JP2018135561A - Copper-clad multilayer substrate, manufacturing method thereof, and wiring substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem caused by using a nickel-chromium alloy as a base metal layer in a two-layer copper-clad laminate manufactured by a metallizing method, and to improve high peel strength and insulation reliability. It provides a laminated substrate. SOLUTION: In a copper-clad laminated substrate provided with a base layer provided on at least one surface of an insulator film without using an adhesive and a copper conductor layer on the surface of the base layer, the base layer contains nitrogen. A copper-clad laminated substrate which is titanium nitride containing 18 to 22.6% by mass and has a functional group having a nitrogen atom arranged on the surface of an insulating film provided with a base layer thereof. [Selection diagram] None

Description

  The present invention relates to a copper-clad laminate having a laminated structure of a base layer and a copper conductor layer formed on the surface of the base layer without an adhesive on at least one surface of the insulator film, and a method for producing the same More specifically, the present invention relates to a copper-clad laminate using titanium nitride as the underlying layer.

  A flexible printed wiring board includes a three-layer copper-clad laminate (for example, see Patent Document 1) in which a copper foil serving as a conductor layer is bonded onto an insulator film using an adhesive, and an adhesive on the insulator film. And a two-layer copper-clad laminate in which a copper coating layer as a conductor layer is directly formed by a dry plating method or a metallizing method of a wet plating method without using the above.

  By the way, with the recent increase in the density of electronic devices, a wiring board with a narrowed wiring width has been required. To obtain a wiring board from a copper-clad laminate through wiring such as etching, a copper-clad board is required. Instead of a three-layer copper-clad laminate substrate, a two-layer copper-clad laminate substrate is mainly used as the laminate substrate.

  In this two-layer copper-clad laminate, a copper coating layer having a uniform thickness is formed on at least one surface of an insulator film, and as a means for that, an electroplating method is usually employed. In order to perform electroplating, it is common to form a thin metal layer on an insulator film before electroplating to impart conductivity to the entire surface, and to perform electroplating on the surface ( For example, see Patent Document 2). The thin metal layer formed on the insulator film is formed using a dry plating method such as a vacuum deposition method or an ion plating method.

In such circumstances, the adhesion between the insulator film and the copper coating layer becomes very weak when a brittle layer such as CuO or Cu ₂ O is formed at the interface, so that the copper conductor required for a printed wiring board is required. In order to maintain the adhesion strength with the layer, a nickel-chromium alloy layer is provided as a base metal layer between the insulator film and the copper coating layer (see Patent Document 3).

  In a two-layer copper clad laminated substrate manufactured by the current metallizing method, a nickel-chromium alloy is used for the base metal layer. The advantage of using a nickel-chromium alloy for the base metal layer is that when a nickel-20% chromium alloy is used, the peel strength is high at 150 ° C. and after 168 hours in heat resistance. On the other hand, the nickel-chromium alloy tends to remain on the polyimide surface of the insulator film because the bond with insulation is strong, and if it remains between the wires, nickel will migrate out of the nickel and chromium remaining on the surface. However, the insulation resistance deteriorates, and in some cases, there is a problem of insulation reliability that a short circuit is caused.

JP-A-6-132628 Japanese Patent Laid-Open No. 8-139448 JP-A-6-120630 Japanese Patent Laying-Open No. 2015-101778

  In order to solve the problem of using a nickel-chromium alloy for a base metal layer in a two-layer copper clad laminated substrate manufactured by a metallizing method, the present invention provides a base layer instead of using a nickel-chromium alloy. The present invention provides a copper-clad laminate having improved peel strength and insulation reliability using titanium nitride.

  According to a first aspect of the present invention, there is provided a base layer provided on at least one surface of the insulator film without an adhesive, and a copper-clad laminate including a copper conductor layer on the surface of the base layer. It is a copper clad laminated substrate characterized in that the base layer is titanium nitride containing 18 to 22.6% by mass of nitrogen.

  According to a second aspect of the present invention, there is provided a copper-clad laminate, wherein a functional group having a nitrogen atom is arranged on the surface of an insulating film provided with the underlayer in the first aspect.

  According to a third aspect of the present invention, there is provided a copper-clad laminate, wherein the film thickness of the underlayer in the first and second aspects is 5 to 300 nm.

  A fourth invention of the present invention is a copper-clad laminate, wherein the insulator film in the first to third inventions is polyimide.

  According to a fifth aspect of the present invention, there is provided a base layer provided on at least one surface of an insulator film without an adhesive, and a method for producing a copper-clad laminate having a copper conductor layer on the surface of the base layer. In the present invention, the surface of the insulating film on the base layer side is subjected to plasma treatment or ion beam treatment in a mixed gas atmosphere with nitrogen gas or a rare gas containing 2% by volume or more of nitrogen gas. And a method for producing a copper-clad laminate.

  According to a sixth aspect of the present invention, there is provided a method for producing a copper-clad laminate, wherein the underlayer in the fifth aspect is formed by a dry plating method.

  According to a seventh aspect of the present invention, there is provided a method for producing a copper-clad laminate, wherein the dry plating method for forming the underlayer in the sixth aspect is a sputtering method and a nitride target is used. is there.

  According to an eighth aspect of the present invention, a wiring having a laminated structure in which a base layer is disposed on at least one surface of an insulator film without using an adhesive, and a copper conductor layer is disposed on the surface of the base layer. The wiring board is characterized in that the underlying layer is titanium nitride containing 18 to 22.6% by mass of nitrogen.

  A ninth invention of the present invention is a wiring board characterized in that a functional group having a nitrogen atom is arranged on the surface of an insulating film provided with the underlayer in the eighth invention.

  The copper clad multilayer substrate according to the present invention provides a copper clad multilayer substrate in which a copper conductor layer having high adhesion and high insulation reliability is formed by using titanium nitride as an underlayer. Can do. In addition, by using this substrate, it is possible to efficiently obtain a wiring substrate having a highly reliable narrow width and narrow pitch wiring portion having a wiring portion with high adhesion. Therefore, the effect is large industrially.

It is an example of the roll-to-roll sputtering apparatus suitable for continuous manufacture of the copper clad laminated substrate which concerns on this invention.

  The copper-clad laminate according to the present invention includes a titanium nitride underlayer without an adhesive on at least one surface of an insulator film, and a copper conductor layer having a desired thickness on the surface of the underlayer. This is a copper-clad laminate.

(1) Insulator film The insulator film may be a film having electrical insulation, and it is desirable to use a resin film. Examples of the insulator film that can be used in the present invention include polyimide films, polyamide films, polyester films such as polyethylene terephthalate (PET) and polyethylene terephthalate (PEN), polytetrafluoroethylene films, polyphenylene sulfide films, and polyethylene. An insulating resin film selected from naphthalate film or liquid crystal polymer film is used according to the application in consideration of heat resistance, dielectric properties, electrical insulation, wiring board manufacturing process and chemical resistance in the next process, etc. It can be selected as appropriate. Among these, a polyimide film is desirable from the viewpoint of electrical insulation, heat resistance, and chemical resistance.
Further, the thickness of the insulator film is desirably 10 μm to 100 μm from the viewpoint of handling and flexibility.

(2) Underlayer In the copper clad laminated substrate according to the present invention, titanium nitride containing 18 to 22.6 mass% of nitrogen is used for the underlayer. Conventionally known copper-clad laminates use a nickel-chromium alloy for the underlayer, but when processing a copper-clad laminate to a wiring board, complete removal of the nickel remaining on the insulator film is not possible. desirable. Therefore, several underlayers that do not contain nickel have been proposed, but they are less prone to oxidation-reduction reactions due to electrochemical reactions between wires, and have insulation reliability due to migration resistance, which is electrochemical corrosion. Titanium-based underlayers are promising.

  However, in the case of forming a film using titanium metal as an underlayer, titanium metal is very active, and is easily oxidized by a small amount of oxygen during sputtering. There is a problem that the strength is significant.

  In addition, in order to improve the adhesion between the insulator film and the base layer, that is, the peel strength, usually in the process of manufacturing the copper-clad laminate, the insulator film molecules present on the insulator film surface are uncured oligomers. Etc., and oxygen plasma treatment for introducing an oxygen functional group into a polymer constituting the insulator film from which the fragile layer has been removed are performed.

  For example, a functional group having oxygen atoms is formed on the polyimide film of the insulator film by oxygen plasma treatment or the like, and a treatment for increasing the bond with the nickel-chromium alloy is performed. However, in the case of a titanium-based underlayer, this oxygen plasma treatment also causes oxidation of the underlayer during film formation due to oxygen-containing functional groups introduced into the insulator film, causing deterioration in peel strength. The analysis of the oxidation of the underlayer can be known from the bond between oxygen atoms and titanium atoms from chemical shifts observed from XPS analysis (X-ray Photoelectron Spectroscopy), Auger electron analysis, and the like.

In the copper clad laminated substrate of the present invention, it is necessary that the titanium of the underlayer is not bonded to oxygen.
Therefore, in the copper clad laminated substrate according to the present invention, it is desirable to form a functional group having nitrogen atoms on the surface of the insulator film before the formation of the underlayer to prevent oxidation.
Here, taking the polyimide film to the insulator film as an example, one of the cyclic bonds of nitrogen atoms constituting the imide bond of the polyimide molecule is cut to produce an amide bond, and at the same time, the imide bond is cut. On the other hand, a nitrogen atom is introduced, and the introduced nitrogen atom becomes an amino group.
In order to introduce a functional group having a nitrogen atom on the surface of the insulator film, the atmosphere should be plasma treatment or ion beam treatment using nitrogen gas or a mixed gas containing 2% by volume or more of nitrogen gas. Is desirable. Here, the rare gas is argon, xenon, krypton, or helium, and argon is desirable from the viewpoint of availability.

  From the viewpoint of atmospheric gas pressure control, ion beam treatment is preferable to plasma treatment. When an applied voltage of 800 V to 2600 V is applied in the plasma treatment and an applied voltage of 600 V to 2600 V is applied in the ion beam treatment, the fragile layer of the insulator film can be removed and a functional group having a nitrogen atom can be introduced. The applied voltage may be appropriately selected in consideration of the characteristics of the insulator film.

  The underlayer is formed by a dry plating method, and a sputtering method is preferable among the dry plating methods. The underlayer can be formed by reactive sputtering in which a sputtering cathode is provided with a metal titanium target and nitrogen gas is added to a rare gas such as argon as a sputtering gas. Further, it is more desirable to form a film using a titanium nitride target, and the use of the titanium nitride target prevents oxidation of the underlayer even if oxygen or water adsorbed on the sputtering apparatus is released into the sputtering atmosphere. it can.

The film thickness of the underlayer is preferably 5 to 300 nm.
If the thickness of the underlying layer is less than 5 nm, a dense underlying layer cannot be formed, and if it is thin, it cannot exist as a film, resulting in island-like precipitates, and the corrosion resistance of the finally obtained copper-clad laminated substrate or wiring substrate , And oxidation proceeds under the influence of oxygen. On the other hand, if the film thickness of the underlayer exceeds 300 nm, it becomes difficult to remove the underlayer by etching during wiring processing.

  The composition of the titanium nitride of the underlayer includes 18 to 22.6% by weight of nitrogen. If the nitrogen content of titanium nitride is 18 to 22.6 mass%, the underlying layer will not be altered even if the finally obtained copper-clad laminate or wiring board is heat-treated at 150 ° C. in the atmosphere. .

(3) Copper conductor layer In the copper clad laminated substrate according to the present invention, a copper conductor layer is formed on the surface of the base layer. The copper conductor layer preferably has a thickness of 1 to 20 μm.
The copper conductor layer may have a laminated structure of a copper thin film layer and a copper electroplated layer formed on the surface of the underlayer. The copper thin film layer preferably has a thickness of 50 nm to 1000 nm. The copper thin film layer can be formed by a dry plating method such as a sputtering method or a vapor deposition method.
The copper thin film layer is provided on the surface of the titanium nitride underlayer even if it is a titanium nitride underlayer having conductivity, since the resistance value of the underlayer is high when the underlayer is 5 nm to 100 nm. It is difficult to provide a copper electroplating layer of a copper conductor layer by plating. Therefore, when the underlayer is 100 nm or less, it is desirable to provide a copper thin film layer on the surface of the underlayer. On the other hand, when the copper thin film layer can be omitted depending on the film thickness of the underlayer, a copper-clad laminate in which the underlayer and the copper electroplating layer of the copper conductor layer are laminated is obtained.

The copper electroplating layer can be formed on the surface of the copper thin film layer by electroplating. Electroplating can be performed by a known electroplating method using a known copper electroplating bath or the like.
The sum total of the film thickness of a copper thin film layer and a copper electroplating layer should just be 1-20 micrometers.

(4) Method for Producing Copper Clad Multilayer Substrate One example of a method for producing a copper clad multilayer substrate according to the present invention is to form a base layer and, if necessary, a copper thin film layer on a surface of at least one surface of an insulator film by a dry plating method. Then, a copper electroplating layer of a copper conductor layer is formed by known copper electroplating, and is completed.

FIG. 1 is an example of a roll-to-roll sputtering apparatus 10 suitable for continuous production of a copper-clad laminate. A procedure for forming a base layer and a copper thin film layer with the roll-to-roll sputtering apparatus 10 will be described.
The roll-to-roll sputtering apparatus 10 includes a rectangular parallelepiped casing 11 that accommodates most of the components.
The casing 11 may have a cylindrical shape, and the shape thereof is not limited as long as the decompressed state can be maintained in a range of 10 ⁻⁴ Pa to 1 Pa.

  In this housing 11, a polyimide film F, which is a long insulator film substrate, is fed with an unwinding roll 12, guide rolls 13a, 13b, 13c, 13d, 13f, 13g, 13h, 13i, 13j, a can The roll 14, the ion irradiation source 15, the front feed roll 16a, the can roll 17, the sputtering cathodes 18a, 18b, 18c and 18d, the rear feed roll 16b, and the take-up roll 19 are stored. The guide rolls 13f and 13g are provided with a tension sensor for measuring the transport tension of the insulating film. The unwinding roll 12, the can roll 14, the can roll 17, the front feed roll 16 a, and the take-up roll 19 are provided with power by a servo motor. The unwinding roll 12 and the winding roll 19 are configured such that the tension balance of the polyimide film F, which is a long insulator film, is maintained by torque control using a powder clutch or the like.

  The sputtering cathodes 18a to 18d are of a magnetron cathode type and are arranged to face the can roll 17. The width direction dimension of the polyimide film F of the sputtering cathodes 18a to 18d only needs to be wider than the width of the polyimide film F.

  In the polyimide film F, functional groups having nitrogen atoms are formed on the surface of the polyimide film F, which is an insulator film, by the ion irradiation source 15 disposed facing the can roll 14. Therefore, a mixed gas obtained by adding nitrogen gas to a rare gas is supplied to the ion irradiation source. Here, when the functional group having nitrogen atoms is introduced by the plasma treatment, the plasma treatment is performed by arranging plasma irradiation means instead of the ion irradiation source 15.

  The polyimide film F is transported through the roll-to-roll sputtering apparatus 10 and is formed by sputtering cathodes 18 a to 18 d facing the can roll 17, and a base layer is formed and processed into a polyimide film F 2 with a base layer. For example, a titanium nitride target is attached to the sputtering cathode 18a, a copper target is attached to the sputtering cathodes 18b, 18c, and 18d, and a copper thin film layer is formed on the surface of the titanium nitride underlayer. It becomes. Of course, it is also possible to provide a polyimide film F2 with an underlayer in which a titanium nitride target is attached to all of the sputtering cathodes 18a to 18d and only the underlayer is formed.

The underlayer of titanium nitride can be formed by reactive sputtering in an atmosphere in which nitrogen gas is added to argon as a sputtering gas.
The surfaces of the can rolls 14 and 17 are finished with hard chrome plating, and a coolant and a heating medium supplied from the outside of the housing 12 are circulated in the can rolls 14 and 17 to be adjusted to a substantially constant temperature.

Further, after forming the base layer by sputtering, the copper thin film layer may be formed by vapor deposition.
A copper-clad laminate is completed by forming a copper electroplating layer on a polyimide film with an underlayer obtained by the roll-to-roll sputtering apparatus 10 using a known roll-to-roll continuous electroplating apparatus.
Note that the roll-to-roll sputtering apparatus 10 can continuously perform plasma treatment or ion beam treatment on a long insulator film, and then perform underlayer film formation. Needless to say, the underlayer may be formed not by continuous processing but by plasma processing or ion beam processing in a single wafer type in a vacuum chamber.

(5) Wiring board The copper-clad laminate according to the present invention can be processed by a known semi-additive method or a known subtractive method.
In the subtractive method, an opening is provided in the resist layer where the copper conductor layer or the like is to be removed on the surface of the copper conductor layer of the copper-clad laminate, and an unnecessary copper conductor layer exposed by the opening In this method, the formation is removed by etching or the like. Ferric chloride aqueous solution or the like can be used for etching removal of the copper conductor layer, and for removing the underlayer, hydrogen peroxide, fluoride ion supply source, phosphonobutane tricarboxylic acid disclosed in Patent Document 4 is used. And an azole compound, an etching solution containing a mixture of hydrochloric acid, sulfuric acid and aromatic sulfonic acid, or an etching solution containing ammonia and hydrogen peroxide can be used.

  On the other hand, in the semi-additive method, an opening (not shown) of a resist layer is provided at a position where a wiring pattern is to be formed on the surface of the copper conductor layer of the copper-clad laminate, and the copper conductor exposed through the opening. After forming a wiring part with a desired film thickness by electro copper plating using the layer as a cathode, the resist layer is removed, and the underlying layer and the copper conductor layer other than the wiring part are removed by flash etching or the like In this way, the wiring board is completed. The copper conductor layer can be removed by using a commercially available semi-additive copper removal solution, and the underlayer can be removed by etching using a mixed solution of hydrochloric acid, sulfuric acid and aromatic sulfonic acid as in the subtractive method. A liquid can be used.

  So far, the copper-clad laminate according to the present invention has been described. The copper-clad laminate according to the present invention forms a functional group having a nitrogen atom on the surface of an insulator film, prevents oxidation, prevents oxidation of Ti during sputtering, and bonds with oxygen by reaction with a polyimide film. This improves the adhesion of the copper-clad laminate. Furthermore, since a nickel-based alloy that is likely to remain on the surface of the insulator film after wiring processing is not used for the underlayer, it is obtained from a copper-clad laminate having no migration of nickel and excellent in migration resistance, and the copper-clad laminate It is possible to provide a wiring board.

Examples of the present invention will be described below together with comparative examples. Characteristic evaluation was performed by the following measurement methods.
[Peel strength]
The peel strength was measured by a measurement method based on IPC-TM-650 and NUMBER 2.4.9. However, the lead width was 1 mm and the peel angle was 90 °.
The test sample was prepared by a subtractive method using a ferric chloride etchant for etching the lead and a mixed solution of hydrochloric acid, sulfuric acid and aromatic sulfonic acid to remove the underlayer. After measuring the 90 ° peel strength (normal peel strength) of the obtained sample, a part of the sample was stored in an oven, then left at 150 ° C. for 168 hours, taken out, and left to reach room temperature. The heat resistance of the peel strength (heat-resistant peel strength [based on IPC-TM-650, NUMBER 2.4.9]) was evaluated.

[HHBT test]
The HHBT (High Temperature High Bias Test) test, which is an indicator of electrochemical corrosion resistance and is an environmental resistance test, is a 30 μm pitch (line / space = 15/15 μm) formed by a subtractive method on a test piece. A comb tooth test piece was used. Etching was performed with a ferric chloride etching solution and a mixed solution of hydrochloric acid, sulfuric acid and aromatic sulfonic acid (SX-621 manufactured by ADEKA Corporation) for removing the underlayer.

The measurement is based on JPCA-ET04, 85 ° C., 85% R.D. H. Under the environment, DC 60V is applied between the terminals, and the resistance change for 1000 hours after the application is observed. When the resistance became 10 ⁶ Ω or less, it was judged as a short circuit failure, and after 1000 hours, it was judged as acceptable if it was 10 ⁶ Ω or more.

[Evaluation of corrosion resistance]
Next, as an index of corrosion resistance, back surface discoloration can be mentioned. This was performed by observing the back surface of the sample after the HHBT test.
When significant discoloration was seen, it was judged as defective “x”, and when no discoloration was seen or slight, it was judged as acceptable “◯”.

A 38 μm-thick polyimide film (product name “Kapton 150EN” manufactured by Toray Diupon Co., Ltd.) was cut into a size of 12 cm × 12 cm and placed in a vacuum chamber. One side of the polyimide film was plasma-treated at a voltage of 2000 V in a nitrogen gas atmosphere with a purity of 99.995 wt%. Thereafter, a sputtering cathode having a titanium nitride target containing 20% by mass of nitrogen was formed, and a base layer was formed on the polyimide film to a thickness of 20 nm, and a copper target was attached to the surface of the base layer with another sputtering cathode. A thin film layer was formed to a thickness of 200 nm to obtain a polyimide film with an underlayer.
Next, the obtained polyimide film with an underlayer was taken out of the vacuum chamber, and an electroplating method using a copper sulfate electroplating bath having a pH of 1 was used to form a copper electroplating layer on the surface of the copper thin film layer to 8 μm. 1 was obtained.

A sample for peel strength test and a comb-tooth test piece for HHBT test were prepared from the obtained copper-clad laminated substrate by a subtractive method and used for each test.
The results are summarized in Table 1.

In the copper clad laminated substrate of Example 1, the thickness of the titanium nitride underlayer was set to 300 nm, and a polyimide film with an underlayer without a copper thin film layer provided on the surface of the underlayer was obtained. The copper-clad laminate board according to Example 2 was obtained by manufacturing under the same conditions as in Example 1 except that a copper electroplating layer was formed to a thickness of 8 μm on the surface of the copper-clad laminate. Evaluation was performed in the same manner as in 1.
The test results are summarized in Table 1.
In addition, in the copper clad laminated substrate of Example 2, since the TiN layer as the base layer has conductivity, it is possible to directly form a copper plating layer, which can be a merit in process.

(Comparative Example 1)
In the production of the copper-clad laminate of Example 1, Example 1 was performed except that the atmosphere of the plasma treatment was a mixed gas containing 10 vol% of 99.995 wt% oxygen gas in 99.995 wt% purity nitrogen gas. A copper-clad laminated substrate according to Comparative Example 1 was produced under the same conditions as those described above. The obtained copper clad laminated substrate according to Comparative Example 1 was evaluated in the same manner as in Example 1, and is shown in Table 1. Further, after measuring the heat-resistant peel strength, the peeled surface of the peeled lead from the insulator film was subjected to Auger electron analysis, and the spectrum of titanium oxide was confirmed.

(Comparative Example 2)
In the production of the copper-clad laminate of Example 1, the plasma treatment atmosphere was a mixed gas containing 10 vol% of 99.995 wt% purity oxygen gas in 99.995 wt% purity nitrogen gas, and an underlayer A copper-clad laminate according to Comparative Example 2 was produced under the same conditions as in Example 1 except that a titanium target was formed using a sputtering cathode. That is, in the copper-clad laminate according to Comparative Example 2, the base layer is a titanium layer having a thickness of 20 nm.
Each characteristic of the produced copper clad laminated substrate according to Comparative Example 2 was evaluated, and Table 1 summarizes the results. Similarly to Comparative Example 1, Auger electron analysis of the peeled surface of the peeled lead after measurement of heat resistant beep strength with the insulator film confirmed the spectrum of titanium oxide.

  In addition, in the present Example, although the example of preparation about the single-sided flexible wiring board obtained from the board | substrate which has a wiring pattern on the single side | surface of a polyimide film by the subtractive method was shown, both surfaces which have a wiring part on both surfaces of an insulator film Similar excellent results have been obtained with flexible wiring boards or single-sided or double-sided flexible wiring boards produced by the semi-additive method.

DESCRIPTION OF SYMBOLS 10 Roll to roll sputtering apparatus 11 Housing | casing 12 Unwinding roll 13a-13j Guide roll 14, 17 Can roll 15 Ion irradiation source 16a Front feed roll 16b Rear feed roll 18a-18d Sputtering cathode 19 Winding roll F Polyimide film F2 Underlayer With polyimide film

Claims (9)

In the base layer provided without an adhesive on at least one surface of the insulator film, and a copper-clad laminate having a copper conductor layer on the surface of the base layer,
The copper-clad laminate, wherein the underlayer is titanium nitride containing 18 to 22.6% by mass of nitrogen.   The copper clad laminated substrate according to claim 1, wherein a functional group having a nitrogen atom is arranged on a surface of an insulating film provided with the base layer.   The copper-clad multilayer substrate according to claim 1 or 2, wherein the underlayer has a thickness of 5 to 300 nm.   The said insulator film is a polyimide, The copper clad laminated board of any one of Claims 1-3 characterized by the above-mentioned. In a method for producing a copper-clad laminate having an underlayer provided without an adhesive on at least one surface of an insulator film, and a copper conductor layer on the surface of the underlayer, the underlayer side of the insulator film A method for producing a copper-clad laminate, wherein the surface is subjected to plasma treatment or ion beam treatment in an atmosphere of nitrogen gas or a mixed gas with a rare gas containing 2% by volume or more of nitrogen gas.   6. The method for producing a copper-clad multilayer substrate according to claim 5, wherein the underlayer is formed by a dry plating method.   The method for producing a copper-clad laminate according to claim 6, wherein the dry plating method for forming the underlayer is a sputtering method, and a nitride target is used. A wiring board on which at least one surface of the insulator film is provided with a base layer without using an adhesive, and a wiring of a laminated structure in which a copper conductor layer is provided on the surface of the base layer,
The wiring substrate, wherein the underlayer is titanium nitride containing 18 to 22.6% by mass of nitrogen.   The wiring board according to claim 8, wherein a functional group having a nitrogen atom is disposed on a surface of an insulating film provided with the base layer.

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