JP4762533B2 - Copper metallized laminate and method for producing the same - Google Patents

Description

  The present invention relates to a copper metallized laminate used for a flexible printed wiring board and a method for producing the same, and more particularly to a copper metallized laminate suitable for fine pattern processing and / or COF mounting and a method for producing the same.

At present, LCDs, mobile phones, digital cameras, and various electric devices are required to be thin, small, and light. The electronic components mounted on the electronic component have been reduced in size, and the printed wiring board forming the electronic circuit has been devised.
Substrates for forming an electronic circuit include a hard plate-like “rigid printed wiring board” and a film-like “flexible printed wiring board (FPC)” that can be bent flexibly and freely.
In particular, FPC can be used in places where flexibility is required, such as hinge parts for LCD driver wiring boards, HDDs, DVD modules, mobile phones, etc. ing.
A material used for the FPC is a copper clad laminate (CCL = Copper Clad Laminate) in which a copper foil (conductor layer) is bonded on an insulating film such as polyimide or polyester.

There are two types of CCL. One type is CCL (usually referred to as “3-layer CCL”) with an insulating film and copper foil (conductor layer) pasted with an adhesive, and the other type is an insulating film and copper foil (conductor layer). Is a CCL (usually referred to as “two-layer CCL”) that is compounded directly by a casting method, a laminating method, a metalizing method, etc. without using an adhesive.
Comparing “3-layer CCL” and “2-layer CCL”, the manufacturing cost is lower in price because the 3-layer CCL is easier to manufacture, such as material costs and handling properties of insulating films, adhesives, etc. is there. On the other hand, the two-layer CCL is superior in characteristics such as heat resistance, thin film thickness, and dimensional stability, and it can be thinned although it is expensive due to fine patterning and high-density mounting of the circuit. The demand for strata CCL is expanding.

In addition, as a method of mounting an IC on an FPC, after forming a wiring pattern on the CCL, COF mounting that detects the position of the IC by light transmitted through the film (from the place where the IC is directly mounted on the FPC to the chip on film (COF )) Is the mainstream, and the thinness of the material itself and the transparency of the insulating material are required. From this point of view, the two-layer CCL is advantageous.
The manufacturing method of the two-layer CCL is divided into three. One is a method of affixing an insulating film to an electrolytic copper foil or a rolled copper foil by a casting method, two is a method of affixing an electrolytic copper foil or a rolled copper foil to an insulating film by a laminating method, and three are on an insulating film A thin metal film is provided on an insulating film by a dry process (where dry process refers to sputtering, ion plating, cluster ion beam, vacuum deposition, CVD, etc.) There is a method of forming a copper layer by performing electrolytic copper plating on the top. This third method is usually called a metalizing method.

Of the above manufacturing methods, when the electrolytic copper foil is attached to the insulating film by the casting method or the laminating method, the uneven surface of the roughened electrolytic copper foil bites into the insulating film surface, so that stable peel strength can be obtained. Can keep.
However, when forming a wiring pattern by etching the copper foil on the insulating film, the cross-sectional shape of the wiring pattern tends to become a trapezoid with a skirt spread due to the irregularities on the surface of the copper foil, making it difficult to cut the fine pattern. It has been pointed out. Therefore, when considering fine pattern processing, the use of electrolytic copper foil with large irregularities is not very suitable.
Therefore, recently, the electrolytic copper foil surface has been smoothed and thinned. Smoothing the surface of the copper foil is effective for cutting fine patterns, but on the other hand, the adhesion to the insulating film is reduced, and a copper foil having both fine pattern processability and adhesion has been obtained. Absent.

Moreover, if the thickness of the copper foil is thick, there is a disadvantage that it takes an etching time to cut the circuit and the productivity is deteriorated. For this reason, thinning of the foil is progressing. However, if the foil becomes thin, wrinkles easily enter the foil, and handling becomes difficult. Therefore, the thickness is currently limited to 9 μm.
Furthermore, in COF mounting, if the surface roughness of the copper foil is rough, the trace is left on the film surface, and the surface roughness is not preferable because it deteriorates the permeability of the film.

The rolled copper foil is smoother than the electrolytic copper foil in terms of surface roughness. However, even in the rolled copper foil, a copper foil having both fine pattern processability and adhesion has not been obtained.
Moreover, since it is difficult to handle a copper foil having a thickness of less than 9 μm as in the case of an electrolytic copper foil, it is currently necessary to use a copper foil having a thickness of 9 μm or more.
Furthermore, since the surface roughness of the rolled copper foil is smaller than that of the electrolytic copper foil in COF mounting, the surface of the insulating film is not roughened (roughened). It is not fully satisfied by the influence of rolling stripes.

For this reason, dry processes such as sputtering and ion plating are performed on the insulating film because fine patterns can be cut, and the insulating film after pattern etching is excellent in transparency and convenient for COF mounting. A two-layer CCL by metallizing method, in which a thin copper layer is used and electrolytic copper plating of 8 μm or less is applied thereon, has attracted particular attention as a material for COF mounting.
However, as one problem of this material, there is a problem that the peel strength cannot be secured. As a solution to this problem, a method of forming a layer of Cr, Ti, Fe, Co, Ni, W, Mo and their compounds as an intermediate layer (seed layer) between an insulating film and a copper layer has been studied. Peel strength has been improved.

  However, when the two-layer CCL by the metalizing method is subjected to a heat resistance test that is allowed to stand at a high temperature of about 150 ° C. for a long time, the peel strength tends to be significantly reduced as compared with the initial peel strength. Therefore, heat of about 100 to 150 ° C. is applied at the time of drying after applying the liquid resist in the pattern forming process, and heat of about 250 ° C. is also applied in bonding and soldering when mounting an IC or the like on the formed pattern. In view of the addition, the two-layer CCL manufactured by the conventional metallizing method is not suitable for forming a fine pattern and / or COF mounting at a high temperature, and thus improving heat resistance has become an indispensable problem. Yes.

  The present inventors provided a seed layer by a dry process on the surface of an insulating film, formed a copper thin film thereon by a dry process, and further formed a copper layer by performing electrolytic copper plating thereon. Regarding the plate (two-layer CCL), the inventors investigated the problem of why the adhesion strength with the insulating film decreases when the two-layer CCL is left at a high temperature of about 150 ° C. for a long time. As a result, copper near the interface between the copper layer and the insulating film is oxidized by oxygen permeating through the insulating film to form copper oxide, and the oxidation reaction is accelerated by the subsequent thermal load, The copper oxide layer is formed at the interface part of the insulating film, and the strength of the copper oxide layer is weak, so the adhesion strength at the interface part of the copper layer and the insulating film is deteriorated and the opinion that the adhesive strength is lowered is obtained. It was.

  The present invention relates to a copper metallized laminate, particularly a fine pattern formed and / or formed, in which adhesion strength (peel strength) between an insulating film and a copper layer is not significantly reduced even when left at a high temperature of about 150 ° C. for a long time. Another object is to provide a copper metallized laminate suitable for COF mounting and a method for manufacturing the same.

In order to achieve the above object, a copper metallized laminate according to the first aspect of the present invention has a seed layer provided by a dry process on at least one surface of an insulating film, and is in contact with the seed layer, Zn, Sn At least one element layer selected from Al is provided, and a copper-containing layer made of copper or / and a copper alloy is provided on the element layer.

The copper metallized laminate according to the second aspect of the present invention has a seed layer provided by a dry process on at least one surface of an insulating film, and is in contact with the seed layer to form a Cu-Zn alloy, a Cu-Sn alloy, At least one alloy layer selected from Ni—Co alloys is provided, and a copper-containing layer made of copper or / and a copper alloy is provided on the alloy layer.

  The copper metallized laminate of the third aspect of the present invention has a seed layer provided by a dry process on at least one surface of an insulating film, and is in contact with the seed layer, following the element layer and the element layer. A composite layer comprising the alloy layer is provided, and a copper-containing layer made of copper or / and a copper alloy is provided on the composite layer.

  The copper metallized laminate according to the fourth aspect of the present invention has a seed layer provided by a dry process on at least one surface of an insulating film, and is in contact with the seed layer, followed by the alloy layer and the alloy layer. A composite layer comprising an element layer is provided, and a copper-containing layer made of copper or / and a copper alloy is provided on the composite layer.

  The copper metallized laminate of the present invention is characterized in that the element layer, the alloy layer, and the composite layer in contact with the seed layer are formed by a dry process.

  The copper metallized laminate of the present invention is preferably subjected to a roughening treatment on the surface of the copper-containing layer.

  In the copper metallized laminate of the present invention, it is preferable that at least one metal layer of Ni, Co, Cr, Zn, Sn, In, Ag, or an alloy thereof is formed on the surface of the copper-containing layer.

  In the copper metallized laminate of the present invention, the surface of the copper-containing layer is preferably subjected to rust prevention treatment.

  In the copper metallized laminate of the present invention, the surface of the copper-containing layer is preferably subjected to silane coupling treatment.

The method for producing a copper metallized laminate of the fifth aspect of the present invention has a seed layer provided by a dry process on at least one surface of an insulating film, and is selected from Zn, Sn, and Al in contact with the seed layer And a copper-containing layer made of copper or / and a copper alloy is provided on the element layer.

The method for producing a copper metallized laminate of the sixth aspect of the present invention has a seed layer provided by a dry process on at least one surface of an insulating film, and is in contact with the seed layer to form a Cu—Zn alloy, Cu— At least one alloy layer selected from Sn alloy and Ni—Co alloy is provided, and a copper-containing layer made of copper or / and a copper alloy is provided on the alloy layer.

  The manufacturing method of the copper metallized laminated copper metallized laminated board according to the seventh aspect of the present invention has a seed layer provided by a dry process on at least one surface of the insulating film, and is in contact with the seed layer to form the element layer. Subsequently, a composite layer provided with the alloy layer is provided, or a composite layer provided with the element layer is provided subsequent to the alloy layer, and a copper-containing layer made of copper or / and a copper alloy is provided on the composite layer. This is a manufacturing method characterized by the above.

  The method for producing a copper metallized laminate of the present invention is characterized in that the element layer, the alloy layer, and the composite layer in contact with the seed layer are formed by a dry process.

  The present invention is a copper metallized laminate, particularly fine pattern formation, in which the adhesion strength (peel strength) between the insulating film and the copper-containing layer is not significantly reduced even when left at a high temperature of about 150 ° C. for a long period of time. A copper metallized laminate suitable for COF mounting and a method for manufacturing the same can be provided.

The insulating film used in the present invention is preferably a polyimide film, a polyester film, a liquid crystal polymer, or the like.
In the present invention, a seed layer is provided on the insulating film by a dry process.
The seed layer is made of Cr, Ti, Fe, Co, Ni, W, Mo, and their compounds (alloys), and is formed in a thin film on the insulating film. The thickness of the seed layer is preferably 1 to 50 nm. This is because if the thickness is less than 1 nm, it does not play a role as a seed layer for improving the adhesion to an insulating film (for example, a polyimide film), and if it exceeds 50 nm, there is a risk that the etching property is deteriorated.

In the first aspect of the present invention, the seed layer provided by a dry process is provided on at least one surface of the insulating film, and at least one element layer selected from Zn, Sn, and Al is provided in contact with the seed layer. A copper metallized laminate comprising a copper-containing layer made of copper or / and a copper alloy on the element layer.

In the second aspect of the present invention, an alloy layer containing at least two kinds of elements is formed on the surface in contact with the seed layer. The alloy layer is an alloy selected from a Cu—Zn alloy, a Cu—Sn alloy, and a Ni—Co alloy . Furthermore, the alloy layer on the surface in contact with the seed layer is formed by a dry process. By employing a dry process, it is basically possible to form at least two types of alloy layers of the above elements on the seed layer with an arbitrary composition by using an alloy as a target.

  According to a third aspect of the present invention, a composite layer in which the alloy layer is provided following the element layer is provided in contact with the seed layer, or a composite layer in which the element layer is provided following the alloy layer, A copper-containing layer made of copper or / and a copper alloy is provided on the composite layer.

When an element layer, an alloy layer, or a composite layer is deposited on the seed layer, the deposition thickness is preferably 50 nm to 1,000 nm. This is because when the thickness is 50 nm or less, there are many pinholes, and the plating layer becomes non-uniform in electroplating for forming a copper-containing layer thereon. Moreover, it is because it takes process time to attach the alloy layer exceeding 1,000 nm, and it is not practical.
One method for depositing the seed layer is to first subject the insulating film surface to a low temperature plasma treatment. This low-temperature plasma treatment is performed by glow discharge of a gas of oxygen, nitrogen, argon, or the like, preferably 10 ⁻³ to 10 Torr, with a direct current, low frequency, or high frequency power source.
The processing time varies depending on the plasma concentration, energy, and the type of insulating film. For example, when polyimide is used as the insulating film and oxygen of 3 × 10 ⁻² Torr is glow-discharged with a high frequency power source of 13.56 MHz. (Without removing the altered substance), the adhesion strength reaches its peak value in about 10 to 40 seconds. Therefore, it is desirable that the plasma treatment time be 10 to 40 seconds or longer.

  After performing the plasma treatment as described above, the degenerated material generated by the plasma treatment is removed by immersing the insulating film in a solvent, an aqueous solution or the like. In this case, when polyimide is used for the insulating film, an aqueous surfactant solution in which sodium pyrosulfite is added to an anionic surfactant such as sodium alkylbenzene sulfonate, sodium hydroxide is used to remove the altered substance (low molecular weight compound). Further, a degreasing agent such as an aqueous alkali solution composed of sodium carbonate, sodium orthosilicate and a surfactant is used. It should be noted that an alkaline aqueous solution having a high alkali concentration has an etching action on polyimide and impairs the effect of the plasma treatment, so it is necessary to be careful to use one having an appropriate concentration.

  Next, a seed layer is deposited by a dry process on the insulating film from which the altered substance has been removed. After depositing a metal that enhances adhesion with an insulating film such as Cr, Ti, Fe, Co, Ni, W, Mo and their compounds (alloys) as a seed layer to a thickness of 1 to 50 nm, An alloy layer and a composite layer are formed. After forming the element layer, the alloy layer, and the composite layer, a copper layer is further deposited to 50 nm to 1,000 nm, and then a copper-containing layer made of copper or / and a copper alloy is provided thereon.

  The formation of the copper or / and copper alloy layer is preferably performed by electroplating after the above layers are formed. Examples of the bath type include a sulfuric acid bath, a sulfamic acid bath, a pyrophosphoric acid bath, and a cyan bath, and the surface is smooth. In the case of crystallization, an organic or / and inorganic additive is added to these baths for plating.

The surface of the copper layer or / and copper alloy (surface opposite to the insulating film adhesion surface) is subjected to a roughening treatment. By performing the roughening treatment, it is possible to increase the adhesive strength when an insulating film is further adhered thereon.
As a roughening treatment method, it is preferable to perform an electrochemical etching treatment using hydrochloric acid, nitric acid, sulfuric acid or the like, a chemical etching treatment, or a treatment for attaching roughening particles by plating.
In the case of the treatment for attaching roughening particles by plating, Cu, or alloy particles of Cu and Mo, or alloy particles of Cu and at least one element selected from the group of Ni, Co, Fe and Cr, or Fine roughening particles, which are a mixture of alloy particles and an oxide of at least one element selected from the group consisting of V, Mo and W, are adhered to the surface.
By attaching these metal particles, alloy particles, or a mixture of various particles as fine roughened particles, the fine roughened particles adhere to the smoothed surface of the copper foil, and the insulating film is further bonded to this. Strength can be increased. These deposited metals are desirably deposited at least 0.01 mg / dm ² or more and 100 mg / dm ² or less. This is because if the amount is 0.01 mg / dm ² or less, the effect of increasing the adhesive strength is poor, and even if the amount exceeding 100 mg / dm ² is coated, the effect of increasing the adhesive strength is saturated.

The copper metallized laminate having the above structure is subjected to metal coating treatment, rust prevention treatment, silane coupling treatment, or a combination of these two types or three types. In the metal coating treatment, it is preferable that at least one metal layer of Ni, Co, Cr, Zn, Sn, In, Ag, or an alloy thereof is formed on the surface of the copper-containing layer.
The coating of these metals not only serves to prevent rust in the atmosphere, but also prevents heat discoloration in a heat process that takes place when a printed wiring board is produced. In these metal coating treatments, it is desirable to deposit at least 0.01 mg / dm ^{2 to} 30 mg / dm ² . This is because heat discoloration cannot be prevented at 0.01 mg / dm ² or less, and the heat discoloration-resistant effect is saturated even when 30 mg / dm ² or more is adhered.

The rust prevention treatment is preferably an organic coating such as benzotriazole and an inorganic coating such as chromate treatment. When a printed wiring board is subjected to chromate treatment, more preferably electrolytic chromate treatment, an anti-oxidation layer is formed on the surface, and at the same time, the adhesion strength when an insulating film is further adhered thereon can be increased. preferable. As the amount of chromium formed, it is desirable to attach chromium oxide of about 0.01 to 0.2 mg / dm ² or its hydrate, thereby imparting an excellent rust prevention function to the copper foil. Can do.
For silane coupling agents, vinyl silane, epoxy silane, styryl silane, methacryloxy silane, acryloxy silane, amino silane, ureido silane, chloropropyl silane, mercapto silane, sulfide silane, isocyanate It is preferable to use a silane or the like. The type of silane coupling agent is preferably selected according to the cover film resin to be used. Also in this case, when the insulating film is further bonded as a cover film, the adhesive strength can be increased.

Example 1:
A 25 μm-thick polyimide film (Toray DuPont, trade name: KAPTONN-150EN) was used as the insulating film, and plasma treatment was performed for 20 seconds using oxygen as the carrier gas. The conditions for the plasma treatment are gas pressure: 3 × 10 ⁻² Torr, high frequency power supply: 13.56 MHz, 100 W. Next, the denatured material was removed by immersing the plasma-treated polyimide film in an alkaline aqueous solution at 50 ° C. for 3 minutes, washed with water, and dried.
Next, a 10 nm chromium layer is provided as a seed layer on the polyimide film by sputtering (target: chromium, carrier gas: argon). Subsequently, a zinc layer is formed on the chromium layer by sputtering (target: zinc, carrier gas: Argon) to a thickness of 0.005 μm. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.
[Electrolytic copper plating condition A]
Copper sulfate 50-100g / l
Sulfuric acid 50-100g / l
Additive Trace Current Density 0.1-1A / dm ²

Example 2:
In the same manner as in Example 1, a 10 nm chromium layer (seed layer) was provided on a polyimide film by sputtering, and then a nickel layer was formed on the chromium layer by sputtering (target: nickel, carrier gas: argon). The thickness was 0.002 μm. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Example 3:
In the same manner as in Example 1, a 10 nm chromium layer (seed layer) was provided on a polyimide film by sputtering, and then an aluminum layer was formed on the chromium layer by sputtering (target: aluminum, carrier gas: argon). The thickness was 0.002 μm. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Example 4:
In the same manner as in Example 1, a 10 nm chromium layer was formed on a polyimide film by sputtering, followed by a copper-zinc alloy layer (target: copper 70% -zinc 30% alloy, carrier gas: argon). ) To a thickness of 0.20 μm by sputtering. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Example 5:
In the same manner as in Example 1, a 10 nm chromium layer was formed on a polyimide film by sputtering, and then a copper-zinc alloy layer (target: copper 90% -zinc 10% alloy, carrier gas: argon). ) To a thickness of 0.20 μm by sputtering. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Example 6:
In the same manner as in Example 1, a 10 nm chromium layer was formed on a polyimide film by sputtering, and then a nickel layer was formed on the chromium layer by sputtering (target: nickel, carrier gas: argon) to a thickness of 0.001 μm. Provided. A copper-zinc alloy layer (target: copper 70% -zinc 30% alloy, carrier gas: argon) was formed thereon with a thickness of 0.20 μm by sputtering. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Example 7:
In the same manner as in Example 1, a 10 nm chromium layer was formed on a polyimide film by sputtering, and then a copper-zinc alloy layer was sputtered on the chromium layer (target: copper 70% -zinc 30% alloy, carrier Gas: Argon) was provided by sputtering to a thickness of 0.20 μm. On top of that, a tin layer (target: tin, carrier gas: argon) was formed by sputtering to a thickness of 0.002 μm. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Example 8:
In the same manner as in Example 1, a 10 nm chromium layer was formed on a polyimide film by sputtering, and then a copper-tin alloy was sputtered as an alloy layer on the chromium layer (target: copper 70% -tin 30 % Alloy, carrier gas: argon) to a thickness of 0.20 μm. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Example 9:
In the same manner as in Example 1, a 10 nm chromium layer was formed on a polyimide film by sputtering, and then a nickel-cobalt alloy was sputtered as an alloy layer on the chromium layer (target: nickel 50% -cobalt 50%). Alloy) was provided at 0.005 μm. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Example 10:
In the same manner as in Example 1, a 10 nm chromium layer was formed on a polyimide film by sputtering, and then a nickel-cobalt alloy was sputtered as an alloy layer on the chromium layer (target: nickel 50% -cobalt 60%). Alloy) was provided at 0.005 μm. A copper-zinc alloy layer (target: copper 70% -zinc 30% alloy, carrier gas: argon) was formed thereon with a thickness of 0.20 μm by sputtering. Further, a copper layer was provided thereon with a thickness of 0.5 μm by sputtering (target: copper, carrier gas: argon). Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

Comparative Example 1:
In the same manner as in Example 1, a 25 μm-thick polyimide film (Toray DuPont, trade name: KAPTONN-150EN) was used as an insulating film, and oxygen was used as a carrier gas, and plasma treatment was performed for 20 seconds. The plasma treatment conditions are gas pressure: 3 × 10 ⁻² Torr, high frequency power supply: 13.56 MHz, 100 W.
Next, the denatured material was removed by immersing the plasma-treated polyimide film in an alkaline aqueous solution at 50 ° C. for 3 minutes, washed with water, and dried. Thereafter, a 10 nm chromium layer is provided on the polyimide film by sputtering (target: chromium, carrier gas: argon), and then a copper layer is formed on the chromium layer by sputtering (target: copper, carrier gas: argon). 0.5 μm was provided. Thereafter, an electrolytic copper plating layer was formed according to condition A so as to have a thickness of 8 μm.

〔Evaluation methods〕
Trial Production of Evaluation Sample The copper clad laminate (size 100 mm × 50 mm) prepared in the above examples and comparative examples was placed in a thermostatic bath at 150 ° C. for 168 hours to prepare a trial sample.

Measurement of peel strength A sample was cut out from the copper clad laminate subjected to the heat treatment, and the peel strength of an 8 μm copper film and a polyimide film was measured at n = 3 using a measurement sample having a width of 1 mm in accordance with the method specified in JISC6511. did.

[Evaluation results]
[Peel strength]
The evaluation results are shown in Table 1. Table 1 shows the average value of n = 3.
As is clear from Table 1, the peel strength of the samples of each example was not significantly deteriorated compared to the strength before the heat treatment, and the product satisfied the strength, but the sample of Comparative Example 1 As a result, the peel strength dropped extremely, and the product value was lost.

[COF mounting]
As the evaluation sample, a circuit having a width of L / S = 25/25 μm was formed on the copper clad laminate prepared in Examples and Comparative Examples, and an IC chip was mounted on the circuit at n = 1,000. The mounting conditions are: chip side temperature: 460 ° C., tape side temperature: 100 ° C., load: 15 kgf (13.6 MPa), time: 3 seconds. As a result, in the samples of Examples 1 to 9, the IC could be normally mounted on the circuit, and separation between the polyimide and the circuit did not occur at all. On the other hand, since the sample of Comparative Example 1 was heated and the peel strength was lowered, peeling between the polyimide circuit and n = 5 occurred.

In the present invention, as shown in Table 1, the adhesion strength (peel strength) between the insulating film and the copper layer was not significantly lowered even when left at a high temperature of about 150 ° C. for a long time. Moreover, it is suitable for fine pattern formation and COF mounting, and an excellent copper metallized laminate and a method for producing the same can be provided.

Claims (7)

  A seed layer provided by a dry process is provided on at least one surface of the insulating film, and at least one alloy layer selected from a Cu—Zn alloy, a Cu—Sn alloy, and a Ni—Co alloy is in contact with the seed layer. A composite layer in which at least one element layer selected from Zn, Sn, and Al is provided is provided after the alloy layer, and a copper-containing layer made of copper or / and a copper alloy is provided on the composite layer. A copper metallized laminate characterized by the above. The copper metallized laminate according to claim 1, wherein the element layer, the alloy layer, and the composite layer in contact with the seed layer are formed by a dry process. The copper metallized laminate according to claim 1 or 2 , wherein a surface of the copper-containing layer is roughened. The surface of the copper-containing layer is formed with at least one metal of Ni, Co, Cr, Zn, Sn, In, Ag, or an alloy thereof, according to any one of claims 1 to 3. The copper metallized laminate as described. The copper metallized laminate according to any one of claims 1 to 4 , wherein a surface of the copper-containing layer is subjected to a rust prevention treatment. The copper metallized laminate according to any one of claims 1 to 5 , wherein the copper-containing layer is subjected to a silane coupling treatment. A seed layer provided by a dry process is provided on at least one surface of the insulating film, and at least one alloy layer selected from a Cu—Zn alloy, a Cu—Sn alloy, and a Ni—Co alloy is in contact with the seed layer. A composite layer in which at least one element layer selected from Zn, Sn, and Al is provided is provided after the alloy layer, and a copper-containing layer made of copper or / and a copper alloy is provided on the composite layer. The manufacturing method of the copper metallized laminated board characterized by the above-mentioned.