JP7043731B2 - Copper-clad laminated board and its manufacturing method, as well as wiring board - Google Patents

Description

The present invention provides a copper-clad laminated substrate having a laminated structure of a base layer and a copper conductor layer formed on the surface of the base layer without using an adhesive on at least one surface of the insulator film, and a method for manufacturing the same. , And more specifically, a copper-clad laminated substrate using titanium nitride as the underlayer.

The flexible printed wiring board consists of a three-layer copper-clad laminated board (see, for example, Patent Document 1) in which a copper foil as a conductor layer is bonded on an insulator film using an adhesive, and an adhesive on the insulator film. It is roughly classified into a two-layer copper-clad laminated substrate in which a copper coating layer to be a conductor layer is directly formed by a metallizing method of a dry plating method or a wet plating method without using the above.

By the way, with the increase in density of electronic devices in recent years, a wiring board having a narrower pitch is required, and in order to obtain a wiring board from a copper-clad laminated board through wiring processing such as etching, copper-clad is used. A two-layer copper-clad laminated substrate is mainly used as the laminated substrate instead of the three-layer copper-clad laminated substrate.

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

Under these circumstances, the adhesion between the insulator film and the copper coating layer becomes very weak when a fragile layer such as CuO or _Cu2O is formed at the interface thereof, 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 the two-layer copper-clad laminated substrate manufactured by the current metallizing method, a nickel-chromium alloy is used as 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 150 ° C. and the heat-resistant peel strength after 168 hours is high. On the other hand, the disadvantage is that the nickel-chromium alloy tends to remain on the polyimide surface of the insulator film due to the strong bond with the insulation, and if it remains between the wires, nickel out of the nickel and chromium remaining on the surface will migrate. However, there is a problem of insulation reliability that the insulation resistance deteriorates and, in some cases, a short circuit occurs.

Japanese Unexamined Patent Publication No. 6-132628 Japanese Unexamined Patent Publication No. 8-139448 Japanese Unexamined Patent Publication No. 6-12630 Japanese Unexamined Patent Publication No. 2015-101778

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

The first invention of the present invention is the insulation 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 body film is polyimide, and the surface of the insulator film on the base layer side has an amide bond formed by cutting an imide bond and a functional group having a nitrogen atom, and the base layer contains nitrogen 18 to 22. It is a copper-clad laminated substrate which is titanium nitride containing 0.6% by mass and has a thickness of the base layer of 5 to 300 nm.

The second invention of the present invention is a copper-clad laminated substrate provided with a titanium nitride underlayer provided on at least one surface of the insulator film without using an adhesive, and a copper conductor layer on the surface of the underlayer. In the manufacturing method of the above, the underlayer is titanium nitride containing 18 to 22.6% by mass of nitrogen, and the thickness of the underlayer is 5 to 300 nm, and the surface of the insulator film on the underlayer side. In a mixed gas atmosphere with nitrogen gas or a rare gas containing 2% by volume or more of nitrogen gas , plasma treatment at an applied voltage of 800 V to 2600 V or ion beam treatment at an applied voltage of 600 V to 2600 V is carried out. It is a method for manufacturing a copper-clad laminated substrate, characterized in that the base layer is provided after forming a functional group having a nitrogen atom on the surface of the insulator film on the base layer side.

A third invention of the present invention is a method for manufacturing a copper-clad laminated substrate, characterized in that the film formation of the base layer in the second invention is a dry plating method.

A fourth aspect of the present invention is a method for manufacturing a copper-clad laminated substrate, wherein the dry plating method for forming a base layer in the third aspect of the present invention is a sputtering method and a nitride target is used. be.

In the fifth aspect of the present invention, a laminated structure wiring in which a base layer is arranged on at least one surface of the insulator film without using an adhesive and a copper conductor layer is arranged on the surface of the base layer is arranged. The insulating substrate is polyimide, and the surface of the insulator film on the base layer side is provided with an amide bond formed by cutting an imide bond and a functional group having a nitrogen atom. It is a wiring substrate characterized in that the base layer is titanium nitride containing 18 to 22.6% by mass of nitrogen and the thickness of the base layer is 5 to 300 nm.

The copper-clad laminated substrate according to the present invention solves the above-mentioned problems by using titanium nitride as the base layer, and obtains a copper-clad laminated substrate having a copper conductor layer having high adhesion and high insulation reliability. Can be done. Further, by using this substrate, it is possible to efficiently obtain a wiring board having a highly reliable narrow-width and narrow-pitch wiring portion having a wiring portion having high adhesion. Therefore, the effect is great industrially.

This is an example of a roll-to-roll sputtering apparatus suitable for continuous production of a copper-clad laminated substrate according to the present invention.

The copper-clad laminated substrate according to the present invention is provided with a titanium nitride underlayer on at least one surface of the insulator film without using an adhesive, and a copper conductor layer having a desired thickness is provided on the surface of the underlayer. It is a copper-clad laminated substrate.

(1) Insulator film The insulator film may be any film having electrical insulation properties, and it is desirable to use a resin film. The insulator film that can be used in the present invention includes a polyimide film, a polyamide film, a polyester film such as polyethylene terephthalate (PET) and polyethylene terenaphthalate (PEN), a polytetrafluoroethylene film, a polyphenylene sulfide film, and polyethylene. Insulating resin film selected from naphthalate film or liquid crystal polymer film can be used according to the application in consideration of heat resistance, dielectric properties, electrical insulation, chemical resistance in the manufacturing process of wiring boards and the next process. It can be selected as appropriate. Of these, the polyimide film is desirable from the viewpoint of electrical insulation, heat resistance, and chemical resistance.
The thickness of the insulator film is preferably 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% by mass of nitrogen is used for the underlayer. Nickel-chromium alloy is used for the base layer in the copper-clad laminated substrate that has been widely known so far, but when the copper-clad laminated substrate is processed into a wiring board, the nickel remaining on the insulator film is completely removed. desirable. Therefore, although some underlayers that do not contain nickel have been proposed, they are less likely to cause redox reactions due to electrochemical reactions between the wirings, and have insulation reliability due to migration resistance, which is electrochemical corrosion. Titanium-based underlayers are promising.

However, when a metal titanium film is formed as a base layer, the metal titanium is very active and is easily oxidized by a small amount of oxygen during sputtering, and when it is oxidized, the peel strength deteriorates (particularly heat-resistant peel). There is a problem that the strength) is remarkable.

Further, normally, in the process of manufacturing a copper-clad laminated substrate, in order to improve the adhesion between the insulator film and the base layer, that is, the peel strength, the molecules of the insulator film existing on the surface of the insulator film are uncured oligomers. The fragile layer containing the above is removed, and an oxygen plasma treatment is performed in which an oxygen functional group or the like is introduced into the polymer constituting the insulator film from which the fragile layer has been removed.

For example, a polyimide film of an insulator film is subjected to a treatment of forming a functional group having an oxygen atom by oxygen plasma treatment or the like to enhance the bond with a nickel-chromium alloy. However, in the case of a titanium-based base layer, this oxygen plasma treatment also causes the base layer to be oxidized during film formation due to the oxygen-containing functional groups introduced into the insulator film, resulting in deterioration of peel strength. The analysis of the oxidation of the underlying layer can be known from the bond between the oxygen atom and the titanium atom from the chemical shift 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 in the base layer 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 a nitrogen atom on the surface of the insulator film before the film formation of the base layer to prevent oxidation.
Here, to explain the polyimide film to the insulator film as an example, one of the cyclic bonds of the nitrogen atoms constituting the imide bond of the polyimide molecule is cleaved to form an amide bond, and at the same time, the imide bond is cleaved. A nitrogen atom is introduced into the other, 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 a nitrogen gas or a mixed gas with a rare gas containing 2% by volume or more of nitrogen gas. Is desirable. Here, the noble gas is argon, xenon, krypton, or helium, and argon is preferable from the viewpoint of availability.

Ion beam treatment is preferable to plasma treatment from the viewpoint of pressure control of atmospheric gas. If 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 the sputtering method is preferable among the dry plating methods. The sputtering film formation of this base layer can also be formed by reactive sputtering in which a metallic titanium target is provided on the sputtering cathode and nitrogen gas is added to a rare gas such as argon as the sputtering gas. Furthermore, it is more desirable to form a film using a titanium nitride target, and if a titanium nitride target is used, it is possible to prevent oxidation of the underlying layer even if oxygen or water adsorbed on the sputtering apparatus is released into the sputtering atmosphere. can.

The film thickness of the base layer is preferably 5 to 300 nm.
If the thickness of the base layer is less than 5 nm, a dense base 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 board. Decreases, and oxidation progresses due to the influence of oxygen. On the other hand, if the film thickness of the base layer exceeds 300 nm, it becomes difficult to remove the base layer by etching during wiring processing.

The composition of titanium nitride in the base layer contains 18 to 22.6% by mass of nitrogen. If the nitrogen content of titanium nitride is 18 to 22.6% by mass, the underlying layer will not be deteriorated even if the finally obtained copper-clad laminated substrate 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 film thickness of 1 to 20 μm.
The copper conductor layer may have a laminated structure of a copper thin film layer and a copper electroplating layer formed on the surface of the base layer. The copper thin film layer preferably has a film 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 thin film deposition method.
The reason why the copper thin film layer is provided on the surface of the titanium nitride base layer is that even if the base layer is a conductive titanium nitride base layer, the resistance value of the base layer is high when the base layer is 5 nm to 100 nm. It is difficult to provide a copper electroplating layer of a copper conductor layer by the plating method. Therefore, when the base layer is 100 nm or less, it is desirable to provide a copper thin film layer on the surface of the base layer. On the other hand, if the copper thin film layer can be omitted due to the thickness of the base layer, a copper-clad laminated substrate in which the base layer 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 an electroplating method. The electroplating can be formed by a known electroplating method using a known copper electroplating bath or the like.
The total film thickness of the copper thin film layer and the copper electroplating layer may be 1 to 20 μm.

(4) Method for manufacturing a copper-clad laminated substrate In an example of the method for manufacturing a copper-clad laminated substrate according to the present invention, a base layer and, if necessary, a copper thin film layer are formed on at least one surface of an insulator film by a dry plating method. A film is formed, and then a copper electroplating layer of a copper conductor layer is formed by known copper electroplating to complete the process.

FIG. 1 is an example of a roll-to-roll sputtering apparatus 10 suitable for continuous production of a copper-clad laminated substrate. 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 housing 11 that houses most of its components.
The housing 11 may have a cylindrical shape, and the shape thereof is not limited, but it is sufficient that the housing 11 can be maintained in a depressurized state in the range of 10 ^-4 Pa to 1 Pa.

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

The sputtering cathodes 18a to 18d are magnetron cathode type and are arranged to face the canroll 17. The dimension in the width direction of the polyimide film F of the sputtering cathodes 18a to 18d may be wider than the width of the polyimide film F.

In the polyimide film F, a functional group having a nitrogen atom is formed on the surface of the polyimide film F, which is an insulator film, by an ion irradiation source 15 arranged opposite to the can roll 14. Therefore, a mixed gas in which nitrogen gas is added to the noble gas is supplied to the ion irradiation source. Here, when introducing a functional group having a nitrogen atom in the plasma treatment, a plasma irradiation means is arranged in place of the ion irradiation source 15 to carry out the plasma treatment.

The polyimide film F is conveyed in the roll-to-roll sputtering apparatus 10 and is formed into a film on the sputtering cathodes 18a to 18d facing the can roll 17, and the underlayer is formed and processed into the polyimide film F2 with the underlayer. For example, a titanium nitride target is attached to the sputtering cathode 18a, and a copper target is attached to the sputtering cathodes 18b, 18c, 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 attach a titanium nitride target to all of the sputtering cathodes 18a to 18d to obtain a polyimide film F2 with a base layer in which only the base layer is formed.

The base layer of titanium nitride can also be formed by reactive sputtering in an atmosphere in which nitrogen gas is added to argon as a sputtering gas.
The surface of the can rolls 14 and 17 is finished with hard chrome plating, and a refrigerant or a hot medium supplied from the outside of the housing 12 circulates inside the can rolls 14 and 17, and the temperature is adjusted to a substantially constant temperature.

Further, the copper thin film layer may be formed by a vapor deposition method after the underlayer is formed by sputtering.
A copper-clad laminated substrate is completed by forming a copper electroplating layer on a polyimide film with a base layer obtained by the roll-to-roll sputtering apparatus 10 using a known roll-to-roll continuous electroplating apparatus.
The roll-to-roll sputtering apparatus 10 can continuously perform plasma treatment or ion beam treatment on a long insulator film, and then continuously form an underlayer film. Of course, instead of continuous treatment, the underlayer may be formed from plasma treatment or ion beam treatment in a single-wafered manner in a vacuum chamber.

(5) Wiring board The copper-clad laminated board according to the present invention can be wired by a known semi-additive method or a known subtractive method.
In the subtractive method, an opening is provided in the resist layer at the place where the copper conductor layer or the like is to be removed on the surface of the copper conductor layer of the copper-clad laminated substrate, and the unnecessary copper conductor layer exposed by the opening and the bottom. This is a method of removing the formation layer by etching or the like. An aqueous solution of ferric chloride or the like can be used to remove the etching of the copper conductor layer, and hydrogen chloride, a fluoride ion source, and a phosphonobutane tricarboxylic acid disclosed in Patent Document 4 can be used to remove the underlying layer. An etching solution containing an azole compound, an etching solution containing a mixed solution of hydrochloric acid, sulfuric acid and an 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 the resist layer is provided at a position where a wiring pattern is desired to be formed on the surface of the copper conductor layer of the copper-clad laminated substrate, and the copper conductor exposed by the opening is provided. After electrolytic copper plating is performed using the layer as a cathode to form a wiring portion having a desired thickness, the resist layer is removed, and the base layer and the copper conductor layer of the copper-clad laminated substrate other than the wiring portion are removed by flash etching or the like. By doing so, it is a method of completing the wiring board. A commercially available semi-additive method copper removing solution can be used to remove the copper conductor layer, and the underlying layer can be removed by etching a mixed solution system of hydrochloric acid, sulfuric acid, and aromatic sulfonic acid in the same manner as in the subtractive method. A liquid can be used.

So far, the copper-clad laminated substrate according to the present invention has been described. The copper-clad laminated substrate according to the present invention forms a functional group having a nitrogen atom on the surface of the insulator film to prevent oxidation, prevent oxidation of Ti during sputtering, and bond with oxygen by reaction with the polyimide film. And improves the adhesion of the copper-clad laminated substrate. Furthermore, since a nickel-based alloy that easily remains on the surface of the insulator film after wiring processing is not used for the base layer, it can be obtained from a copper-clad laminated substrate having excellent migration resistance without nickel residue and a copper-clad laminated substrate thereof. It becomes possible to provide a wiring board.

Hereinafter, examples of the present invention will be described together with comparative examples. The characteristic evaluation was performed by each measurement method shown below.
[Peel strength]
The peel strength was measured by a measuring 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 using a ferric chloride etching solution for lead etching and a mixed solution of hydrochloric acid, sulfuric acid and aromatic sulfonic acid to remove the underlying layer, and forming it by a subtractive method. After measuring the 90 ° peel strength (normal peel strength) of the sample at room temperature, a part of the sample is stored in an oven, then left at 150 ° C. for 168 hours, taken out, left to room temperature, and then 90. ° Heat resistance of peel strength (heat resistant peel strength [based on IPC-TM-650, NUMBER 2.4.9]) was evaluated.

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

The measurement is based on JPCA-ET04, 85 ° C., 85% R.M. H. Under the environment, energize DC60V between the terminals and observe the resistance change for 1000 hours after energization. When the resistance became ¹⁰⁶ Ω or less, it was judged that the short circuit was defective, and if it was ¹⁰⁶ Ω or more even after 1000 hours had passed, it was judged to be acceptable.

[Corrosion resistance evaluation]
Next, as an index of corrosion resistance, discoloration of the back surface can be mentioned, which was performed by observing the back surface of the sample after the HHBT test.
When a significant discoloration was observed, it was judged as a defective "x", and when no discoloration was observed or even a slight discoloration was observed, it was judged as a pass "○".

A polyimide film having a thickness of 38 μm (manufactured by Toray Industries, Inc., product name “Kapton 150EN”) was cut into a size of 12 cm × 12 cm and placed in a vacuum chamber. One side of the polyimide film was subjected to plasma treatment at a voltage of 2000 V under a nitrogen gas atmosphere having a purity of 99.9995 wt%. Then, with a sputtering cathode equipped with a titanium nitride target containing 20% by mass of nitrogen, a base layer was formed on a polyimide film to a thickness of 20 nm, and copper was used with another sputtering cathode equipped with a copper target on the surface of the base layer. A thin film layer was formed to a thickness of 200 nm to obtain a polyimide film with a base layer.
Then, the obtained polyimide film with a base layer was taken out from a vacuum chamber, and a copper electroplating layer was formed up to 8 μm on the surface of the copper thin film layer by an electroplating method using a copper sulfate electroplating bath having a pH of 1 to be an example. A copper-clad laminated substrate according to No. 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 base layer of titanium nitride was set to 300 nm, a polyimide film with a base layer was obtained without providing a copper thin film layer on the surface of the base layer, and this base layer was obtained. A copper-clad laminated substrate according to Example 2 was obtained by manufacturing under the same conditions as in Example 1 except that a copper electroplating layer was formed on the surface of the above to a thickness of 8 μm, and the copper-clad laminated substrate was used in Examples. It was evaluated in the same manner as 1.
The test results are summarized in Table 1.
In the copper-clad laminated substrate of Example 2, since the TiN layer of the base layer has conductivity, it is possible to directly form the copper plating layer, which may be a merit in the process.

(Comparative Example 1)
In the production of the copper-clad laminated substrate of Example 1, the atmosphere of the plasma treatment was the same as that of Example 1 except that a mixed gas containing 10 vol% of a nitrogen gas having a purity of 99.995 wt% and an oxygen gas having a purity of 99.995 wt% was used. Under the same conditions as in the above, the copper-clad laminated substrate according to Comparative Example 1 was produced. The obtained copper-clad laminated substrate according to Comparative Example 1 was evaluated in the same manner as in Example 1, and is summarized in Table 1. In addition, after measuring the heat-resistant peel strength, Auger electron analysis of the peeled surface of the peeled lead with the insulator film confirmed the spectrum of titanium oxide.

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

In this embodiment, a production example of a single-sided flexible wiring board obtained from a substrate having a wiring pattern on one side of the polyimide film by the subtractive method is shown, but both sides having wiring portions on both sides of the insulator film are shown. Similar excellent results have been obtained for the flexible wiring board or the single-sided or double-sided flexible wiring board manufactured by the semi-additive method.

10 Roll-to-roll sputtering device 11 Housing 12 Unwinding rolls 13a to 13j Guide rolls 14, 17 Can rolls 15 Ion irradiation source 16a Front feed roll 16b Rear feed rolls 18a to 18d Sputtering cathode 19 Winding roll F Polyimide film F2 Base layer With polyimide film

Claims (5)

In a copper-clad laminated substrate having 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 insulator film is polyimide,
The surface of the insulator film on the base layer side has an amide bond formed by cleaving an imide bond and a functional group having a nitrogen atom.
The base layer is titanium nitride containing 18 to 22.6% by mass of nitrogen.
A copper-clad laminated substrate characterized in that the film thickness of the base layer is 5 to 300 nm. In a method for manufacturing a copper-clad laminated substrate having a titanium nitride underlayer provided on at least one surface of an insulator film without using an adhesive and a copper conductor layer on the surface of the underlayer.
The base layer is titanium nitride containing 18 to 22.6% by mass of nitrogen, and the film thickness of the base layer is 5 to 300 nm.
Plasma treatment at an applied voltage of 800V to 2600V or an applied voltage of 600V to 2600V under a mixed gas atmosphere with nitrogen gas or a rare gas containing 2% by volume or more of nitrogen gas on the surface of the insulator film on the base layer side. A method for producing a copper-clad laminated substrate, which comprises performing the ion beam treatment of the above to form a functional group having a nitrogen atom on the surface of the insulator film on the base layer side, and then providing the base layer. The method for manufacturing a copper-clad laminated substrate according to claim 2, wherein the film formation of the base layer is a dry plating method. The method for manufacturing a copper-clad laminated substrate according to claim 3, wherein the dry plating method for forming the underlying layer is a sputtering method, and a nitride target is used. A wiring substrate in which a base layer is arranged on at least one surface of an insulator film without using an adhesive, and wiring having a laminated structure in which a copper conductor layer is arranged on the surface of the base layer is arranged.
The insulator film is polyimide,
The surface of the insulator film on the base layer side has an amide bond formed by cleaving an imide bond and a functional group having a nitrogen atom.
The base layer is titanium nitride containing 18 to 22.6% by mass of nitrogen.
A wiring board characterized in that the film thickness of the base layer is 5 to 300 nm.

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