microscope on the surface of the tin-plated copper wiring polyimide film of Example 4 of the present invention. It is the image obtained by the metallographic microscope of the tin-plated copper wiring polyimide film surface of the comparative example 4 of this invention.

Explanation of symbols

1: Tin-plated copper wiring, 2: polyimide film surface from which copper foil has been removed, 3: tin-plated abnormally deposited portion.

Claims (13)

At least one surface of a heat-resistant resin substrate is a metal foil surface-treated with at least one metal selected from Ni, Cr, Co, Zn, Sn and Mo or an alloy containing at least one of these metals (hereinafter referred to as surface treatment). A metal wiring heat-resistant resin substrate having a metal wiring on a heat-resistant resin substrate is manufactured using a metal foil heat-resistant resin substrate obtained by directly laminating a surface-treated surface of a used metal is called a surface-treated metal. In the method
Preparing a laminated substrate in which a metal foil is directly laminated on at least one side of the heat resistant resin substrate;
Patterning the metal foil by etching to form metal wiring on the surface of the heat-resistant resin substrate;
A cleaning step of cleaning the surface of the heat-resistant resin substrate on the side having the metal wiring with an etching solution capable of removing at least one of the surface-treated metals to improve the adhesion of the heat-resistant resin substrate ;
A step of pressing and laminating an ACF, an adhesive, or a bonding sheet on the heat-resistant resin substrate after the cleaning step;
A method for producing a metal wiring heat-resistant resin substrate, comprising: The heat-resistant resin substrate is polyimide, polyamide, aramid, liquid crystal polymer, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyetherketone, polyetheretherketone, polybenzazole, and BT (bismaleimide-triazine) resin. The method for producing a metal wiring heat-resistant resin substrate according to claim 1, wherein: 2. The method of manufacturing a metal wiring heat resistant resin substrate according to claim 1, wherein the heat resistant resin substrate is polyimide . The said ACF or a bonding sheet contains an epoxy resin, The manufacturing method of the metal wiring heat resistant resin substrate in any one of Claims 1-3 characterized by the above-mentioned. The method for producing a metal wiring heat-resistant resin substrate according to any one of claims 1 to 4 , wherein the etching solution can remove at least one kind of surface-treated metal at a faster rate than the metal wiring material. In the laminated surface of the heat resistant resin substrate and the metal foil, at least one of the surface of the heat resistant resin substrate or the metal foil surface is treated with a silane coupling agent,
The method for producing a metal wiring heat-resistant resin substrate according to any one of claims 1 to 5 , wherein the cleaning step is performed so that the silicon atom concentration on the surface after the processing is higher than that before the processing. Heat-resistant resin substrate, method for producing a metal wire heat resistant resin substrate according to claim 1, characterized in that it is a polyimide film of heat resistance. Etchant, any metal wire heat resistant resin substrate manufacturing method according to the claims 1 to 7, characterized in that the acidic etching liquid. Etchant, any metal wire heat resistant resin substrate manufacturing method according to the claims 1-7, characterized in that the Ni-Cr alloy for etchant.   The method for producing a metal wiring heat-resistant resin substrate according to any one of claims 1 to 9, wherein the metal foil is a copper foil.   The method for producing a metal wiring heat-resistant resin substrate according to any one of claims 1 to 10, further comprising a metal plating step after the cleaning step. The metal wiring heat resistant resin substrate according to any one of claims 1 to 11, wherein a laminated substrate in which a metal foil is directly laminated on at least one surface of the heat resistant resin substrate is prepared by thermocompression using a pressure roll or a double belt press. Manufacturing method. A heat-resistant resin substrate;
Surface treatment is performed with at least one kind of metal selected from Ni, Cr, Co, Zn, Sn, and Mo or an alloy containing at least one kind of these metals, which is directly laminated on this board and the lamination surface with this board is used. the metal used for the surface treatment, that surface treated metal.) and the metal wire being,
A metal wiring heat resistant resin substrate having an ACF, an adhesive, or a bonding sheet, the metal wiring heat resistant resin substrate manufactured by the manufacturing method according to any one of claims 1 to 12.

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