TW202136531A - Composite copper wiring line and multilayer body having resist layer - Google Patents

Abstract

The purpose of the present invention is to provide: a novel composite copper wiring line; and a multilayer body having a resist layer, said multilayer body being used for the production of a composite copper wiring line. The present invention provides a composite copper wiring line wherein a copper wiring line, which has a first surface, a second surface and a third surface, has a layer containing a first copper oxide on the first surface, while being provided with a first plating layer that contains a metal other than copper on the surface of the layer containing the first copper oxide.

Description

Composite copper wiring and laminate with photoresist layer

The present invention relates to a composite copper wiring and a laminate with a photoresist layer.

In the manufacture of semiconductor integrated circuits, etc., in the thermal compression bonding of copper as a conductor to a resin printed circuit board, 1) laminate a photoresist material containing photosensitive material, 2) selectively irradiate energy rays such as light After the exposure process is performed, 3) a mask pattern (also called a photoresist pattern) is obtained on the substrate by a development process, 4) the pattern is used as a mask, and the conductor is etched to form a circuit. Photoresist materials are divided into positive type photoresist materials and negative type photoresist materials. The positive type photoresist material is removed by the development process where the light is irradiated. On the contrary, the negative type photoresist material is removed by the light irradiation part. The development process remains. In recent years, with the need for higher integration and miniaturization of semiconductor integrated circuits, more complex patterns have also been required for mask patterns.

As the mask pattern becomes complicated, the reflection of exposure light from the printed substrate becomes a problem. The reflected light produces a halo, which causes the mask pattern to be distorted and uneven. Therefore, in order to suppress reflected light, it is known to provide a film to prevent reflection of exposure light on a printed circuit board (Japanese Patent Application Laid-Open No. 7-86127).

In addition, it is also known that the copper surface of the conductor constituting the printed circuit board is oxidized and blackened, thereby suppressing the reflection of exposure light (Japanese Patent Application Publication No. 2016-119396).

The present invention provides a novel laminate having a photoresist layer and a manufacturing method thereof, and a printed circuit board including a composite copper wiring manufactured using the laminate having a photoresist layer, and a manufacturing method thereof.

As a result of their intensive research, the inventors have discovered that deliberately laminating metals other than copper on a layer containing copper oxide blackened by oxidation treatment has successfully suppressed brightness and can produce a laminate suitable for circuit formation. In addition, it has been newly discovered that while the copper oxide-containing layer removed during circuit formation remains in the state, it is possible to fabricate composite copper wiring that can withstand use as an electronic circuit and can be turned on.

The present invention has the following implementation aspects: [A1] A laminate having a structure, the first surface and the second surface of the structure are surfaces made of copper, and a part or all of the first surface of the structure There is a first copper oxide-containing layer, a part or all of the surface of the first copper oxide-containing layer is formed with a first plating layer containing a metal other than copper, and a part or all of the first plating layer The surface has a photoresist layer. [A2] The layered body as in [A1], wherein ^{the value of the lightness L*} of the surface on which the first plating layer is formed is less than 50. [A3] A laminate such as [A1] or [A2], wherein the color change of the surface on which the first plating layer is formed before and after the heat treatment is 10 or less when heat-treated at 225°C for 30 minutes. [A4] The laminate of any one of [A1] to [A3], wherein the Rz of the part or all of the photoresist layer on the surface on which the first plating layer is formed is 0.2 μm or more and 1.0 Below μm. [A5] The laminate according to any one of [A1] to [A4], wherein the RSm of the part or all of the photoresist layer on the surface on which the first plating layer is formed is 600 nm or less. [A6] The laminate according to any one of [A1] to [A5], wherein the first plating layer contains nickel. [A7] The laminate according to any one of [A1] to [A6], wherein the average thickness of the first plating layer is 30 nm or more and 70 nm or less. [A8] The laminated body as in any one of [A1] to [A7], wherein the photoresist layer is a dry film photoresist, a positive liquid photoresist or a negative liquid photoresist. [A9] A laminate as in any one of [A1] to [A8], wherein the structure is a piece of copper foil. [A10] The laminate as [A9], wherein a part or all of the second surface has a second copper oxide-containing layer, and a part or all of the surface of the second copper oxide-containing layer is formed with copper The second plating layer of other metals. [A11] The layered body as in [A10], in which a part or all of the surface of the second plating layer has a resin substrate. [A12] The laminate of [A11], wherein the peel strength between the resin base material and the second plating layer is 0.5 kgf/cm or more. [A13] A laminate such as [A11] or [A12], wherein the resin substrate contains selected from polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, liquid crystal polymer , Triphenyl phosphite, fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin At least one insulating resin. [A14] A laminate as in any one of [A1] to [A8], wherein the structure is a copper-clad laminate.

[B1] A method for manufacturing a laminate, which is performed on a structure having a first surface and a second surface made of copper, and a part or all of the first surface has a first copper oxide-containing layer, A first plating layer containing a metal other than copper is formed on part or all of the surface of the first copper oxide-containing layer, and the method of manufacturing the laminate includes applying a part of the first plating layer to the structure. Or the step of forming a photoresist layer on the entire surface. [B2] The manufacturing method as [B1], wherein ^{the value of the lightness L*} of the surface on which the first plating layer is formed is less than 50. [B3] The manufacturing method as [B1] or [B2], wherein, when the heat treatment is performed at 225° C. for 30 minutes, the color change of the surface on which the first plating layer is formed before and after the heat treatment is 10 or less. [B4] The manufacturing method of any one of [B1] to [B3], wherein the first plating layer contains nickel. [B5] The manufacturing method of any one of [B1] to [B4], wherein the average thickness of the first plating layer is 30 nm or more and 70 nm or less. [B6] The manufacturing method of any one of [B1] to [B5], wherein the photoresist layer is a dry film photoresist, a positive liquid photoresist or a negative liquid photoresist. [B7] The manufacturing method as in any one of [B1] to [B6], wherein the surface on which the first plating layer is formed is not subjected to soft etching treatment, and the soft etching treatment is polishing wheel grinding, brushing and chemical Grind. [B8] The manufacturing method as in any one of [B1] to [B7], wherein the structure is a piece of copper foil. [B9] The manufacturing method as [B8], wherein a part or all of the second surface of the structure has a second copper oxide-containing layer, and a part or all of the surface of the second copper oxide-containing layer is formed There is a second plating layer containing metals other than copper. [B10] The manufacturing method of [B9], which includes a step of laminating a resin base material on a part or all of the surface on which the second plating layer is formed. [B11] The manufacturing method as in [B10], wherein the peel strength between the resin substrate and the second plating layer is 0.5 kgf/cm or more. [B12] The manufacturing method as [B10] or [B11], wherein the resin substrate contains selected from polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, liquid crystal polymer , Triphenyl phosphite, fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin At least one insulating resin. [B13] The manufacturing method as in any one of [B1] to [B7], wherein the structure is a copper-clad laminate. [B14] The manufacturing method of any one of [B10] to [B13], further comprising: irradiating a part of the photoresist layer with light, and after developing, etching the first surface to form wiring on the structure A step of patterning; and a step of peeling off the photoresist layer after the etching process from the laminate. [B15] The manufacturing method as in [B14], wherein the Rz of the surface on which the first plating layer is formed after the photoresist layer is peeled off is 0.2 μm or more and 1.0 μm or less. [B16] The manufacturing method as in [B14] or [B15], wherein the RSm of the surface on which the first plating layer is formed after the photoresist layer is peeled off is 600 nm or less.

[C1] A method of manufacturing a printed circuit board, including: The step of irradiating a part of the photoresist layer of the laminate of any one of [A11] to [A14] with light, and after developing, etching the first surface to form a wiring pattern on the structure; and The step of peeling off the photoresist layer after the etching process from the laminate. [C2] The manufacturing method as in [C1], wherein the Rz of the surface on which the first plating layer is formed after the photoresist layer is peeled off is 0.2 μm or more and 1.0 μm or less. [C3] The manufacturing method as [C1] or [C2], wherein the RSm of the surface on which the first plating layer is formed after the photoresist layer is peeled off is 600 nm or less.

[D1] A composite copper wiring, on the first side of a wiring formed of copper having a first side, a second side, and a third side, with a first layer containing copper oxide, and the first layer containing copper oxide A first plating layer containing a metal other than copper is formed on the surface of the material layer. [D2] The composite copper wiring as in [D1], wherein the wiring formed of copper is conductive with the first plating layer. [D3] A composite copper wiring such as [D1] or [D2], wherein a second copper oxide-containing layer is provided on the second surface, and the surface of the second copper oxide-containing layer is formed with copper other than copper The second plating layer of metal. [D4] The composite copper wiring as in [D3], wherein the wiring formed of copper is conductive with the second plating layer. [D5] The composite copper wiring as in any one of [D1] to [D4], wherein a copper wiring protective layer is provided on the third surface, and the copper wiring protective layer is selected from a copper oxide layer and a blackening treatment layer , A group consisting of anti-rust agent layer and coupling treatment layer.

[E1] A printed circuit board with a resin base material on the second area layer of the composite copper wiring as in any one of [D1] to [D5]. [E2] The printed circuit board such as [E1], wherein the first side is equipped with electronic components. Cross-reference with related documents: This application is based on the Japanese Patent Application 2020-052151 filed on March 24, 2020, which claims priority, and is included in this specification by citing the basic application.

The preferred embodiments of the present invention will be described in detail below using additional drawings, but it is not limited thereto. In addition, based on the description of this specification, a person with ordinary knowledge in the technical field of the invention can understand the purpose, features, advantages, and concept of the present invention, and a person with ordinary knowledge in the technical field of the invention can easily reproduce it from the description of this specification. this invention. The embodiments and specific examples of the invention described below represent preferred embodiments of the invention, and are used for illustration and description, and do not limit the invention. Those having ordinary knowledge in the technical field to which the invention pertains will understand that various changes and modifications can be made based on the description of this specification within the intent and scope of the invention disclosed in this specification.

<Structure> One embodiment of the present invention is a structure whose first surface and second surface are surfaces formed of copper. Copper is preferably pure copper with a copper purity of 99.9% by mass or more, more preferably formed of toughened copper, deoxidized copper, and oxygen-free copper, and more preferably formed of oxygen-free copper with an oxygen content of 0.001% to 0.0005% by mass . The structure can be a piece of copper foil or a piece of copper plate such as electrolytic copper foil or rolled copper foil. In addition, several copper foils or copper plates may be laminated. When the structure is a copper foil, its thickness is not particularly limited, but it is preferably 0.1 μm or more and 100 μm or less, and more preferably 0.5 μm or more and 50 μm or less. When the structure is a copper plate, its thickness is preferably more than 100 μm. The thickness is not particularly limited, but is more preferably 1 mm or more, 2 mm or more, or 10 mm or more, and more preferably 10 cm or less, 5 cm or less, or 2.5 cm or less. Or the structure may also be a copper clad laminate (Copper Clad Laminate: CCL). The resin-impregnated sheet (called a resin substrate or a prepreg) is laminated on a substrate such as paper or glass, and the insulation board obtained by thermal compression bonding is called a laminated board, and copper foil is applied on both sides of the board. Copper laminate. There are three-layer CCL and two-layer CCL, etc. You can use either one. The three-layer CCL is mainly used for TAB (tape-automated bonding) packaging. The copper foil and resin substrate are bonded together with an adhesive. The two-layer CCL is used It is packaged in COF (chip on film) method and does not use adhesive. In addition, the insulating plate may be a resin sheet that does not contain paper, glass, etc., and an adhesive sheet or an adhesive layer may exist at the interface between the copper and the insulating layer. The resin contained in the resin substrate is not particularly limited, and may be a thermoplastic resin or a thermosetting resin, preferably polyphenylene ether (PPE), epoxy resin, polyoxyxylene (PPO), polybenzoxazole (PBO), poly Tetrafluoroethylene (PTFE), liquid crystal polymer (LCP), triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low Permittivity polyimide, cyanate resin or mixed resin of these. The resin substrate may further include inorganic fillers or glass fibers. The thickness of the resin substrate is not particularly limited, but is preferably 1 μm or more and 100 mm or less.

A part or all of the surface of the structure preferably has a layer containing copper oxide. When the structure is copper foil, the copper oxide-containing layer is preferably present on both sides of the structure. When the structure is CCL, the copper oxide-containing layer may exist on one side of the structure or may exist. On both sides. The layer containing copper oxide contains copper oxide (CuO) and/or cuprous oxide (Cu ₂ O). The layer containing copper oxide can be formed by oxidizing the surface of the structure. With this oxidation treatment, the surface of the structure is roughened. For the layer containing copper oxide, a dissolving agent can be used to adjust the protrusions on the surface of the oxidized structure. In addition, the surface of the layer containing copper oxide can be reduced by a reducing agent. The resistivity of pure copper is 1.7×10 ^-8 (Ωm). In contrast, the resistivity of copper oxide is 1-10 (Ωm), and the resistivity of cuprous oxide is 1×10 ⁶ ～1×10 ⁷ (Ωm). ), so the conductivity of the copper oxide-containing layer formed by the oxidation treatment is lower than that of pure copper.

A part or all of the surface of the copper oxide-containing layer of the structure may include a metal other than copper. When the structure is copper foil, metals other than copper are preferably present on both sides of the structure. The included metal is not particularly limited, and may include at least one metal selected from the group consisting of tin, silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold, and platinum. In particular, in order to have acid resistance and heat resistance, it is preferable to include metals with higher acid resistance and heat resistance than copper, such as nickel, palladium, gold, and platinum. Metals other than copper may exist as a layer on the surface of the layer containing copper oxide. The layer containing a metal other than copper can form a plating layer by, for example, plating the surface of the layer containing copper oxide with a metal other than copper. The plating method is not particularly limited, and examples include electroplating, electroless plating, vacuum vapor deposition, chemical conversion treatment, etc., and it is preferable to form a uniform thin plating layer, so electroplating is preferred.

When electroplating is applied to the surface of the structure after oxidation treatment, the copper oxide on the surface is first reduced to form cuprous oxide or pure copper. Therefore, there is a time delay until the plating is formed, and then the metal layer is formed. Metal began to precipitate. The amount of charge varies depending on the type of plating solution or the amount of copper oxide. For example, when nickel plating is applied to a copper member, in order to make the thickness within a preferable range, it is better to give every dm of the copper member to be electroplated ² Charges with an area of 15C or more and 75C or less are more preferably given with a charge of 25C or more and 65C or less. By plating, a part of the copper oxide formed by oxidation is reduced to copper, and the conductivity of the copper oxide-containing layer is improved. The copper that forms the conductor of the structure and the same conductor that contains metals other than copper Can be connected between the layers.

The method of confirming the continuity is not particularly limited. For example, with respect to the planar observation area of 4μm ² of the plating layer containing a metal other than copper, the copper forming the conductor of the structure and the layer containing the metal other than copper which are also conductors In the current image of an atomic force microscope (AFM) when a voltage of -0.5V is applied, the area with a current value of -60nA or less is 2.5% or more and 5% per unit plane observation area of the plating layer containing metals other than copper Above or above 10%, the copper forming the conductor of the structure and the layer containing a metal other than copper, which is also the conductor, can be regarded as conductive. Or, when a structure is used to form a wiring pattern, and when a printed circuit board is manufactured, electronic parts are mounted on a layer containing a metal other than copper to function as a circuit, and the copper that forms the conductor of the structure is the same as the conductor that contains copper. The layers of other metals can be regarded as conducting. The average thickness in the vertical direction of the layer containing a metal other than copper formed on the surface of the structure by plating is not particularly limited, but is preferably 10 nm or more, 20 nm or more, 30 nm or more, or 40 nm or more. However, it is more preferably 80 nm or less, and more preferably 70 nm or less and 65 nm or less. In addition, for metals other than copper contained in the copper oxide-containing layer, the average thickness in the vertical direction can be such that the copper oxide-containing layer can be dissolved in an acid solution, and the amount of metal can be measured by ICP analysis, and the measured amount can be divided by Calculate the area of the structure when viewed from the plane.

^{The L*} a ^* b ^* value of the lightness L ^{* in} the color system on the surface on which the plating layer is formed is preferably less than 60, less than 55, less than 50, less than 45, less than 40, less than 35, Less than 30, less than 25, or less than 20. The smaller the value, the more the reflection of exposure light can be suppressed.

On the surface on which the plating layer is formed, it is preferable that a weak layer (Weak Boundary Layer: WBL) does not occur due to oxidation or deterioration of the surface. If the fragile layer is formed, the adhesion to the photoresist layer will be affected. The heat resistance (the degree to which a fragile layer is easily generated) can be evaluated by the color change of the surface on which the plating layer is formed during the heat treatment. When the color change is small, a fragile layer is not easy to produce, and good adhesion of the photoresist layer can be obtained. ^{When heat treatment at 225°C for 30 minutes, the color change (ΔE *} ab) of the surface on which the plating layer is formed before and after the heat treatment is preferably 10 or less, 5 or less, 3 or less, 2 or less, or 1, but not limited Here.

When the structure is copper foil, the maximum height roughness (Rz) of the surface on which the plating layer is formed is preferably 1.0 μm or less, 0.9 μm or less, or 0.8 μm or less, and more preferably 0.1 μm or more and 0.2 μm or more Or 0.3μm or more. The Rz system represents the sum of the maximum value of the peak height Zp and the maximum value of the valley depth Zv of the profile curve (y=Z(x)) in the reference length l. Rz can be calculated according to the method specified in JIS B 0601:2001 (based on the international standard ISO13565-1).

在此，算數平均粗度（Ra）的10%作為凹凸的最小高度，基準長度（lr）的1%作為最小長度以定義一個週期量的凹凸。算數平均粗度（Ra）係表示基準長度l中，以下式表示之輪廓曲線（y=Z(x)）中Z(x)（即峰高及谷深）之絕對值的平均值。 數式2：

舉例如，Rsm可根據「利用原子力顯微鏡之精密陶瓷薄膜的表面粗度測定方法（JIS R 1683:2007）」來測定並算出。When the structure is copper foil, the average length (RSm) of the roughness curve parameter of the surface where the plating layer is formed is preferably 750nm or less, 700nm or less, 650nm or less, 600nm or less, 550nm or less, 450nm or less, or 350nm or less , And preferably more than 100 nm, more than 200 nm, or more than 300 nm. RSm represents the average of the length (that is, the length of the profile curve parameter: Xs1 ~ Xsm) of the unevenness of one period included in the roughness curve of a reference length (lr), and is calculated by the following formula. Mathematical formula 1:

Here, 10% of the arithmetic average roughness (Ra) is taken as the minimum height of the concavity and convexity, and 1% of the reference length (lr) is taken as the minimum length to define a period of concavity and convexity. The arithmetic average roughness (Ra) is the average value of the absolute value of Z(x) (namely peak height and valley depth) in the contour curve (y=Z(x)) represented by the following formula in the reference length l. Mathematical formula 2:

For example, Rsm can be measured and calculated according to "Method for Measuring Surface Roughness of Precision Ceramic Thin Films Using Atomic Force Microscope (JIS R 1683:2007)".

<Method for manufacturing a structure having a layer containing copper oxide and a plating layer> One embodiment of the present invention is a method for manufacturing a structure having a layer containing copper oxide and a plating layer, including forming a structure containing copper oxide with an oxidizing agent The first step of the layer; and the second step of plating the surface of the structure on which the layer containing copper oxide is formed. With this manufacturing method, a structure having a first surface and a second surface can be manufactured. The first surface and the second surface are surfaces made of copper. A part or all of the first surface has a first layer containing copper oxide. A part or all of the surface of a layer containing copper oxide has a first plating layer containing a metal other than copper.

First, in the first step, the structure is oxidized with an oxidizing agent to form a copper oxide layer, and fine irregularities are formed on the surface. The oxidation treatment can be single-sided or double-sided. Before this oxidation step, roughening treatment steps such as soft etching or etching are not required, but it can be carried out. Furthermore, it is also possible to perform degreasing treatment before oxidation treatment, acid cleaning by removing natural oxide film for homogenization treatment, or alkali treatment after acid cleaning to prevent acid from being carried into the oxidation step. The method of alkali treatment is not particularly limited, preferably 0.1-10g/L alkaline aqueous solution, more preferably 1-2g/L alkaline aqueous solution, alkaline aqueous solution such as sodium hydroxide aqueous solution, treated at 30-50°C for 0.5 ~2 minutes is enough.

The oxidizing agent is not particularly limited. For example, aqueous solutions such as sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, and potassium persulfate can be used. Various additives (such as phosphate such as trisodium phosphate dodecahydrate) or surface-active molecules can be added to the oxidizing agent. Surface-active molecules include, for example, porphyrin, porphyrin macrocycles, expanded porphyrin, condensed porphyrin, porphyrin linear polymers, porphyrin-sandwich coordination complexes, porphyrin arrays, silanes, tetraorgano-silanes , Aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea) (l- [3-(Trimethoxysilyl)propyl]urea), (3-aminopropyl)triethoxysilane, (3-epoxypropyloxypropyl)trimethoxysilane, (3-chloropropyl)trimethoxy Silane, (3-epoxypropyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriethoxysilane , Triethoxy (isobutyl) silane, triethoxy (octyl) silane, ginseng (2-methoxyethoxy) (vinyl) silane, chlorotrimethylsilane, methyltrichlorosilane , Silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, vinyl-trimethoxysilane, amine, sugar, etc.

The oxidation reaction conditions are not particularly limited, and the liquid temperature of the oxidation chemical solution is preferably 40 to 95°C, more preferably 45 to 80°C. The reaction time is preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.

In the first step, a dissolving agent can be used to dissolve a part of the layer containing copper oxide.

The dissolving agent used in this step is not particularly limited, and is preferably a chelating agent, especially a biodegradable chelating agent, etc., for example, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid diacetic acid Tetrasodium, ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-imino sodium disuccinate, trisodium methylglycine diacetate, aspartic acid diacetate Sodium, disodium N-(2-hydroxyethyl)iminodiacetate, sodium gluconate, etc.

The pH of the solution for dissolving is not particularly limited, but it is preferably alkaline, more preferably pH 8 to 10.5, still more preferably pH 9.0 to 10.5, and still more preferably pH 9.8 to 10.2.

In addition, in the first step, a chemical solution containing a reducing agent (reduction chemical solution) may be used to partially reduce the copper oxide contained in the formed copper oxide-containing layer.

The reducing agent can be DMAB (dimethylamine borane), diborane, sodium borohydride, hydrazine, etc. In addition, the chemical solution for reduction is a liquid containing a reducing agent, an alkaline compound (sodium hydroxide, potassium hydroxide, etc.), and a solvent (pure water, etc.).

Next, the surface of the structure on which the layer containing copper oxide is formed is plated with a metal other than copper, thereby manufacturing a structure having a layer containing copper oxide and a plating layer.

In the range that does not impair the technical characteristics of the present invention, the structure manufactured by these steps can be subjected to coupling treatment using silane coupling agent or the like, molecular bonding treatment, and anti-rust treatment using benzotriazoles and the like.

<Laminated body> One embodiment of the present invention is a laminated body having a photoresist layer on a part of the surface of the structure. The photoresist layer is preferably laminated on a part or all of the surface of the plating layer.

The photoresist layer is a layer containing a material that can be hardened or dissolved by light exposure, and is preferably formed of dry film photoresist (DFR), positive liquid photoresist or negative liquid photoresist, but is not particularly limited. DFR preferably contains a binder polymer (including alkaline developing type and solvent developing type) that contributes to film formation and monomers that generate photopolymerization by UV irradiation (such as acrylate or methacrylate monomers). Body) and photopolymerization initiator. In order to form DFR, it is preferable to use a dry film with a three-layer structure of cover film/photoresist/carrier film. By peeling off the cover film while thermally compressing the photoresist to the structure and lamination, after lamination, the carrier film is peeled off to form a photoresist layer, or DFR, on the structure. The positive liquid photoresist and the negative liquid photoresist may, for example, be phenolic resin (Novolak) dissolved in an organic solvent. Regarding the liquid photoresist, the photoresist layer can be formed by coating on the surface of the structure and drying. The thickness of the photoresist layer is not particularly limited, but is preferably 5 μm to 200 μm.

The Rz of the surface on which the plated layer is formed on which the photoresist layer is formed is preferably 1.0 μm or less, 0.9 μm or less, or 0.8 μm or less, and more preferably 0.1 μm or more, 0.2 μm or more, or 0.3 μm or more. In addition, the RSm of the plated surface on which the photoresist layer is formed is preferably 750nm or less, 700nm or less, 650nm or less, 600nm or less, 550nm or less, 450nm or less, or 350nm or less, and preferably 100nm or more, 200nm or more, or 300nm or more. The above-mentioned surface roughness relates to the adhesion and peelability of the photoresist layer. If Rz is too small, the adhesion to the photoresist layer will be insufficient, and if it is too large, the photoresist layer will be difficult to peel off after etching. On the other hand, if RSm is too large, the adhesion to the photoresist layer is insufficient, and if it is too small, the photoresist layer is difficult to peel off after etching.

The laminate may have a resin base material on the surface of the structure opposite to the surface on which the photoresist layer is formed. The resin substrate is preferably laminated on the structure by thermocompression bonding. The adhesion between the resin substrate and the structure is better. Adhesion can be measured based on a 90-degree peel test (Japanese Industrial Standards (JIS) C5016 "Test Method for Flexible Printed Wiring Boards"; corresponding international standards IEC249-1:1982, IEC326-2:1990) as the peel strength. The peel strength between the resin substrate and the structure is preferably 0.40 kgf/cm or more, 0.50 kgf/cm or more, or 0.60 kgf/cm or more, but it is not limited to this.

<Method of Manufacturing Laminated Body> One embodiment of the present invention is a method of manufacturing a laminated body including a structure and a photoresist layer, and the manufacturing method includes the step of forming a photoresist layer on the structure of the present invention. The step of forming the photoresist layer may include: using a dry film and attaching the photoresist while heating; applying a positive liquid photoresist or a negative liquid photoresist at room temperature and drying.

Generally, before forming the photoresist layer, a soft etching process is performed in order to increase the adhesion. However, in the case of the structure of the present invention having a layer containing copper oxide and a plating layer, the structure can be combined with the photoresist Because of the adhesion of the layer, the soft etching process may not be performed before the step of forming the photoresist layer. The soft etching treatment can include buff roll polishing, scrubbing, jet scrubbing, chemical polishing, and combinations of these. Chemical polishing can include: immersion in an aqueous solution containing sulfuric acid and hydrogen peroxide; an aqueous solution containing copper chloride; an aqueous solution containing persulfate; an organic solvent containing benzotriazole; an aqueous solution containing permanganic acid, and the like.

In addition, it may include a step of laminating the resin substrate by thermal press fitting on the surface opposite to the surface on which the photoresist layer is formed. This step can be performed before or after the step of forming the photoresist layer, or can be performed at the same time, and is preferably performed before the step of forming the photoresist layer.

The conditions for thermocompression bonding of the resin substrate on the surface opposite to the surface on which the photoresist layer is formed can be the conditions recommended by each substrate manufacturer (such as temperature, pressure, and time). For the conditions recommended by each substrate manufacturer, the following conditions can be considered, for example.

1) In the case where the resin substrate contains epoxy resin or is formed of epoxy resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 300°C for 1 minute to 5 hours to heat the composite copper component. Crimped to the resin substrate. E.g, 1-1) When the resin substrate is R-1551 (manufactured by Panasonic), it is heated at a pressure of 1 MPa, and after reaching 100°C, the temperature is maintained at that temperature for 5 to 10 minutes, and then further heated at a pressure of 3.3 MPa to reach After 170-180°C, maintain the temperature for 50 minutes to perform thermocompression bonding. 1-2) When the resin substrate is R-1410A (manufactured by Panasonic), heat it at a pressure of 1 MPa. After reaching 130°C, maintain the temperature for 10 minutes, and then further heat it at a pressure of 2.9 MPa to reach 200°C. After that, the temperature was maintained for 70 minutes to perform thermocompression bonding. 1-3) When the resin base material is EM-285 (manufactured by EMC), heat it at a pressure of 0.4 MPa. After reaching 100°C, increase the pressure to 2.4 to 2.9 MPa and then further heat it. After reaching 195°C, it will be heated at this temperature. Maintain for 50 minutes for thermocompression bonding. 1-4) When the resin substrate is GX13 (manufactured by Ajinomoto), heat it under a pressure of 1.0 MPa and maintain it at 180°C for 60 minutes to perform thermocompression bonding.

2) When the resin base material contains PPE resin or is formed of PPE resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 350°C for 1 minute to 5 hours, thereby thermocompression bonding of the composite copper member For resin substrate. E.g, 2-1) When the resin substrate is R5620 (manufactured by Panasonic Co., Ltd.), after heating to 100°C under a pressure of 0.5 MPa, after thermo-compression bonding, the temperature and pressure are increased to 2.0-3.0 MPa, 200- Maintain at 210°C for 120 minutes for further thermocompression bonding. 2-2) When the resin substrate is R5670 (manufactured by Panasonic Co., Ltd.), after heating to 110°C under a pressure of 0.49 MPa, after thermo-compression bonding, the temperature and pressure are increased and maintained at 2.94 MPa and 210°C at 120°C. Minutes to further heat and crimp. 2-3) When the resin substrate is R5680 (manufactured by Panasonic Co., Ltd.), after heating to 110°C under a pressure of 0.5 MPa, after thermo-compression bonding, raise the temperature and pressure to 3.0 to 4.0 MPa, 195°C Maintain for 75 minutes for further thermo-compression bonding. 2-4) When the resin base material is N-22 (manufactured by Nelco), heat it at a pressure of 1.6 to 2.3 MPa, maintain it at 177°C for 30 minutes, then heat it further, and hold it at 216°C for 60 minutes to perform hot pressing catch.

3) When the resin base material contains PTFE resin or is formed of PTFE resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 400°C for 1 minute to 5 hours, thereby thermocompression bonding of the composite copper member For resin substrate. E.g, 3-1) When the resin substrate is NX9255 (manufactured by Park Electrochemical), heat to 260°C under a pressure of 0.69 MPa, increase the pressure to 1.03 to 1.72 MPa and heat to 385°C, and maintain at 385°C for 10 minutes. Hot crimping. 3-2) When the resin substrate is RO3003 (manufactured by Rogers), 50 minutes (approximately 220°C) after the start of pressing, pressurize to 2.4 MPa and maintain at 371°C for 30 to 60 minutes to perform thermocompression bonding.

<Composite Copper Wiring> One embodiment of the present invention is a composite copper wiring, which has a layer containing copper oxide on a part of the surface of a wiring formed of copper, and the surface of the layer containing copper oxide has copper other than copper. The metal plating layer. Figure 2 shows a schematic diagram of an example of composite copper wiring. Wiring is a conductive conductor, and an electronic circuit is formed by mounting electronic parts (resistors, capacitors, diodes or transistors, etc.) on it. The layer containing copper oxide is preferably conductive. The layer containing copper oxide has conductivity, thereby enabling conduction between the wiring formed of copper and the plating layer containing a metal other than copper. The composite copper wiring can be manufactured by the structure or laminate of the present invention.

<Printed substrate> One embodiment of the present invention is a printed substrate containing the composite copper wiring of the present invention. The printed circuit board includes a printed wiring board (Printed Wiring Board: PWB) and a printed circuit board (Printed Circuit Board: PCB). Soldering, as the state of the electronic circuit in action.

<The manufacturing method of composite copper wiring and printed circuit board> One embodiment of the present invention is a manufacturing method of composite copper wiring and a printed circuit board containing composite copper wiring, including irradiating light to a part of the photoresist layer included in the laminate of the present invention After development, the surface where the photoresist layer is formed is etched to remove unnecessary parts, and a predetermined wiring pattern is formed on the structure, thereby forming a circuit.

The light to be irradiated may be light that hardens or dissolves the resin contained in the photoresist layer. In the case of a dry film, it is preferably light with a wavelength of 100 nm to 500 nm. In the case of a positive type liquid photoresist or a negative type liquid photoresist, it is preferably light with a wavelength of 10 nm to 900 nm. The amount of light irradiation and the irradiation time are related to the thickness of the photoresist layer. Preferably, it is an irradiation dose of 1, 10, or 100 to 1000 mJ/cm ² , but it is not particularly limited.

By developing, the photoresist layer unnecessary for the mask pattern is removed. When the adhesive polymer contained in the photoresist is an alkaline developing type, it is preferable to perform an alkaline treatment, but it is not particularly limited. The alkali treatment is preferably at 25°C to 35°C, immersed in a 0.5% to 1.5% sodium carbonate aqueous solution 1.5 to 2.5 times the minimum development time and then washed with water.

By etching, dissolve and remove metals other than copper, copper oxide, and copper that are not protected by the photoresist layer. The conditions for this removal are not particularly limited. Preferably, it is immersed in hydrogen peroxide/hydrochloric acid mixed liquid, hydrogen peroxide/sulfuric acid mixed liquid, 20%-50% copper chloride or ferric chloride aqueous solution at 20℃～60℃ Wash with water after waiting. A layer containing a metal other than copper, a layer containing copper oxide, and copper protected by a photoresist layer form a composite copper wiring. Before the photoresist layer is peeled off, the copper oxide layer can be formed, blackened, and rust-prevented on the copper-made side surface of the composite copper wiring formed by etching (for example, the third surface in Figure 2 is an example) Treatment, coupling treatment, etc., forming copper oxide layer, blackening treatment layer (black chromate layer), rust inhibitor layer (including benzotriazole, etc.), coupling treatment layer (including silane coupling agent, etc.) Wiring protection layer. Alternatively, a process of roughening the side surface made of copper may be performed.

In addition, it may include a step of peeling off the photoresist layer after the etching process. The peeling method is not particularly limited. When the adhesive polymer contained in the photoresist is an alkaline developing type, it is preferably immersed in a 1-5% sodium hydroxide aqueous solution at 40°C to 60°C within 180 seconds, within 120 seconds, or Within 90 seconds, remove the photoresist layer and wash with water.

The Rz of the surface on which the plating layer is formed after the photoresist layer is peeled off is preferably 1.0 μm or less, 0.9 μm or less, or 0.8 μm or less, and more preferably 0.1 μm or more, 0.2 μm or more, or 0.3 μm or more. In addition, the Rsm of the surface on which the plating layer is formed after the photoresist layer is stripped is preferably 750nm or less, 700nm or less, 650nm or less, 600nm or less, 550nm or less, 450nm or less, or 350nm or less, and preferably 100nm or more, 200nm or more Or more than 300nm. By setting the Rz and Rsm of the surface on which the plating layer is formed after the photoresist layer is peeled off, the adhesion with the resin substrate and the solder resist to be further laminated in the next step can be obtained by setting the Rz and Rsm in the above range.

After the photoresist layer is peeled off, the copper oxide layer can be formed on the copper side of the composite copper wiring formed by etching (for example, the third surface in Figure 2 is an example), and the copper oxide layer can be formed, blackened, and rust-proof. Treatment or/and coupling treatment to form copper oxide layer, blackening treatment layer (black chromate layer), rust inhibitor layer (including benzotriazoles, etc.), coupling treatment layer (including silane coupling agent, etc.), etc. Copper wiring protective layer. Alternatively, a process of roughening the side surface made of copper may be performed. These treatments preferably do not affect the thickness of the layer containing a metal other than copper and the surface of the composite copper wiring, and the conduction between the wiring made of copper and the layer containing a metal other than copper.

After peeling off the photoresist layer, in order to protect the circuit, a step of applying a solder resist, which is an ink for forming an insulating film, may be included. Preferably, the solder resist is applied except for the part where the electronic component is attached. The solder resist can include 1) Expose and develop the unhardened part with a dilute alkali developer to form a fine pattern alkaline developing type solder resist; 2) Print the pattern by screen printing and irradiate UV light (ultraviolet rays) A type of UV-curing solder resist that is hardened by this; and 3) A type of solder resist that is hardened by heating by printing a pattern by a screen printing method, that is, a heat-curing solder resist.

For the surface where the plating layer is formed on the part that has not been processed by the solder resist, a soldering process may be included. Through this step, the natural oxidation of the metal forming the circuit can be suppressed, and the welding efficiency when mounting electronic parts can be improved.

After the soldering process, another step of soldering electronic parts may be included.

Alternatively, after peeling off the photoresist layer, it may include a step of thermocompression bonding the resin base material on the surface on which the plating layer is formed to produce a multilayer circuit board.

＜A. Structure＞ 1. Manufacturing the structure In Examples 1, 2 and Comparative Examples 1, 2, 3, 5, 6, and 7, copper foil (DR-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd. was used as the structure. Example 1 uses a glossy surface (flat surface when compared with the opposite surface: Rz=0.3μm) as the laminated dry film surface, and Example 2 uses a non-glossy surface (rough surface when compared with the opposite surface: Rz=0.8 μm) As the surface of the laminated dry film, Comparative Examples 1 to 3 and 5 used the glossy surface as the surface of the laminated dry film, and Comparative Examples 6 and 7 used the non-glossy surface as the surface of the laminated dry film. Example 3 and Comparative Example 4 used CCL (manufactured by Panasonic Co., Ltd., model R5775, thickness: 0.1 mm) as a structure, and a CCL-based H-VLP copper foil with a thickness of 18 μm was laminated on both sides of a prepreg R5670KJ.

(1) In the oxidation treatment of Examples 1 to 3 and Comparative Examples 1, 6, and 7, the structure was immersed in an oxidizing agent (sodium chlorite 60g/L; sodium hydroxide 9g/L; KBM-403 (3 -Glyoxypropyloxypropyltrimethoxysilane; Shin-Etsu Silicone Co., Ltd.) 2g/L) for 1.5 minutes to oxidize both sides of the structure. After the oxidation treatment, the structure is washed with water and dried. (2) Electroplating treatment in Examples 1 to 3 and Comparative Examples 6 and 7, then use nickel electroplating solution (nickel sulfate 240g/L; boric acid 30g/L) at 50°C and current density 0.5A/dm ² for structure Electroplating on both sides of the body. Example 1 was energized for 35 seconds, Example 2 was energized for 50 seconds, Example 3 was energized for 40 seconds, Comparative Example 6 was energized for 35 seconds, and Comparative Example 7 was energized for 70 seconds. After the electroplating process, the structure is washed with water and dried.

Regarding the structures of Examples and Comparative Examples, several test pieces were produced under the same conditions (Table 1). Table 1 Comparative example 7 Copper foil Non-glossy Oxidation plating 9 60 2 73°C for 1.5 minutes 240 30 1 70 without 82 0.80 612 51 1 0.57 0.57 1 ╳ without without without Comparative example 6 Copper foil Non-glossy Oxidation plating 9 60 2 73°C for 1.5 minutes 240 30 1 35 Have 36 0.91 232 15 1 0.27 - 7 ╳ without Have Have Comparative example 5 Copper foil Glossy surface without - - - - - - - - Have* - 1.12 889 53 3 0.59 0.55 0 ╳ without Have Have Comparative example 4 CCL - without - - - - - - - - Have - 0.73 745 58 3 0.59 - 10 ╳ CZ8101 Have Have Comparative example 3 Copper foil Glossy surface without - - - - - - - - Have - 0.55 709 62 3 0.58 - 12 ╳ CZ8101 Have Have Comparative example 2 Copper foil Glossy surface without - - - - - - - - Have - 0.55 718 63 3 0.28 - 12 ╳ without Have Have Comparative example 1 Copper foil Glossy surface Oxidation 9 60 2 73°C for 1.5 minutes - - - - without - 0.38 248 14 13 0.32 0.05 26 ND without Have Have Example 3 CCL - Oxidation plating 9 60 2 73°C for 1.5 minutes 240 30 1 40 without 41 0.65 320 twenty four 0 0.64 0.64 0 ○ without without without Example 2 Copper foil Non-glossy Oxidation plating 9 60 2 73°C for 1.5 minutes 240 30 1 50 without 63 0.86 528 41 0 0.64 0.62 0 ○ without without without Example 1 Copper foil Glossy surface Oxidation plating 9 60 2 73°C for 1.5 minutes 240 30 1 35 without 35 0.32 220 15 1 0.63 0.61 2 ○ without without without g/L g/L g/L - g/L g/L A/dm ² - Soft etching treatment nm μm nm kgf/cm kgf/cm Φ50 point peeling quantity (each 64) Wiring formability (EF L/S=40/40) Coarse processing on wiring Expansion of solder resist (240℃) Swelling of solder paste (240℃) Starting material Evaluation surface Material surface treatment Sodium hydroxide Sodium chlorite 3-Glyoxypropyloxypropyltrimethoxysilane - Nickel Sulfate Boric acid Current density Processing time [sec] Ni thickness Rz RSm L ^* (C light source 2 ^o ) Heat-resistant discoloration (ΔE ^* ab) normal After heat resistance test Oxidant Processing conditions Deployment Peel strength Oxidation treatment Plating treatment Evaluation before DFR is formed Evaluation after DFR is formed Evaluation after wiring formation *Comparative Example 5 uses CZ-8101 (manufactured by MEC Corporation) for etching instead of soft etching.

2. Evaluation of the test piece (results are shown in Table 1) For the test pieces of Comparative Examples 2, 3, 4, and 6, an aqueous solution of 1.8% hydrogen peroxide and 5% sulfuric acid was applied to the evaluation surface and treated at 25° C. for 43 seconds to perform a soft etching treatment for evaluation. For the test piece of Comparative Example 5, MEC etch BOND CZ-8101 (manufactured by MEC Co., Ltd.), which is an organic acid-based micro-etching agent, was used for evaluation after etching treatment at a spray pressure of 0.2 MPa for 30 seconds.

(1) Rz For the dry film-attached surface of the test pieces of the Examples and Comparative Examples, the contour curves were made from the observation results using a conjugate focus scanning electron microscope OPTELICS H1200 (manufactured by Lasertec Co., Ltd.), as specified in JIS B 0601:2001 The method to calculate Rz. The measurement conditions are the scan width of 100μm, the scan type is Area, the light source is blue light, and the Cut-off value is 1/5. Attach objective lens x100, eyepiece x14, digital zoom x1, and set Z pitch to 10nm, and obtain data at 3 positions, and Rz is the average of 3 positions.

(2) Rsm The dry film-attached surface of the test pieces of the Examples and Comparative Examples were observed with an atomic force microscope (AFM: Atomic Force Microscope), and the RSm was calculated according to JIS R 1683:2007. Device: Hitachi High-Tech Science system probe station AFM5000II Connected model: AFM5300E Cantilever: SI-DF40 Use the automatic setting function of AFM5000II to set (Amplitude attenuation rate, scanning frequency, I gain, P gain, A gain, S gain) Scanning area: 5μm square Number of pixels: 512x512 Measurement mode: DFM Measuring field of view: 5μm SIS mode: not used Scanner: 20μm scanner Measurement method: Make 3 corrections to measure. ◆RSm: Analysis of average cross section (lr=5μm)

(3) Lightness L ^*The dry film surface of the test piece of the example and the comparative example is measured on the lightness L ^{* in the L*} a ^* b ^* color system, using the spectral color difference manufactured by Nippon Denshoku Industries Co., Ltd. Calculate NF999 (lighting conditions: C; viewing angle conditions: 2; measurement items: L ^* a ^* b ^* ).

(4) Thickness of plating The method for measuring the average thickness of the plating in the vertical direction of the dry film surface of the test piece of the embodiment and the comparative example is to dissolve the test piece in 12% nitric acid, and use the ICP emission spectrometer 5100 SVDV ICP for the resulting liquid -OES (manufactured by Agilent Technologies) analyzes and measures the concentration of the metal, and calculates the thickness of the layered metal layer by considering the metal density and the surface area of the metal layer.

(5) Heat resistance The test pieces of the examples and comparative examples were tested for heat resistance by the color change caused by heating. After measuring the color difference (L*, a*, b*) of the test piece before heat treatment, put it in an oven at 225°C for 30 minutes to measure the color difference of the test piece after heat treatment. ^{Calculate ΔE*} ab from the obtained value according to the following formula. Mathematical formula 2: ΔE ^* ab=[(ΔL ^* ) ² +(Δa ^* ) ² +(Δb ^* ) ² ] ^1/2

(6) Peel strength with resin substrate For the dry film surface of the test pieces of the Examples and Comparative Examples, the laminated prepreg R5670KJ (manufactured by Panasonic, thickness 100μm) was used with a vacuum high-pressure press at a pressure of 2.9MPa, a temperature of 210°C, and a pressing time The condition of 120 minutes for thermocompression bonding. For the test piece after thermocompression bonding, one remains in its original state (normal state), and the other is placed in an oven at 180°C for 48 hours after the heat resistance test (after the heat resistance test) as the test sample. A 90° peel test (Japanese Industrial Standards (JIS) C5016) was performed on these measurement samples, and the peel strength (kgf/cm) was measured. (7) Stability of wettability The wettability of the dry film-attached surface of the test pieces of the examples and comparative examples was confirmed by the contact angle with water. Measure the contact angle of the test piece when the test piece is made (day 0) and after being placed at 25°C for 10 days. Specifically, it was performed with a contact angle meter (DropMaster500) at room temperature, and the contact angle with water after 60 seconds was measured with a liquid volume of 1 μmL. As shown in Figure 3, the wettability of the dry film-attached surface was maintained for 10 days after the test piece was made. This means that the surface roughness of the dry film surface does not change even after 10 days.

＜B. Multilayer body＞ (1) Thermal compression bonding of resin substrate The laminated prepreg R5670KJ (manufactured by Panasonic, thickness 100μm) of the test pieces of Examples 1, 2 and Comparative Examples 1 to 3, and 5 to 6 on the unattached surface of the test piece, used a vacuum high-pressure press to add The thermocompression bonding is performed under the conditions of a pressing pressure of 2.9 MPa, a temperature of 210° C., and a pressing time of 120 minutes. (2) Soft etching treatment For the test piece of Comparative Example 4 and the dry film surface of the test piece of Comparative Examples 2, 3, and 6 after thermocompression bonding of the resin substrate, apply 1.8% hydrogen peroxide; 5% sulfuric acid in water at 25 The temperature is processed for 43 seconds, thereby performing soft etching treatment. For the test piece of Comparative Example 5, MEC etch BOND CZ-8101 (manufactured by MEC Co., Ltd.) stock solution of an organic acid-based micro-etching agent was used for etching treatment at a spray pressure of 0.2 MPa for 30 seconds. The test piece was washed with water and dried after etching treatment. (3) Attach dry film For the test pieces of (1) and (2), dry film AK3021 (manufactured by Asahi Kasei) was attached at a roller temperature of 105° C. and a conveying speed of 0.4 m/min to obtain laminate test pieces of the Examples and Comparative Examples.

蝕刻因子（E.F.）計算式 （4）與阻焊劑之密著性 對於貼附乾膜後之實施例及比較例的積層體，曝光使佈線為L/S=40/40μm、長度5cm並顯影。顯影後，使用鹽酸1.3 mol/L；過氧化氫31.6 mol/L之水溶液，以於45℃、1.82m/min之速度條件進行蝕刻處理，藉此形成佈線。之後，浸漬於氫氧化鈉3%水溶液（水溫40℃）之溶液，剝離佈線上殘留的DFR。在剝離後之佈線上塗佈液狀阻焊劑：APB-300（田村製作所），以DI曝光機於100mJ/cm² 之條件曝光並覆膜，藉此形成阻焊劑圖案。在未形成阻焊劑圖案之佈線上的0.5mm×2mm之開口部（亦稱表面處理部）塗佈助焊劑ES1100（千住金屬製），以氮驅氣1500ppm、240℃進行加熱處理。加熱處理後，以外觀觀察確認阻焊劑有無膨脹。 （5）與錫膏（solder paste）之密著性 對於貼附乾膜後之實施例及比較例的積層體，曝光使佈線為L/S=40/40μm、長度5cm並顯影。顯影後，使用鹽酸1.3 mol/L；過氧化氫31.6 mol/L之水溶液，以於45℃、1.82m/min之速度條件進行蝕刻處理，藉此形成佈線。之後，浸漬於氫氧化鈉3%水溶液（水溫40℃）之溶液，剝離佈線上殘留的DFR。比較例3、4在之後使用有機酸系微蝕刻劑之MEC etch BOND CZ-8101（MEC股份有限公司製），以原液、噴壓0.2MPa、時間30秒進行蝕刻處理。在佈線上塗佈液狀阻焊劑：APB-300（田村製作所），以DI曝光機於100mJ/cm² 之條件曝光並覆膜，藉此形成阻焊劑圖案。在未形成阻焊劑圖案之佈線上的0.5mm×2mm之開口部進行預焊（preflux）處理後，塗佈錫膏（千十金屬工業社製，型號RGS800）。之後，以氮驅氣1500ppm、240℃進行加熱處理。加熱處理後，以外觀觀察確認錫膏有無膨脹。2. Evaluation of the laminate (results are shown in Table 1) (1) DFR peeling time For the laminate after the dry film is attached, expose to form a DFR with a width of 45μm and a length of 5cm, and 1% by mass at 30°C The sodium carbonate aqueous solution was developed under the condition of spray pressure of 2kg/cm ^2. After development, use an aqueous solution of hydrochloric acid 1.3 mol/L and hydrogen peroxide 31.6 mol/L to perform etching treatment at 45°C and a speed of 1.82 m/min. After the etching treatment, it was immersed in a solution of 3% sodium hydroxide aqueous solution (water temperature 40°C), and the time until DFR was completely peeled off was measured. (2) The number of Φ50 dots to be peeled off. The layered body is exposed to form several Φ50μm dot-shaped DFR and developed. After development, use an aqueous solution of hydrochloric acid 1.3 mol/L and hydrogen peroxide 31.6 mol/L to perform etching treatment at 45°C and a speed of 1.82 m/min. After the etching process, a CCD camera was used to count the number of dots remaining without being etched. If the DFR is not sufficiently adhered, the DFR will peel off after exposure and development, and dots will fall off after the etching process. (3) Wiring formability For the laminated body, the wiring is exposed to L/S=40/40μm and the length is 5cm and developed. After development, an aqueous solution of hydrochloric acid 1.3 mol/L and hydrogen peroxide 31.6 mol/L was used for etching at 45° C. and 1.82 m/min to form wiring. After that, it was immersed in a solution of 3% sodium hydroxide aqueous solution (water temperature 40°C), and the DFR remaining on the wiring was peeled off. After peeling off the DFR, the etch factor (etch factor) was calculated from the SEM cross-sectional image of the test piece using the following formula. Figure 4 shows the SEM cross-sectional image of Example 2. The larger the value of the etching factor, the better the etching accuracy, and it is generally about 2.5 to 3.5. From this index, 4.0 or more is regarded as ○, and less than 4.0 is regarded as ╳. Mathematical formula 3:

Etching factor (EF) calculation formula (4) and adhesiveness of solder resist For the laminated body of the embodiment and the comparative example after the dry film is attached, the wiring is exposed to L/S=40/40μm and the length is 5cm and developed. After development, an aqueous solution of hydrochloric acid 1.3 mol/L and hydrogen peroxide 31.6 mol/L was used for etching at 45° C. and 1.82 m/min to form wiring. After that, it was immersed in a solution of 3% sodium hydroxide aqueous solution (water temperature 40°C), and the DFR remaining on the wiring was peeled off. Coat liquid solder resist: APB-300 (Tamura Manufacturing Co., Ltd.) on the stripped wiring, expose it with a DI exposure machine at 100mJ/cm ² and cover it to form a solder resist pattern. Apply flux ES1100 (manufactured by Senju Metals) on the 0.5mm×2mm openings (also called surface treatment parts) on the wiring where the solder resist pattern is not formed, and heat it with nitrogen purging gas at 1500ppm and 240°C. After the heat treatment, the appearance of the solder resist was observed to confirm whether or not the solder resist had swelled. (5) Adhesion to solder paste For the laminates of the examples and comparative examples after the dry film is attached, the wiring is exposed to L/S=40/40μm and the length is 5cm and developed. After development, an aqueous solution of 1.3 mol/L hydrochloric acid and 31.6 mol/L hydrogen peroxide was used to perform etching treatment at 45° C. and 1.82 m/min to form wiring. After that, it was immersed in a solution of 3% sodium hydroxide aqueous solution (water temperature 40°C), and the DFR remaining on the wiring was peeled off. In Comparative Examples 3 and 4, MEC etch BOND CZ-8101 (manufactured by MEC Co., Ltd.), which is an organic acid-based micro-etching agent, was used to perform etching treatment with a stock solution at a spray pressure of 0.2 MPa for 30 seconds. Coat liquid solder resist: APB-300 (Tamura Manufacturing Co., Ltd.) on the wiring, ^{expose and coat with a DI exposure machine at 100mJ/cm 2} to form a solder resist pattern. After preflux treatment is performed on the 0.5mm×2mm openings on the wiring where the solder resist pattern is not formed, a solder paste (manufactured by Senju Metal Industry Co., Ltd., model RGS800) is applied. After that, heat treatment was performed with nitrogen purging gas at 1500 ppm and 240°C. After the heat treatment, visually observe whether the solder paste has swelled or not.

3. Conclusion The ΔE ^* ab of Comparative Example 1 is large, and the copper oxide-containing layer on the non-adherent surface of the resin is oxidized when the laminate is heated to form a fragile layer. Therefore, the adhesion with DFR is weak, and DFR peels off on the way, so the circuit cannot be formed. In Comparative Examples 2 to 4, even if the soft etching treatment was performed, the adhesive force with DFR was still weak, and dots were dropped. Also, as in Comparative Example 3, after lamination, soft etching was performed in order to achieve both the adhesion and peelability with DFR, and the roughening treatment after wiring formation was required to obtain adhesion with solder resist, etc., which required stages. Surface treatment is applied to the conductor, which increases the number of steps. In Comparative Example 5, the adhesion to DFR was too strong, and it was difficult to peel off the DFR after the circuit was formed by the etching process. In Comparative Example 6, a part of the nickel plating was peeled off due to soft etching, so the EF was lowered. Too thick nickel plating also reduces EF (Comparative Example 7). On the other hand, the adhesion between Examples 1 to 3 and DFR is strong, and after the circuit is formed by the etching process, the DFR can be easily peeled off. And EF is also good. In addition, in Examples 1 to 3, after peeling off DFR, even without any surface treatment, there are 1) high adhesion between the solder resist and the surface on which the nickel plating layer is formed, and 2) the difference between the solder and the surface on which the nickel plating layer is formed. The adhesion is also high. In addition, continuity can also be confirmed between the copper foil part of the conductor and the solder.

Industrial Applicability: According to the present invention, it is possible to provide a laminate with a photoresist layer, which is suitable for manufacturing printed wiring boards in which wiring is formed by exposure, development and etching. Suppressing the reflection of exposure light also helps to form a solder resist layer that is hardened by illumination. Also, compared with conventional methods. There is no need for a soft etching step before attaching the dry film, and no wiring surface treatment after the DFR is peeled off (Figure 1), so the time and cost for manufacturing the printed circuit board can be reduced.

1: the first side 2: second side 3: third side

[Figure 1] Shows the manufacturing steps of a printed circuit board containing composite copper wiring and the manufacturing steps of a general printed circuit board in an embodiment of the present invention. [Figure 2] A composite copper wiring showing one embodiment of the present invention, a printed circuit board in which the composite copper wiring is laminated on one side of a resin substrate, and a printed circuit board in which the composite copper wiring is laminated on both sides of the resin substrate Schematic drawing of the cross-section. The composite copper wiring system has a plating layer containing a metal other than copper and a layer containing copper oxide on the first surface (1) of the wiring formed of copper. Whether there is a plating layer containing a metal other than copper or a layer containing copper oxide on the second surface (2) of the thermocompression bonding surface with the resin substrate. The second surface (2) can be roughened by copper particles. The third surface (3) can maintain the wiring formed by copper, and can also have a copper wiring protective layer such as a copper oxide layer or a rust-proof layer. [Figure 3] Shows the change with time in the contact angle between the surface of the plating layer on which the laminated photoresist layer is formed and the water in the structure of one embodiment of the present invention. [Figure 4] Scanning electron microscope (SEM) cross-sectional image of the composite copper wiring before stripping of the photoresist layer produced in Example 2 of the present invention (upper: 3000 times, lower: 30,000 times). The surface on which the photoresist layer is laminated has fine irregularities formed by a plating layer containing a metal other than copper and a layer containing copper oxide.

Claims (40)

A composite copper wiring is provided on the first side of a wiring formed of copper having a first side, a second side, and a third side, and has a first copper oxide-containing layer, and the first copper oxide-containing layer A first plating layer containing a metal other than copper is formed on the surface. The composite copper wiring of claim 1, wherein there is conduction between the wiring formed of copper and the first plating layer. The composite copper wiring of claim 1 or 2, wherein a second copper oxide-containing layer is provided on the second surface, and the surface of the second copper oxide-containing layer is formed with a second plating containing a metal other than copper Cladding. The composite copper wiring of claim 3, wherein the wiring formed of copper and the second plating layer are electrically connected. The composite copper wiring according to any one of claims 1 to 4, wherein a copper wiring protective layer is provided on the third surface, and the copper wiring protective layer is selected from a copper oxide layer, a blackening treatment layer, and a rust inhibitor layer And a group of coupled processing layers. A printed substrate is provided with a resin base material in the second area layer of the composite copper wiring according to any one of claims 1 to 5. Such as the printed circuit board of claim 6, wherein the first surface is mounted with electronic components. A laminated body has a structure, the first surface and the second surface of the structure are surfaces made of copper, a part or all of the first surface of the structure has a first layer containing copper oxide, the first A part or all of the surface of a copper oxide-containing layer is formed with a first plating layer including a metal other than copper, and a part or all of the first plating layer has a photoresist layer on the surface. ^{The layered body of claim 8, wherein the value of the lightness L*} of the surface on which the first plating layer is formed is less than 50. The layered body of claim 8 or 9, wherein the color change of the surface on which the first plating layer is formed before and after the heat treatment is 10 or less when heat-treated at 225°C for 30 minutes. The laminate according to any one of claims 8 to 10, wherein the Rz of the part or all of the photoresist layer on the surface on which the first plating layer is formed is 0.2 μm or more and 1.0 μm or less. The laminate according to any one of claims 8 to 11, wherein the RSm of the part or all of the photoresist layer on the surface on which the first plating layer is formed is 600 nm or less. The laminate according to any one of claims 8 to 12, wherein the first plating layer contains nickel. The laminate according to any one of claims 8 to 13, wherein the average thickness of the first plating layer is 30 nm or more and 70 nm or less. The laminate according to any one of claims 8 to 14, wherein the photoresist layer is a dry film photoresist, a positive liquid photoresist, or a negative liquid photoresist. The laminate according to any one of claims 8 to 15, wherein the structure is a piece of copper foil. The laminate of claim 16, wherein a part or all of the second surface has a second copper oxide-containing layer, and a part or all of the surface of the second copper oxide-containing layer is formed with a metal other than copper The second plating layer. The laminate of claim 17, wherein a part or all of the surface of the second plating layer has a resin base material. The laminate of claim 18, wherein the peel strength between the resin substrate and the second plating layer is 0.5 kgf/cm or more. The laminate of claim 18 or 19, wherein the resin base material contains selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, liquid crystal polymer, and triphenyl phosphite At least one insulating property from the group consisting of ester, fluororesin, polyether imide, polyether ether ketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin Resin. The laminate according to any one of claims 8 to 15, wherein the structure is a copper-clad laminate. A method for manufacturing a laminate is performed on a structure having a first surface and a second surface made of copper, a part or all of the first surface has a first layer containing copper oxide, the first A first plating layer containing a metal other than copper is formed on part or all of the surface of the layer containing copper oxide, and the manufacturing method of the laminate includes forming a photoresist layer on part or all of the surface of the first plating layer A step of. The method for manufacturing a laminate of claim 22, wherein ^{the value of the lightness L*} of the surface on which the first plating layer is formed is less than 50. The method for manufacturing a laminate according to claim 22 or 23, wherein when the heat treatment is performed at 225° C. for 30 minutes, the color change of the surface on which the first plating layer is formed before and after the heat treatment is 10 or less. The method for manufacturing a laminate according to any one of claims 22 to 24, wherein the first plating layer contains nickel. The method for manufacturing a laminate according to any one of claims 22 to 25, wherein the average thickness of the first plating layer is 30 nm or more and 70 nm or less. The method for manufacturing a laminate according to any one of claims 22 to 26, wherein the photoresist layer is a dry film photoresist, a positive liquid photoresist, or a negative liquid photoresist. The method for manufacturing a layered body according to any one of claims 22 to 27, wherein the surface on which the first plating layer is formed is not subjected to soft etching treatment, and the soft etching treatment is buff polishing, brush polishing, and chemical polishing. The method for manufacturing a laminate according to any one of claims 22 to 28, wherein the structure is a piece of copper foil. The method of manufacturing a laminate of claim 29, wherein a part or all of the second surface of the structure has a second copper oxide-containing layer, and a part or all of the surface of the second copper oxide-containing layer A second plating layer containing a metal other than copper is formed. The method for manufacturing a laminate according to claim 30, which includes a step of laminating a resin base material on a part or all of the surface on which the second plating layer is formed. The method for manufacturing a laminate according to claim 31, wherein the peel strength between the resin base material and the second plating layer is 0.5 kgf/cm or more. The method for manufacturing a laminate according to claim 31 or 32, wherein the resin base material contains selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, liquid crystal polymer, and At least one of the group consisting of triphenyl phosphate, fluororesin, polyether imine, polyether ether ketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin An insulating resin. The method for manufacturing a laminate according to any one of claims 22 to 28, wherein the structure is a copper-clad laminate. For example, the method of manufacturing a laminate of any one of claims 31 to 34, which additionally includes: The step of irradiating a part of the photoresist layer with light and developing, etching the first surface to form a wiring pattern on the structure; and The step of peeling off the photoresist layer after the etching process from the laminate. The method for manufacturing a laminate according to claim 35, wherein Rz of the surface on which the first plating layer is formed after peeling off the photoresist layer is 0.2 μm or more and 1.0 μm or less. The method for manufacturing a laminate of claim 35 or 36, wherein the RSm of the surface on which the first plating layer is formed after the photoresist layer is peeled off is 600 nm or less. A manufacturing method of a printed substrate, including: The step of irradiating a part of the photoresist layer of the laminated body according to any one of claims 18 to 21, and developing, etching the first surface to form a wiring pattern on the structure; and The step of peeling off the photoresist layer after the etching process from the laminate. The method of manufacturing a printed circuit board according to claim 38, wherein Rz of the surface on which the first plating layer is formed after peeling off the photoresist layer is 0.2 μm or more and 1.0 μm or less. The method for manufacturing a printed circuit board according to claim 38 or 39, wherein the RSm of the surface on which the first plating layer is formed after the photoresist layer is peeled off is 600 nm or less.

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