JP2014233891A - Plated laminate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide, by targeting a plated laminate of a liquid crystal polymer film consisting of a fully aromatic polyester and a metallic layer, etc., a plated laminate entailing, while preserving interfacial smoothness, scarce dimensional variations after the etching of the metallic layer and thermal dimensional variations; and a method for manufacturing the same.SOLUTION: The provided plated laminate is a plated laminate obtained by configuring a plating layer on at least one surface of a long liquid crystal polymer film without using an interposing adhesive wherein the long liquid crystal polymer film is a film made of a fully aromatic polyester and extruded from an extrusion mold by using a melt extrusion molding method, wherein the plated laminate exhibits, following an etching operation of partially removing the plating layer, dimensional variation behaviors of shrinking or stretching along length and width directions thereof in a state where ratios of the dimensional variations are being confined to -0.05% to +0.05%, and wherein the plated laminate exhibits, following a 150°C×30 min post-etching heat treatment, dimensional variation ratios confined to a range of -0.1% to +0.1%.

Description

  The present invention relates to a plating laminate in which a plating layer is provided on the surface of a liquid crystal polymer film made of wholly aromatic polyester, and a method for producing the same.

The demand for miniaturization and weight reduction of portable electronic devices such as mobile communication has become stronger, and the expectation for high-density mounting has further increased. Along with this, multilayered printed wiring boards, narrowing of wiring pitch, miniaturization of via holes, miniaturization of IC packages and miniaturization of pins have been promoted, and miniaturization and surface mounting of passive elements such as capacitors and resistors have been combined. It is being advanced.
In particular, the technology that directly forms these components on the surface or inside of a printed wiring board can not only achieve high-density mounting, but also contribute to improving reliability. The required level of accuracy, that is, the accuracy of the wiring pitch, has become higher, and further, thermal stability of dimensions has been required.

By the way, liquid crystal polymer films made of wholly aromatic polyesters have excellent electrical properties such as low water absorption and low dielectric loss at high frequencies, so we are considering expanding into insulating films for printed wiring boards such as copper-clad laminates. Has been.
As a method for producing a copper-clad laminate using the liquid crystal polymer film as a substrate, a method of laminating an electrolytic copper foil used for a conductor forming a circuit and a liquid crystal polymer film by a thermocompression bonding (laminate) method, or a liquid crystal polymer film A thin metal film is formed on a liquid crystal polymer film by dry plating (for example, sputtering, ion plating, vacuum deposition, etc.), and a copper layer is formed thereon by electrolytic copper plating. Two of the rising methods are listed as typical manufacturing methods.

  Regarding the metallizing method, Patent Document 1 discloses a technique in which a Ni—Cr alloy is sputtered on a liquid crystal polymer support base, then copper is sputtered, and copper is formed on the surface of the copper sputtering film by electrolytic plating. Yes. When a film such as a liquid crystal polymer is used as a support substrate and a dry plating process such as sputtering film formation is performed, a sputtering film coater is generally used.

  Moreover, in the copper clad laminated board manufactured by the metalizing method compared with the thermocompression bonding method, since the copper layer-liquid crystal polymer film interface is smooth, the transmission loss in high-speed transmission becomes low. Non-Patent Document 1 shows the relationship between the surface roughness of the interface and the transmission loss. The smoother the interface, the lower the transmission loss. Patent Document 2 reports that the metalizing method has a lower transmission loss than the thermocompression bonding method.

  However, the liquid crystal polymer film has a problem of dimensional anisotropy that the dimensional stability in the longitudinal direction and the width direction are different from those of other printed wiring board resin films such as polyimide. This problem of dimensional anisotropy leads to problems such as misalignment in mounting components such as elements in printed wiring boards.

  Therefore, in the production of a metal-clad laminate by a thermocompression bonding method, Patent Document 3 proposes a heat treatment using a heated roll with irregularities as a method for improving the dimensional anisotropy of the liquid crystal polymer film. However, when heat treatment is performed with a heated roll having irregularities, there is concern that the surface roughness of the liquid crystal polymer film may be affected, and it is not expected to obtain a printed wiring board with low transmission loss due to the smoothness of the interface.

Japanese Patent No. 4341023 JP 2012-140552 A JP 2002-331589 A

M.M. M.M. R. Howlader, et. al, Journal of Materials Science, vol. 40 (2005) 3177-3184.

  In view of such a situation, the present invention provides a liquid crystal polymer film made of wholly aromatic polyester and a plating laminate such as a metal layer, while maintaining the smoothness of the interface, and the dimensional change after etching of the metal layer and thermal An object of the present invention is to provide a plated laminate having a small dimensional change and a method for producing the same.

  A first invention of the present invention is a plating laminate in which a plating layer is provided on at least one surface of a long liquid crystal polymer film without using an adhesive, and the long liquid crystal polymer film is melt-extruded. In the wholly aromatic polyester film extruded from the extrusion mold using the method, the plating laminate after etching after removing a part of the plating layer of the plating laminate by etching treatment is the plating lamination before etching treatment It shows a dimensional change behavior that contracts or expands in the longitudinal direction and the width direction with respect to the body, and the dimensional change rate in the longitudinal direction and the width direction of the post-etch plating laminate in the dimensional change behavior is −0.05% to +0. Dimensions in the longitudinal direction and width direction of the heat-treated plated laminate after heat-treating the plated laminate after etching at 150 ° C. for 30 minutes in the range of 05% Ratio is a plated laminate, which is a range of -0.1% + 0.1%.

  In the second invention of the present invention, the plating layer in the first invention is a metal layer, and in the third invention, the plating layer in the second invention is made of nickel, chromium, nickel from the long liquid crystal polymer film side. A plating laminate comprising a first metal layer made of an alloy containing or an alloy containing chromium, and having a second metal layer of a copper layer on the surface of the first metal layer.

  A fourth invention of the present invention is a printed wiring board having a wiring layer provided on the surface of a liquid crystal polymer film without an adhesive, and plating the plating laminate according to the second and third inventions The printed wiring board is characterized in that the layer is formed into a wiring layer by wiring processing by an etching process.

According to a fifth aspect of the present invention, a liquid crystal polymer film comprising a wholly aromatic polyester filmed using a melt extrusion molding method is applied to a liquid crystal polymer film while applying a tension of 80 to 4000 kN / m ² in the longitudinal direction. The temperature of the liquid crystal polyester film after the heat treatment in a temperature range of 120 ° C. or higher and 20 ° C. lower than the α relaxation temperature of the liquid crystal polymer film measured by a tensile mode in the MD direction with a dynamic viscoelastic device. It is a method for producing a plated laminate, wherein film formation is performed on at least one surface using a dry plating method.

  In a sixth aspect of the present invention, the processing steps from the heat treatment to the film formation process in the fifth aspect are performed in a reduced-pressure atmosphere, and a surface modification process is performed between the heat treatment and the film formation process. It is a manufacturing method of the plating laminated body characterized by the above-mentioned.

  The seventh invention of the present invention is a plating characterized in that the film forming process in the fifth and sixth inventions is a sputtering film forming process, and the film formed by the film forming process is a metal layer. It is a manufacturing method of a laminated body.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the plating laminated body which consists of the liquid crystal polymer film which consists of a wholly aromatic type polyester, and a metal plating layer, and has a small dimensional change rate, and its manufacturing method, Therefore Obtaining a high performance printed wiring board And has a significant industrial effect.

The plated laminate in the present invention has a plated layer formed on one side or both sides of a thermotropic liquid crystal polymer film containing a wholly aromatic polyester as a main component, and a copper layer in which the surface of the plated layer is formed of copper. A plated laminate according to the present invention will be described by taking a copper clad laminate made of as an example.
The copper-clad laminate is a first metal layer having a thickness of 2 nm to 30 nm that serves as an underlayer formed by sputtering on the surface of the film without using an adhesive, and a second metal layer formed by sputtering or It is comprised from the electroplating method or the copper layer with a film thickness of 0.1-20 micrometers formed of both.

  The wholly aromatic polyester, which is the main component of the liquid crystal polymer substrate used in the plating laminate of the present invention, has a melting point of 230 ° C. or higher in consideration of solder heat resistance, which is essential when used as an electric / electronic component. A polyester selected from “copolymer compound (I)” and “copolymer compound (II)” exemplified below can be used.

  For the liquid crystal polymer film mainly composed of wholly aromatic polyester used in the present invention, polyether ether ketone, polyether sulfone, polyimide, polyether imide, polyamide, polyamide imide, polyarylate, polytetra Polymers such as fluoroethylene, polyvinylidene fluoride and polycarbonate; additives such as lubricants and antioxidants; fillers such as inorganic particles and fibers can be blended.

  The thickness of the liquid crystal polymer film mainly composed of wholly aromatic polyester used in the plating laminate in the present invention is not particularly limited, but is preferably 10 μm or more. When the thickness is less than 10 μm, the film is too thin, so that wrinkles are easily generated during plating conveyance for forming the metal layer, and productivity is lowered.

  The liquid crystal polymer film mainly composed of wholly aromatic polyester used in the plated laminate of the present invention must have a root mean square roughness (RMS) and an arithmetic mean roughness (Ra) of less than 50 nm. is there.

The liquid crystal polymer film used for the plating laminate in the present invention is preferably produced by a known method such as an extrusion method such as a T-die method or an inflation method using an extrusion die, and has a heat deformation temperature and a melting point. You may use the liquid crystal polymer film heat-processed for the purpose of improving the heat resistance represented.
In particular, the present invention exhibits a good effect on a liquid crystal polymer formed into a film by the T-die method.

  By the way, the liquid crystal polymer film is difficult to be formed into a film due to the strong alignment of the liquid crystal polymer molecules. Specifically, in the process of producing a liquid crystal polymer film, biaxial stretching performed in the process of producing a polyimide film is difficult, and as a result, the obtained film has a difference in dimensional stability between the longitudinal direction and the width direction. It had a direction.

  This liquid crystal polymer film is produced by a solvent casting method in which the solvent is volatilized from the raw material dissolved in the solvent, a T-die method in which the solvent is extruded from a T-die, and a raw material is extruded from an inflation die and injected into a gas to inflate like a balloon Inflation methods for film formation are known.

The solvent casting method has a problem of residual solvent because the solvent remains, although fluctuations in the thickness of the film are suppressed.
In the T-die method, fluctuations in film thickness are suppressed, but since the raw material is extruded in one direction from a kind of T-die, the liquid crystal polymer molecules tend to be oriented in the extrusion direction (longitudinal direction). There is a problem of providing anisotropy in shrinkage or extension in the direction and width direction.
Further, the inflation method has a problem that the thickness of the film varies greatly and a problem of anisotropy in dimensional stability similar to the T-die method in which the die is extruded from a kind of inflation die and the inflation direction.

  The anisotropy of dimensional stability generated in the liquid crystal polymer produced by such a conventional production method leads to problems such as detachment of elements mounted on the printed wiring board.

Therefore, in both the T-die method and the inflation method, the liquid crystal polymer film is extruded from the die and stretched in the direction selected as appropriate after melt film formation, and the film is formed into a film by controlling the molecular orientation. Residual strain is left inside.
Therefore, even if the molecular orientation of the liquid crystal polymer is controlled, this residual strain affects the dimensional stability in the longitudinal and width directions of the liquid crystal polymer film. That is, the dimensional stability of the liquid crystal polymer film due to residual strain is a problem inherent to the liquid crystal polymer.
In addition, since the liquid crystal polymer formed into a film by the inflation method is easily stretched in the longitudinal direction and the width direction, the anisotropy of dimensional stability is lower than that of the liquid crystal polymer formed into a film by the T-die method.

  In the copper clad laminate as an example of the plated laminate according to the present invention, the liquid crystal polymer film composed of the above-described smoothness wholly aromatic polyester is subjected to heat treatment, and surface modification such as plasma irradiation is performed on one side or both sides thereof. After the quality treatment, a first metal layer is formed by a sputtering method, and subsequently a copper thin film layer constituting a part of the copper layer is formed by a sputtering method. Further, electrolytic copper plating is applied to the surface of the copper thin film layer. A copper electrolytic plating layer constituting a part of the copper layer is formed by a method, and the second metal layer is formed by the copper thin film layer and the copper electrolytic plating layer.

The liquid crystal polymer film has poor flexibility as shown by the polyimide film due to the fact that the liquid crystal polymer molecules are rigid. If it is a polyimide film etc., even if it performs the heat drying process which raises film temperature to 120 degreeC or more with the tension | tensile_strength of 4000 kN / m < ² > or more, a polyimide molecule can entangle and can respond | correspond to tension | tensile_strength.
On the other hand, in the liquid crystal polymer film, when a tension of 4000 kN / m ² or more is applied at a high temperature, the liquid crystal polymer molecules tend to be aligned in the direction in which the tension is applied. Therefore, it is known that when the liquid crystal polymer film is heated and stretched, the stretching treatment is performed while being sandwiched by a support.

  However, in the method for producing a plated laminate of the present invention, it is desirable to perform a film forming process continuously with the heat treatment, and a support cannot be used, but a laminate in which a metal layer is provided on the surface of a liquid crystal polymer film. In the heat treatment of a certain copper clad laminate, even if the metal layer is formed as a plating layer, the metal layer becomes a support, and the degree of freedom in selecting the heat treatment conditions is high.

Therefore, in the present invention, the temperature of the heat treatment is such that the film temperature is 120 ° C. or higher and 20 ° C. or less lower than the α relaxation temperature of the liquid crystal polymer film, more preferably 180 ° C. or higher than the α relaxation temperature of the liquid crystal polymer film. The temperature is preferably 40 ° C. or lower.
The α relaxation temperature is a temperature derived from the micro-Brownian motion of the main chain segment of the liquid crystal polymer film, and a value measured by a dynamic thermoelastic device (DMA) is used.

  When the film temperature is lower than 120 ° C., not only the effect of improving dehydration but also the removal of distortion in the film becomes insufficient. On the other hand, if the temperature exceeds 20 ° C. lower than the α relaxation temperature of the liquid crystal polymer film, the film may be deformed by heat shrinkage. This is due to the rigidity of the liquid crystal polymer molecules, and as the film becomes softer as the temperature increases, the entanglement of the liquid crystal polymer molecules becomes weaker and it becomes easier to align in the direction of tension. In particular, when the temperature is high, when a film is conveyed by roll-to-roll, tension may be applied and the film may be broken.

For this reason, the tension applied is 4000 kN / m ² or less, preferably 2500 kN / m ² or less. The tension is desirably 80 kN / m ² or more. If the tension is too weak, there will be a bias in removing the strain and the film being heated may wave.
Further, the tension needs to be taken into consideration by the width and thickness of the film. The narrower the width of the film, the lower the thickness of the film. There is no restriction | limiting in particular in heat processing time, It can be set short as temperature rises.

The time when the film temperature is in the range of 120 ° C. to 20 ° C. lower than the α relaxation temperature of the liquid crystal polymer film is 2 to 200 seconds, preferably 2 to 60 seconds.
On the other hand, the water absorption of the liquid crystal polymer film is about 0.04%, which is lower than that of a polyimide film or a polyethylene terephthalate film. However, since it volatilizes during processing in vacuum, there is a concern that the sputtering film may be oxidized. . Therefore, the atmosphere for the heat treatment may be in the air (atmospheric pressure), but it is desirable to perform the heat treatment while exhausting with a vacuum pump in a reduced pressure atmosphere.

In the production of a copper clad laminate, it is desirable to perform a surface modification treatment before forming a metal layer on the surface of the liquid crystal polymer film.
As a method, plasma treatment, ion beam irradiation, or ultraviolet irradiation can be used. By these treatments, the surface of the liquid crystal polymer film can be cleaned by etching, the fragile layer can be removed, and the polar group can be introduced to enhance the adhesion at the interface. However, it is desirable that the surface roughness after the surface treatment is almost the same as that before the surface treatment.

Examples of the metal forming the first metal layer (underlying metal layer) include nickel, chromium, molybdenum, titanium, vanadium, tin, gold, silver, zinc, palladium, ruthenium, rhodium, iron, aluminum, and lead-tin. Examples thereof include a solder alloy, and an alloy containing one or more of these metals is desirable. Furthermore, among these, it is more desirable that it is a kind selected from nickel, chromium, an alloy containing nickel, an alloy containing chromium, and an alloy containing nickel and chromium.
The first metal layer is preferably formed by dry plating such as vapor deposition or sputtering, particularly by sputtering.

The thickness of the first metal layer is desirably 2 nm or more, and the upper limit is desirably 30 nm or less.
When the thickness of the first metal layer is less than 2 nm, the initial stage of film growth by sputtering is island-like, so the skin effect at the interface between the liquid crystal polymer film and the metal layer (a phenomenon in which signals concentrate at the interface as the frequency increases) This increases the possibility that transmission loss will increase. In addition, the higher the frequency, the thinner the film thickness at which the skin effect occurs (for example, about 50 to 60 nm at 10 GHz), so that the first metal layer is preferably less than 30 nm in consideration of film thickness variation.

Next, in the copper layer of the second metal layer formed by the sputtering method or the electrolytic copper plating method, or both, the thickness is preferably in the range of 0.1 to 20 μm.
When the thickness is thinner than 0.1 μm, it is not preferable because power supply is difficult in the wet plating process when wiring is processed by the semi-additive method. When the thickness is greater than 20 μm, not only the productivity of wiring processing by etching is lowered, but also the total thickness as a substrate is increased, which is not preferable. In addition, the film thickness of the copper thin film layer of sputtering method should just be in the range of the film thickness of the said copper layer.

The wiring of the printed wiring board can be formed by a subtractive method or a semi-additive method.
The subtractive method is a method of removing unnecessary portions by performing a chemical etching process on the copper layer of the copper clad laminate. That is, a resist is provided on the surface of the copper layer of the copper clad laminate to be left as a conductor wiring, and unnecessary portions of the copper layer are selectively removed through chemical etching treatment and water washing with an etching solution corresponding to copper. Thus, the conductor wiring is formed.

  The semi-additive method is to form a resist layer on the base metal layer and copper layer of the copper clad laminate, pattern the resist layer by photolithography, and remove the resist layer where the wiring is to be formed. Copper plating is performed on the opening where the obtained copper layer is exposed to form a wiring. In this method, after the wiring is formed, the resist is removed, and the unnecessary copper layer and the base metal layer are chemically etched to remove the ultrathin copper layer and the base metal layer portion.

  The plated laminate obtained by the production method of the present invention is useful for a printed wiring board, for example, a pin insertion mounting method in which a leaded component is mounted on a substrate through a hole, and a cased component on the surface without passing through a hole. Surface-mounted components can be mounted by a known method such as a surface mounting method for mounting on a substrate or an IC chip mounting method for mounting a bare IC chip on a substrate.

  So far, the plated laminate according to the present invention has been described by taking a copper clad laminate in which the plated layer is a metal layer as an example. The plating layer is not limited to a metal layer, and can also be applied to a plating laminate in which an oxide or a nitride is formed by a dry plating method. The present invention is useful when a plating laminate in which an oxide plating layer having improved dimensional stability in the longitudinal direction and the width direction is obtained.

  EXAMPLES Hereinafter, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited by the following examples.

[Heat treatment]
The liquid crystal polymer film is installed in a vacuum device having a roll-to-roll mechanism, and the liquid crystal polymer film is transported in a vacuum chamber evacuated to a pressure of 1 Pa or less by a vacuum pump, and transported by a heating method using an infrared heater. The liquid crystal polymer film was heated from both sides.
The heating state was controlled by setting an ultrafine thermocouple on the liquid crystal polymer film in advance and grasping the relationship between the infrared heater and the film temperature, and then controlling the actual heat treatment at the set temperature of the infrared heater.

[Surface modification by plasma treatment]
The surface treatment amount of the film by plasma also depends on the gas type, applied voltage, current, and treatment time. Further, since the current also changes when the applied voltage is changed, the plasma processing intensity J is determined as shown in the following equation (1).

First, after evacuating until the pressure in the vacuum apparatus becomes 1 × 10 ⁻⁴ Pa or less, the gas is introduced, and the applied voltage V and current I are set to the plasma processing intensity J set by the above equation (1). Then, after appropriately setting the treatment time t and the electrode surface area A, the surface of the liquid crystal polymer film was subjected to plasma treatment by DC discharge plasma.

[Sputtering]
A liquid crystal polymer film that has been subjected to plasma treatment after evacuating until the pressure in the vacuum apparatus becomes 1 × 10 ⁻⁴ Pa or less, and then introducing argon gas into the vacuum chamber to set the pressure in the vacuum apparatus to 0.3 Pa. On the surface, a sputtering layer made of a Ni-20% Cr alloy layer and then a copper layer was laminated using a sputtering method.

[Electro copper plating]
Electro copper plating (plating solution: copper sulfate solution) was performed at a current density of 2 A / dm ² to form a copper plating layer having a thickness of 8 μm on the sputtered layer.

[Characteristic evaluation]
Dimensional stability In the present invention, the dimensional change rate in the length direction of the plated laminate: MD (Machine Direction) and the width direction of the plated laminate: TD (Traverse Direction) is “IPC-TM-650, 2.2. 4, Method B and C ".
Here, in the index “dimensional change rate”, the contraction is expressed by a negative value and the expansion is expressed by a positive value.
The dimensional change rate when the metal layer was etched was measured according to “IPC-TM-650, 2.2.4, Method B”.
Furthermore, the dimensional change rate after heat treatment at 150 ° C. for 30 minutes was measured according to “IPC-TM-650, 2.2.4, Method C”.

Polyester-based liquid crystal polymer film “BIAC (fully aromatic polyester having the structure of copolymer compound II, film thickness 25 μm α relaxation temperature 300 ° C.)” manufactured by Primatec Co., Ltd. formed into a film by the T-die method in a vacuum apparatus In a state where a tension of 800 kN / m ² was applied, heat treatment was performed so that the film temperature was 150 ° C.
Thereafter, oxygen plasma treatment was performed on both surfaces of the liquid crystal polymer film at a plasma treatment strength of 83 kJ / m ² . Subsequently, a Ni-20% Cr alloy is laminated with a thickness of 8 nm and copper with a layer thickness of 100 nm by a sputtering method, and subsequently a copper plating layer is formed to 8 μm by using an electrolytic copper plating method. Was made.

The dimensional change rate (method B) due to etching removal of the metal layer of the plated laminate according to Example 1 was measured.
Furthermore, the dimensional change rate (method C) by heating at 150 ° C. for 30 minutes was measured.
The measurement results are summarized in Table 1.

Using the same liquid crystal polymer film as in Example 1, heat treatment was performed so that the film temperature was 200 ° C. while applying a tension of 400 kN / m ² in a vacuum apparatus. Then, the plating laminated body was produced by the same operation as Example 1, and the dimensional change rate by etching removal and the dimensional change rate by 150 degreeC x 30 minute heating were measured.
The measurement results are summarized in Table 1.

Except for the film thickness being 50 μm, the same type of liquid crystal polymer film as in Example 1 was subjected to heat treatment so that the film temperature was 150 ° C. with a tension of 1200 kN / m ² applied in a vacuum apparatus. . Then, the plating laminated body was produced by the same operation as Example 1, and the dimensional change rate by etching removal and the dimensional change rate by 150 degreeC x 30 minute heating were measured.
The measurement results are summarized in Table 1.

The same liquid crystal polymer film as in Example 3 was heat-treated so that the film temperature was 240 ° C. while applying a tension of 200 kN / m ² in a vacuum apparatus. Then, the plating laminated body was produced by the same operation as Example 1, and the dimensional change rate by etching removal and the dimensional change rate by 150 degreeC x 30 minute heating were measured.
The measurement results are summarized in Table 1.

Except for not performing the plasma treatment, the same operation as in Example 1 was performed to prepare a plated laminate, and the dimensional change rate by etching removal and the dimensional change rate by heating at 150 ° C. for 30 minutes were measured.
The measurement results are summarized in Table 1.

(Comparative Example 1)
The same liquid crystal polymer film as in Example 1 was heat-treated so that the film temperature was 100 ° C. in a state where a tension of 800 kN / m ² was applied in a vacuum apparatus. Then, the plating laminated body was produced by the same operation as Example 1, and the dimensional change rate by etching removal and the dimensional change rate by 150 degreeC x 30 minute heating were measured.
The measurement results are summarized in Table 1.

(Comparative Example 2)
The same liquid crystal polymer film as in Example 1 was subjected to heat treatment so that the film temperature was 150 ° C. while applying a tension of 6400 kN / m ² in a vacuum apparatus. Then, the plating laminated body was produced by the same operation as Example 1, and the dimensional change rate by etching removal and the dimensional change rate by 150 degreeC x 30 minute heating were measured.
The measurement results are summarized in Table 1.

(Comparative Example 3)
The same liquid crystal polymer film as in Example 1 was not subjected to heat treatment, and a plated laminate was prepared by the same operation as in Example 1, and the dimensional change rate by etching removal and the dimensional change rate by heating at 150 ° C. for 30 minutes were measured. .
The measurement results are summarized in Table 1.

(Comparative Example 4)
When the same liquid crystal polymer film as in Example 1 was subjected to a heat treatment so that the film temperature was 300 ° C. in a state where a tension of 400 kN / m ² was applied in a vacuum apparatus, the film was deformed.

Claims (7)

A plating laminate in which a plating layer is provided on at least one surface of the long liquid crystal polymer film without using an adhesive,
The long liquid crystal polymer film is a wholly aromatic polyester film extruded from an extrusion mold using a melt extrusion molding method,
The post-etch plating laminate after removing a part of the plating layer of the plating laminate by an etching process exhibits a dimensional change behavior in which the plating laminate shrinks or extends in the longitudinal direction and the width direction,
The dimensional change rate in the longitudinal direction and the width direction of the post-etch plating laminate in the dimensional change behavior is in the range of -0.05% to + 0.05%,
The dimensional change rate in the longitudinal direction and the width direction of the heat-treated plated laminate after heat-treating the post-etched plated laminate for 30 minutes at 150 ° C. is in the range of −0.1% to + 0.1%. Plating laminate. The plating laminate according to claim 1, wherein the plating layer is a metal layer. The plating layer includes a first metal layer made of nickel, chromium, an alloy containing nickel or an alloy containing chromium from the long liquid crystal polymer film side, and a second metal layer of a copper layer is formed on the surface of the first metal layer. The plated laminate according to claim 2, wherein the plated laminate is a structure provided. A printed wiring board having a wiring layer provided on the surface of a liquid crystal polymer film without using an adhesive,
4. A printed wiring board, wherein the plating layer of the plating laminate according to claim 2 is formed into a wiring layer by wiring processing by etching. While applying a tension of 80 to 4000 kN / m ² in the longitudinal direction to a liquid crystal polymer film made of wholly aromatic polyester formed into a film using a melt extrusion molding method, the temperature of the liquid crystal polymer film is 120 ° C. or more, and the liquid crystal After the heat treatment in a temperature range of 20 ° C. or lower than the α relaxation temperature of the polymer film, at least one surface of the heat-treated liquid crystal polyester film is subjected to film formation using a dry plating method. Production method.   6. The plating according to claim 5, wherein processing steps from the heat treatment to the film forming treatment are performed in a reduced pressure atmosphere, and a surface modification treatment is performed between the heat treatment and the film forming treatment. A manufacturing method of a layered product.   The method for manufacturing a plated laminate according to claim 5 or 6, wherein the film forming process is a sputtering film forming process, and the film formed by the film forming process is a metal layer.