JP6480289B2 - Method for producing thermoplastic liquid crystal polymer film with metal vapor-deposited layer, thermoplastic liquid crystal polymer film with metal vapor-deposited layer using the production method, method for producing metal-clad laminate, and metal-clad laminate - Google Patents

Description

  The present invention relates to a film (hereinafter referred to as “thermoplastic liquid crystal polymer”) comprising a thermoplastic polymer (hereinafter referred to as “thermoplastic liquid crystal polymer”) provided with a metal vapor deposition layer and capable of forming an optically anisotropic melt phase. The present invention relates to a method for producing a liquid crystal polymer film), a thermoplastic liquid crystal polymer film with a metal vapor deposition layer using the production method, a method for producing a metal-clad laminate, and a metal-clad laminate.

  Conventionally, a metal-clad laminate provided with a thermoplastic liquid crystal polymer film has excellent low moisture absorption, heat resistance, chemical resistance and electrical properties derived from the thermoplastic liquid crystal polymer film, and also has excellent dimensional stability. Therefore, it is used as a material for circuit boards such as flexible wiring boards and circuit boards for semiconductor mounting.

  As a method for producing this metal-clad laminate, for example, after performing a surface treatment with plasma on one side of a liquid crystal polymer film, a first metal layer is formed on the surface-treated surface using a sputtering method, A method of forming a copper layer as a second metal layer by forming a copper film by sputtering and a copper film by electrolytic copper plating on the first metal layer, and then performing an annealing treatment in an inert atmosphere Has been proposed. And by such a method, since the surface of the liquid crystal polymer film is roughened so as to have a fine structure, the anchor effect due to the irregularities on the surface of the liquid crystal polymer film is exhibited. As a result, the liquid crystal polymer film and the metal layer It is described that the adhesion strength between them is improved (see, for example, Patent Document 1).

  Further, for example, a method has been proposed in which a metal thin film is deposited on a liquid crystal polymer film by a vacuum deposition method, a metal film is formed by an electrolytic plating method, and then heat treatment is performed. And it is described by such a method that the copper vapor deposition film | membrane with high adhesiveness with a liquid crystal polymer film is provided, and the metal-clad laminated board suitable for a high frequency use can be obtained (for example, refer patent document 2). ).

JP 2014-160738 A JP 2010-165877 A

  Here, in recent years, due to the spread of high-performance small electronic devices such as smartphones, the density of parts has progressed, and the performance of electronic devices has also increased, so the relationship between thermoplastic liquid crystal polymer film and metal film There is a demand for a metal-clad laminate that has excellent adhesion strength and is compatible with high-frequency transmission signals (that is, has high-frequency characteristics).

  However, in the method for producing a metal-clad laminate described in Patent Document 1, if the surface of the liquid crystal polymer film is roughened, the skin effect is increased, so that the high-frequency characteristics are poor and the surface is roughened. When the treatment is insufficient, the adhesion strength between the liquid crystal polymer film and the metal layer is not improved, and as a result, there is a problem that it is difficult to achieve both adhesion characteristics and high frequency characteristics.

  Moreover, in the manufacturing method of the metal-clad laminate described in Patent Document 2, it is necessary to reduce the crystal size of the vapor deposition film in order to improve the adhesion strength, but in order to reduce the crystal size of the vapor deposition film, a vacuum is required. It is necessary to increase the degree of processing and decrease the processing speed, and further, since it is necessary to perform heat treatment after forming the metal film, there is a problem that the manufacturing process becomes complicated and the cost increases. .

  Therefore, the present invention has been made in view of the above-mentioned problems, and has a high-frequency characteristic and an excellent adhesion strength between the thermoplastic liquid crystal polymer film and the metal vapor deposition layer by an inexpensive and simple method. It is an object of the present invention to provide a method for producing a coated thermoplastic liquid crystal polymer film, a thermoplastic liquid crystal polymer film with a metal vapor deposition layer using the production method, a method for producing a metal-clad laminate, and a metal-clad laminate.

  In order to achieve the above object, the method for producing a thermoplastic liquid crystal polymer film with a metal vapor deposition layer of the present invention comprises depositing a metal on a surface of a thermoplastic liquid crystal polymer film at a temperature of 270 ° C. or more and 290 ° C. or less, A metal vapor deposition layer is formed.

  In addition, the method for producing a metal-clad laminate of the present invention includes a metal-deposited layer-attached heat formed by depositing a metal on a surface of a thermoplastic liquid crystal polymer film at a temperature of 270 ° C. or more and 290 ° C. or less. A metal plating layer is formed on the surface of a metal vapor deposition layer by performing a plating process on the plastic liquid crystal polymer film.

  According to the present invention, it is possible to provide a thermoplastic liquid crystal polymer film with a metal vapor deposition layer having high frequency characteristics and excellent adhesion strength between the thermoplastic liquid crystal polymer film and the metal vapor deposition layer by an inexpensive and simple method. .

It is sectional drawing which shows the structure of the metal-clad laminated board which concerns on embodiment of this invention. It is the schematic which shows the whole structure of the vapor deposition apparatus used in the manufacturing method of the thermoplastic liquid crystal polymer film with a metal vapor deposition layer which concerns on embodiment of this invention. It is sectional drawing which shows the structure of the metal-clad laminated board which concerns on the modification of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The present invention is not limited to the following embodiment.

  FIG. 1 is a cross-sectional view showing the structure of a metal-clad laminate according to an embodiment of the present invention.

  As shown in FIG. 1, the metal-clad laminate 1 of the present embodiment is composed of a thermoplastic liquid crystal polymer film 2 and a metal layer 3 laminated on one side of the thermoplastic liquid crystal polymer film 2.

<Metal layer>
There is no restriction | limiting in particular as the metal vapor deposition layer 4 of this invention, For example, copper, gold | metal | money, silver, nickel, aluminum, stainless steel etc. can be mentioned, From viewpoints, such as electroconductivity, handleability, and cost, it is copper. It is preferable to use aluminum or aluminum.

  As thickness of the metal vapor deposition layer 4, 0.05 to 1.0 micrometer is desirable. This is because when the metal plating layer 5 is thin, there is a case in which a current flows through the metal vapor deposition layer 4 and breaks. When the metal vapor deposition layer 4 is thick, the vapor deposition layer is formed. This is because a long time is required and the time for vapor deposition becomes long, so that the productivity is lowered and the cost is remarkably increased.

  The thickness of the metal layer 3 after plating is preferably in the range of 1 μm to 200 μm, and more preferably in the range of 3 μm to 20 μm. This is because when the thickness is smaller than 1 μm, the thickness is too small, and in the manufacturing process of the metal-clad laminate 1, the thickness of the metal foil is so thin that a circuit may be damaged when a large current is passed. Further, when the thickness is larger than 200 μm, the thickness is too large. For example, when used as a flexible wiring board, the bending performance is deteriorated, and it is appropriate because it takes time and costs when performing plating. Thickness is desired.

<Thermoplastic liquid crystal polymer film>
The raw material of the thermoplastic liquid crystal polymer film of the present invention is not particularly limited. Examples thereof include known thermotropic liquid crystal polyesters and thermotropic liquid crystal polyester amides derived from the compounds categorized as (1) to (4) below and derivatives thereof. However, it goes without saying that there is an appropriate range for each combination of raw material compounds in order to obtain a polymer capable of forming an optically anisotropic melt phase.

  (1) Aromatic or aliphatic dihydroxy compounds (see Table 1 for typical examples)

  (2) Aromatic or aliphatic dicarboxylic acids (see Table 2 for typical examples)

  (3) Aromatic hydroxycarboxylic acid (see Table 3 for typical examples)

  (4) Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for typical examples)

  Moreover, the copolymer (a)-(e) which has a structural unit shown in Table 5 as a typical example of the thermoplastic liquid crystal polymer obtained from these raw material compounds can be mentioned.

Further, the thermoplastic liquid crystal polymer used in the present invention is within the range of about 200 to about 400 ° C., particularly within the range of about 250 to about 350 ° C. for the purpose of giving the film desired heat resistance and processability. Those having a melting point (hereinafter referred to as “M ₀ p”) are preferred, but those having a relatively low melting point are preferred from the viewpoint of film production.

  Accordingly, when higher heat resistance and melting point are required, the film obtained once can be heated to the desired heat resistance and melting point. If an example of the conditions of heat processing is demonstrated, even if the melting | fusing point of the film obtained once is 283 degreeC, if it heats at 260 degreeC for 5 hours, melting | fusing point will be 320 degreeC.

M ₀ p can be determined by measuring the temperature at which the main endothermic peak appears with a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC).

  The thermoplastic liquid crystal polymer film 2 of the present invention is obtained by extruding the above polymer. At this time, any extrusion molding method can be used, but the well-known T-die film-forming stretching method, laminate stretching method, inflation method and the like are industrially advantageous. In particular, in the inflation method, stress is applied not only in the mechanical axis (longitudinal) direction of the film (hereinafter referred to as “MD direction”) but also in the direction perpendicular thereto (hereinafter referred to as “TD direction”). A film having a balance of mechanical and thermal properties in the MD and TD directions can be obtained.

  In addition, the thermoplastic liquid crystal polymer film 2 of the present embodiment preferably has a molecular orientation SOR (Segment Orientation Ratio) in the longitudinal direction of the film in a range of 0.90 or more and less than 1.20. A range of 15 or less is more preferable, and a range of 0.97 or more and 1.15 or less is still more preferable.

  The thermoplastic liquid crystal polymer film 2 having a molecular orientation in this range has a good balance of mechanical and thermal properties in the MD and TD directions, and is not only highly practical. There exists an advantage which makes the isotropic and dimensional stability of the metal-clad laminated board 1 for a board | substrate favorable.

  Further, when the degree of molecular orientation SOR is 0.50 or less or 1.50 or more, the orientation of the liquid crystal polymer molecules is remarkably biased, so that the film becomes hard and easily tears in the TD direction or MD direction. For circuit boards that require form stability such as no warping during heating, the molecular orientation degree SOR needs to be in the range of 0.90 or more and less than 1.15, as described above. In particular, when it is necessary to eliminate warping during heating, it is preferably 0.95 or more and 1.08 or less. Moreover, a film dielectric constant can be made uniform by making molecular orientation 0.90 or more and 1.08 or less.

  “Molecular orientation SOR” as used herein refers to an index that gives the degree of molecular orientation of the segments that make up a molecule. Unlike conventional MOR (Molecular Orientation Ratio), the thickness of the object is taken into account. Value.

  The molecular orientation SOR is calculated as follows.

  First, using a known microwave molecular orientation measuring machine, the thermoplastic liquid crystal polymer film 2 is inserted into the microwave resonant waveguide so that the film surface is perpendicular to the traveling direction of the microwave. The electric field intensity (microwave transmission intensity) of the microwave that has passed through is measured.

And based on this measured value, m value (it calls a refractive index) is computed by following Numerical formula (1).
(Equation 1)
m = (Zo / Δz) X [1-νmax / νo] (1)
(Where Zo is the device constant, Δz is the average thickness of the object, νmax is the frequency that gives the maximum microwave transmission intensity when the microwave frequency is changed, and νo is the average thickness of zero (ie This is the frequency that gives the maximum microwave transmission intensity when there is no object.)
Next, when the rotation angle of the object relative to the vibration direction of the microwave is 0 °, that is, the vibration direction of the microwave and the direction in which the molecules of the object are best oriented (usually the longitudinal direction of the extruded film) ) comprising: a m value when the direction giving the minimum intensity of transmitted microwave are coincident m _0, a m value when the rotation angle is 90 ° as m _90, orientation ratio SOR is m ₀ / It is calculated by m _90.

  The thickness of the thermoplastic liquid crystal polymer film 2 of the present invention is not particularly limited. However, when the metal-clad laminate 1 using the thermoplastic liquid crystal polymer film 2 as an electrically insulating material is used as a printed wiring board, the thickness is 20 to 20. The range of 150 μm is preferable, and the range of 20 to 50 μm is more preferable.

  This is because when the film thickness is too thin, the rigidity and strength of the film are reduced, so that when the electronic component is mounted on the obtained printed wiring board, the printed wiring board is deformed by pressure, and the wiring This is because the positional accuracy deteriorates and causes a defect.

  In addition, as an electrically insulating material for a main circuit board such as a personal computer, a composite of the above-described thermoplastic liquid crystal polymer film and another electrically insulating material, for example, a glass substrate can be used. In addition, you may mix | blend additives, such as a lubricant and antioxidant, with a film.

  In addition, the thermoplastic liquid crystal polymer film 2 of the present invention is preferably a film having sufficient material strength and having a small dimensional change in the heat treatment during the vapor deposition step described later. From the above viewpoint, the thermoplastic liquid crystal polymer film preferably has a toughness of 50 to 90 MPa, and more preferably 60 to 90 MPa.

The “toughness of the thermoplastic liquid crystal polymer film” as used herein refers to the elongation measured using a tensile tester (trade name: RTE-210, manufactured by A & D) by a method based on ASTM D882. And the value calculated by the following mathematical formula (2) from the measured value of the maximum tensile strength.
(Equation 2)
Toughness = Elongation × Maximum tensile strength × 1/2 (2)
In addition, the thermoplastic liquid crystal polymer has a thermoplasticity such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyetheretherketone, fluororesin and the like within the scope of the present invention. A polymer and various additives may be added, and a filler may be added as necessary.

  In addition, as the thermoplastic liquid crystal polymer film 2 of the present invention, for example, Bexter CT-Z (manufactured by Kuraray Co., Ltd.) can be used.

  Next, the manufacturing method of the metal-clad laminated board in embodiment of this invention is demonstrated.

  In this embodiment, the surface of the thermoplastic liquid crystal polymer film 2 is provided with a vapor deposition step of forming a metal vapor deposition layer by a vacuum vapor deposition method, and an electrolytic plating step of forming a metal plating layer on the surface of the metal vapor deposition layer. .

(Deposition process)
First, a vapor deposition boat (formed with tungsten or molybdenum as a resistor) containing a vapor deposition source (for example, Cu having a purity of 99% or more) is placed in a vapor deposition chamber in a vacuum vapor deposition apparatus. Next, by applying an electric current to the vapor deposition boat and heating it, a metal is vapor-deposited on the surface of the thermoplastic liquid crystal polymer film 2, and the metal vapor deposition layer 4 is formed on the surface of the thermoplastic liquid crystal polymer film 2.

  In addition, in a vacuum atmosphere, a vapor deposition source is put into a crucible, an electron beam is irradiated to a crucible, and a vapor deposition source is heated, A metal is vapor-deposited on the surface of the thermoplastic liquid crystal polymer film 2, The metal vapor deposition layer 4 May be formed.

  Further, from the viewpoint of improving productivity, the surface of the thermoplastic liquid crystal polymer film 2 is moved by moving the sheet-like thermoplastic liquid crystal polymer film 2 using a roll-to-roll method in a deposition chamber. It is good also as a structure which forms the metal vapor deposition layer 4 continuously on the top.

  FIG. 2 is a schematic view showing the overall configuration of a vapor deposition apparatus used in the method for producing a thermoplastic liquid crystal polymer film with a metal vapor deposition layer according to an embodiment of the present invention.

  The vapor deposition apparatus 20 deposits a metal on the surface of the unwinding roll 12 equipped with the roll-shaped thermoplastic liquid crystal polymer film 2 and the thermoplastic liquid crystal polymer film 2 at a predetermined temperature. A heating roll 13 for forming, a winding roll 14 for winding up the thermoplastic liquid crystal polymer film 2 with the metal vapor deposition layer 4, and a guide for moving the thermoplastic liquid crystal polymer film 2 by a roll-to-roll method. Rolls 15 and 16.

  Then, the crucible 17 disposed below the heating roll 13 is irradiated with an electron beam from the electron gun 18 to heat the vapor deposition source accommodated in the crucible 17, so that the surface of the thermoplastic liquid crystal polymer film 2 is heated. A metal (for example, copper) is vapor-deposited to form a metal vapor-deposited layer 4.

  Here, the present invention is characterized in that the metal vapor deposition layer 4 is formed by vapor-depositing a metal at a temperature of 270 ° C. or higher and 290 ° C. or lower on the surface of the thermoplastic liquid crystal polymer film 2.

  As described above, in the present invention, unlike the above-described conventional technique, the thermoplastic liquid crystal polymer film 2 is softened because the heat treatment is performed during the vapor deposition treatment, not after the metal vapor deposition layer is formed by the vapor deposition treatment. In the vapor deposition step, the metal is more likely to adhere to the surface of the thermoplastic liquid crystal polymer film 2.

  Moreover, since the adhesive force of the thermoplastic liquid crystal polymer film 2 and the metal vapor deposition layer 4 increases by setting the heating temperature in a vapor deposition process to 270 degreeC or more and 290 degrees C or less, peel strength improves. This is because when the vapor deposition is performed at a temperature close to the thermal deformation temperature of the thermoplastic liquid crystal polymer film 2, the vapor deposition particles (particles scattered during the vapor deposition) sink into the softened film by heating. This is probably because the adhesion between the polymer film 2 and the metal vapor deposition layer 4 increases. Incidentally, the particles that enter the film are generally about several tens of millimeters and are sufficiently smaller than the roughness of the film surface.

  Therefore, unlike the above prior art, without performing the roughening treatment on the surface of the thermoplastic liquid crystal polymer film 2, the control of the crystal size of the metal vapor-deposited layer 4, and the heat treatment after forming the metal layer 3, It becomes possible to improve the adhesion strength between the thermoplastic liquid crystal polymer film 2 and the metal vapor deposition layer 4. Therefore, the thermoplastic liquid crystal polymer film 2 with the metal vapor deposition layer 4 having low transmission loss and excellent adhesion strength can be provided by an inexpensive and simple method.

  Further, since it is not necessary to control the size of the crystal of the metal vapor deposition layer 4 to be vapor deposited, the thermoplastic liquid crystal polymer film with the metal vapor deposition layer 4 which is efficient (that is, without reducing productivity) and has excellent adhesion strength. 2 can be provided.

  In addition, it is preferable that the thickness of the metal vapor deposition layer 4 has the thickness of 0.05 micrometer or more and 1.0 micrometer or less.

  In addition, since the present invention performs vapor deposition while heating the thermoplastic liquid crystal polymer film 2 at the time of vapor deposition (for example, while heating the thermoplastic liquid crystal polymer film 2 with a heating roll in the above embodiment), it is formed at the time of vapor deposition. Although the crystal size of the metal vapor deposition layer 4 is increased by heating, in the present invention, the crystal size of the metal vapor deposition layer 4 is not particularly limited, and can be set to be greater than 0.1 μm and 10 μm or less.

  Moreover, in this embodiment, it is preferable to set a vapor deposition rate to 1 nm / s or more and 5 nm / s or less from a viewpoint of improving the productivity in a roll-to-roll system.

  Moreover, in this embodiment, the moving speed of the thermoplastic liquid crystal polymer film 2 in the roll-to-roll method is set to 0.1 m / min to 5 m / min.

(Electrolytic plating process)
Next, the metal plating layer 5 is formed on the surface of the metal vapor deposition layer 4 using an electrolytic plating method. More specifically, the metal vapor deposition layer 4 and the metal plating layer 5 are formed by performing electroplating of metal (for example, copper) on the metal vapor deposition layer (underlying metal film) 4 formed by the above vapor deposition process. A metal layer 3 is formed.

  This electrolytic plating method is not particularly limited. For example, when a copper plating layer is formed as the metal plating layer 5, a normal copper sulfate plating method can be used.

  Moreover, it is preferable that the thickness of the metal plating layer 5 has a thickness of 1 μm or more and 10 μm or less from the viewpoint of productivity and an aspect ratio of the circuit. When the metal plating layer is thin, a circuit having a sharp shape in which the aspect ratio indicated by the upper and lower widths of the circuit is close to “1” is obtained. When the metal plating layer 5 is thick, the circuit has a small trapezoidal shape when the circuit is formed. As a circuit shape of millimeter wave and microwave, a sharp circuit whose aspect ratio is close to “1” is desired.

Further, from the viewpoint of productivity, it is preferable to set the current density to 0.1 A / dm ² or more 0.5A / dm ² or less between the anode and the cathode.

  In addition, as described above, in the present invention, the adhesion strength between the thermoplastic liquid crystal polymer film 2 and the metal layer 3 can be improved, but from the viewpoint of circuit reliability, the thermoplastic liquid crystal polymer film 2 and the metal layer. 3 is preferably 0.8 kN / m or more, and more preferably 0.9 kN / m or more.

  The “peel strength” as used herein refers to a pull measured using a digital force gauge (for example, product name: ZP-500N, manufactured by IMADA) by a method based on IPC-TM650 2.4.3. It means the peel strength value (kN / m).

  In addition, you may change the said embodiment as follows.

  In the above embodiment, the metal-clad laminate 1 in which the metal layer 3 is bonded to one side of the thermoplastic liquid crystal polymer film 2 has been described as an example. However, the present invention is not limited to the thermoplastic liquid crystal polymer film shown in FIG. 2 is also applicable to the metal-clad laminate 10 in which the metal layer 3 is laminated on both sides. That is, the present invention can be applied to a metal-clad laminate in which the metal layer 3 is laminated on at least one surface of the thermoplastic liquid crystal polymer film 2.

  Hereinafter, the present invention will be described based on examples. In addition, this invention is not limited to these Examples, These Examples can be changed and changed based on the meaning of this invention, and they are excluded from the scope of the present invention. is not.

Example 1
<Copper vapor deposition film formation>
First, a thermoplastic liquid crystal polymer film (made by Kuraray Co., Ltd., trade name: Bexter CZ-T) having a thickness of 50 μm was prepared. Next, by adopting a roll-to-roll method using a vacuum evaporation apparatus (manufactured by Rock Giken Kogyo Co., Ltd., trade name: RVC-W-300), by moving the sheet-like thermoplastic liquid crystal polymer film, A metal vapor deposition layer was continuously formed on the surface of the thermoplastic liquid crystal polymer film.

  More specifically, the thermoplastic liquid crystal polymer film is set on the loader side, the open window is completely closed, and then a vacuum is drawn, and at the same time, a heating roll (a roll on which metal is deposited on the thermoplastic liquid crystal polymer film). ) Was set to 100 ° C.

  Next, the copper ingot was taken out, and copper pellets were added so that the total weight of copper was 450 g. The copper pellet was washed with sodium persulfate water as a pretreatment, and then washed with distilled water.

Next, after confirming that the degree of vacuum in the vapor deposition chamber was 7 × 10 ⁻³ Pa, the set temperature of the heating roll was set to 280 ° C. Thereafter, the output of EMI (emission current value of the electron gun) was increased to melt the copper. At this time, the EMI output value was adjusted so that the vapor deposition rate was 2.7 nm / s.

Next, after confirming that the temperature of the heating roll has reached the set temperature (280 ° C.) and the degree of vacuum in the deposition chamber is 5 × 10 ⁻³ Pa or less, the transport speed of the thermoplastic liquid crystal polymer film In the state which set to 0.5 m / min, the copper vapor deposition process was performed and the copper vapor deposition film | membrane which has a thickness of 0.3 micrometer was formed.

<Formation of metal layer>
Next, a copper plating layer (thickness: 12 μm) is formed on the surface of the copper vapor deposition film by electrolytic plating, thereby forming a copper layer 12 μm composed of the copper vapor deposition film and the copper plating layer, and a copper-clad laminate. A plate was made. In addition, the thickness of the copper foil becomes 12 μm by putting it in a bath of a high throw type sulfuric acid basic bath (a copper sulfate plating basic composition containing 40 to 100 g / L copper sulfate and 150 to 250 g / L sulfuric acid). I did it.

<Measurement of peel strength>
Next, a 5 mm wide peel test piece was produced from the produced copper-clad laminate, the adhesive interface between the thermoplastic liquid crystal polymer film and the copper layer was exposed, and then the thermoplastic liquid crystal polymer film layer of the test piece was bonded on both sides. Fix to a flat plate with tape, peel off the copper layer at a rate of 50 mm / min in the 90 ° direction at room temperature, and measure the peeling load using an IMADA digital force gauge (trade name: ZP-500N). The average value (kN / m) of the load at the time of peeling about 5 cm was measured.

  In addition, peeling was continued over about 60 seconds in one measurement, and the load was measured several times (16 times per second) during that time. That is, after obtaining load data for 16 times / second x 60 seconds = 960 times in one measurement, the measurement values at the start and end of measurement are excluded, and the measurement data for 700 times in the middle is averaged. And the average value of the load.

  Moreover, since peel strength of 0.8 kN / m or more is required from the viewpoint of bending resistance and the like, the case where the strength is 0.8 kN / m or more was judged to be good. The results are shown in Table 6.

(Comparative Example 1)
A copper clad laminate was produced in the same manner as in Example 1 except that the set temperature of the heating roll in the vapor deposition step was changed to 260 ° C. Thereafter, peel strength was measured in the same manner as in Example 1 described above. The results are shown in Table 6.

(Comparative Example 2)
A copper clad laminate was produced in the same manner as in Example 1 except that the set temperature of the heating roll in the vapor deposition step was changed to 240 ° C. Thereafter, peel strength was measured in the same manner as in Example 1 described above. The results are shown in Table 6.

  As shown in Table 6, in Example 1 in which the temperature of the heating roll was set to 280 ° C. to form a copper vapor-deposited film, the setting temperature of the heating roll was less than 270 ° C. compared to Comparative Examples 1 and 2, It can be seen that the adhesion strength between the thermoplastic liquid crystal polymer film and the copper layer (that is, the copper deposited film) is excellent.

  As described above, the present invention is particularly useful for a method for producing a thermoplastic liquid crystal polymer film with a metal vapor deposition layer and a thermoplastic liquid crystal polymer film with a metal vapor deposition layer using the same.

DESCRIPTION OF SYMBOLS 1 Metal-clad laminate 2 Thermoplastic liquid crystal polymer film 3 Metal layer 4 Metal vapor deposition layer 5 Metal plating layer 10 Metal-clad laminate 12 Unwinding roll 13 Heating roll 14 Winding roll 17 Crucible 18 Electron gun 20 Deposition apparatus

Claims (4)

  A method for producing a thermoplastic liquid crystal polymer film with a metal vapor deposition layer, comprising depositing a metal on a surface of a thermoplastic liquid crystal polymer film at a temperature of 270 ° C. or more and 290 ° C. or less to form a metal vapor deposition layer.   The said metal is copper, The manufacturing method of the thermoplastic liquid crystal polymer film with a metal vapor deposition layer of Claim 1 characterized by the above-mentioned.   By depositing a metal on the surface of the thermoplastic liquid crystal polymer film at a temperature of 270 ° C. or higher and 290 ° C. or lower and forming a metal vapor deposited layer on the thermoplastic liquid crystal polymer film with the metal deposited layer, A method for producing a metal-clad laminate, comprising forming a metal plating layer on a surface of a metal vapor-deposited layer. The method for producing a metal-clad laminate according to claim 3 , wherein the metal plating layer is a copper layer.

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