WO2020255871A1 - Method for producing metal clad laminate - Google Patents

Abstract

Provided is a method for efficiently producing a formed metal clad laminate. In the producing method, a long one-side metal clad laminate (A) in which a metal layer is bonded to one face of a thermoplastic liquid crystal polymer film, and a long shaped metal sheet (B), at least one surface of which is a shaped surface are prepared, the one-side metal clad laminate (A) and the shaped metal sheet (B) are then arranged so that the surface of the thermoplastic liquid crystal polymer film of the one-side metal clad laminate (A) and the shaped surface of the shaped metal sheet (B) are in contact with each other, and the one-side metal clad laminate (A) and the shaped metal sheet (B) are introduced into a pair of press rolls (r₁, r₂) for thermocompression bonding, to produce a metal clad laminate.

Description

Manufacturing method of metal-clad laminate Related application

This application claims the priority of Japanese Patent Application No. 2019-112341 filed on June 17, 2019, and the entire application is cited as a part of this application by reference.

In the present invention, a film made of a thermoplastic polymer capable of forming an optically anisotropic molten phase (hereinafter, this may be referred to as a thermoplastic liquid crystal polymer) (hereinafter, this is referred to as a thermoplastic liquid crystal polymer film). A metal-clad laminate (or a metal-clad laminate) in which a metal layer is laminated on one surface (which may be), and a metal shaping sheet is laminated on the other surface, the surface of the thermoplastic liquid crystal polymer film side being a shaping surface. The present invention relates to a method for producing a metal-clad laminate) from which the metal shaping sheet on the other surface is peeled off.

Thermoplastic liquid crystal polymer film is known as a material having excellent heat resistance, low hygroscopicity, high frequency characteristics, etc., and has been attracting attention as an electronic circuit material for high-speed transmission in recent years. When used for electronic circuit board applications, a metal-clad laminate of a thermoplastic liquid crystal polymer film and a metal foil is used, but in the bonding process in the circuit processing process, the thermoplastic liquid crystal polymer film provided in the metal-clad laminate is provided. The interlayer adhesiveness between the metal and the bonding sheet may not be sufficient. Conventionally, in a single-sided metal-clad laminate having a metal layer on one surface of a thermoplastic liquid crystal polymer film in order to improve the interlayer adhesiveness with a bonding sheet, an uneven shape is formed on the surface of the thermoplastic liquid crystal polymer film on the other side. The shaping process to be given was being performed.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2016-10967) includes a step of stacking a first metal foil, a liquid crystal polymer film, and a second metal foil in this order and heating and pressurizing the second metal foil. The surface to be laminated on the liquid crystal polymer film is a matte surface, and a method for producing a liquid crystal polymer film with a metal foil in which the matte surface is subjected to a mold release treatment is disclosed.

Further, in Patent Document 2 (Japanese Unexamined Patent Publication No. 2006-179609), at least one surface of each of the thermoplastic resin layers is subjected to a chemical roughening treatment using an alkaline mixed solution as a chemical solution, and the treated surface is subjected to the chemical solution roughening treatment. Disclosed is a method for producing a laminated wiring board, which comprises superimposing a laminate on the surface of another unit substrate to form a laminated plate having two or more layers, and heating and pressurizing the laminated plate. Is disclosed as a liquid crystal polymer.

JP-A-2016-10967 Japanese Unexamined Patent Publication No. 2006-179609

Further, when the metal-clad laminate is used in an electronic circuit for high-speed transmission, the metal layer serving as a transmission line has a skin effect, so that the high-frequency characteristics of the metal layer, that is, the transmission loss depends on its surface roughness. Therefore, it is desirable to use a low-roughness metal layer having a small surface roughness because the transmission loss is small, that is, the high-frequency characteristics are improved.

However, as in Patent Document 1, when the first metal foil, the liquid crystal polymer film, and the second metal foil to be peeled off later for the shaping treatment are laminated and heated and pressed to be laminated and integrated at once. If a low-roughness material is used for the first metal foil, it is necessary to heat the first metal foil to near the melting point (or above the melting point) in order to improve the interlayer adhesiveness between the first metal foil and the liquid crystal polymer film. .. In that case, high-temperature heat is applied even at the interface between the second metal leaf and the liquid crystal polymer film, which will be peeled off later, and even if the second metal leaf is subjected to the mold release treatment, the interlayer adhesion is caused by the anchor effect due to the unevenness of the surface. Since the property is high, it becomes difficult to peel off the second metal foil.

Furthermore, since the liquid crystal polymer molecules of the thermoplastic liquid crystal polymer film are easily oriented by heating and pressurizing, the orientation changes significantly when heated and pressed at a high temperature as described above, and the resulting metal-clad laminate warps. Is large, and the dimensional change is large, which makes it difficult to form a circuit board.

Further, when the chemical solution roughening treatment is performed as in Patent Document 2, fine irregularities can be imparted to the surface of the thermoplastic resin layer, but the treatment steps are increased due to the chemical solution treatment, and the production efficiency is lowered. Further, since it is difficult to completely remove the chemicals adhering to the surface subjected to the chemical treatment, problems may occur due to the presence of impurities in the obtained circuit board.

Therefore, an object of the present invention is to provide a method for producing a metal-clad laminate having a small dimensional change and being efficiently shaped.

As a result of diligent studies to achieve the above object, the inventors of the present invention have independently performed the production of the single-sided metal-clad laminate and the shaping treatment of the single-sided metal-clad laminate, thereby performing the shaping treatment. It has been found that the dimensional change of the metal-clad laminate can be suppressed because the heating and pressurizing at a high temperature can be avoided. Then, a single-sided metal-clad laminate in which a metal layer is adhered to one surface of the thermoplastic liquid crystal polymer film is prepared, and the single-sided metal-clad laminate and the metal shaping sheet are continuously thermocompression bonded to be efficiently applied. It was found that the shape processing can be performed, and the present invention has been completed.

That is, the present invention can be configured in the following aspects.
[Aspect 1]
A long single-sided metal-clad laminate (A) in which a metal layer is adhered to one surface of a thermoplastic liquid crystal polymer film, and a long metal shaping sheet (B) in which at least one surface is a shaping surface. ) And the process of preparing
A pair of pressure rolls (r ₁ , r ₂ ) are arranged so that the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the shaping surface of the metal shaping sheet (B) are in contact with each other. The thermocompression bonding process to be introduced into
A method for manufacturing a metal-clad laminate, which comprises at least.
[Aspect 2]
The method for producing a metal-clad laminate according to the first aspect.
A method for producing a metal-clad laminate, further comprising a peeling step of peeling the metal shaping sheet (B) from the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) after the thermocompression bonding step.
[Aspect 3]
In the method for producing a metal-clad laminate according to the first or second aspect, when the thermocompression bonding temperature is the melting point (Tm) of the thermoplastic liquid crystal polymer film, (Tm-150) ° C. or higher (Tm) ° C. A method for producing a metal-clad laminate, which is less than (preferably (Tm-130) ° C. or higher (Tm-5) ° C. or lower, more preferably (Tm-110) ° C. or higher (Tm-10) ° C. or lower).
[Aspect 4]
The method for producing a metal-clad laminate according to any one of aspects 1 to 3, wherein the peel strength between the single-sided metal-clad laminate (A) and the metal shaping sheet (B) is 0.5 N /. A method for producing a metal-clad laminate, which is mm or less (preferably 0.2 N / mm or less, more preferably 0.1 N / mm or less).
[Aspect 5]
The method for producing a metal-clad laminate according to any one of aspects 1 to 4, wherein the surface roughness (Rz) of the shaped surface of the metal shaping sheet (B) is 1.0 to 7.0 μm. (Preferably 1.5 to 5.5 μm, more preferably 2.0 to 4.5 μm), a method for producing a metal-clad laminate.
[Aspect 6]
The method for producing a metal-clad laminate according to any one of aspects 1 to 5.
In the preparatory process, a longer release cushion material (C) is prepared,
In the thermocompression bonding step, the release cushion material (C) is arranged on at least one of the non-contact side of the single-sided metal-clad laminate (A) and the metal shaping sheet (B), and a pair of pressure rolls (r). _1, is introduced into the _{r 2),} method for producing a metal clad laminate.
[Aspect 7]
In the method for manufacturing a metal-clad laminate according to the sixth aspect, the peel strength between the release cushion material (C) and the single-sided metal-clad laminate (A) or the metal shaping sheet (B) is 0. A method for producing a metal-clad laminate, which is 1 N / mm or less (preferably 0.05 N / mm or less, more preferably 0.03 N / mm or less).
[Aspect 8]
The method for producing a metal-clad laminate according to aspect 6 or 7, wherein the release cushioning material (C) is a heat-resistant resin film, a heat-resistant composite film, a heat-resistant non-woven fabric, and a mold release material on at least one surface. A method for producing a metal-clad laminate selected from the group consisting of a metal foil having a layer.
[Aspect 9]
The method for producing a metal-clad laminate according to any one of aspects 6 to 8, wherein the surface roughness (Rz) of at least one surface of the release cushion material (C) is 2.0 μm or less (preferably). Is 1.8 μm or less, more preferably 1.5 μm or less), a method for producing a metal-clad laminate.
[Aspect 10]
The method for producing a metal-clad laminate according to any one of aspects 6 to 9, wherein (r ₁ ) / between a pair of pressure rolls (r ₁ , r ₂ ) in the thermocompression bonding step. The single-sided metal-clad laminate (A), the metal shaping sheet (B), and the release cushion material (C) are stacked in the order of (C) / (A) / (B) / (r ₂ ). A method for manufacturing a metal-clad laminate to be introduced.
[Aspect 11]
The method for producing a metal-clad laminate according to the tenth aspect, wherein in the thermocompression bonding step, the pressure roll (r ₂ ) has a higher heating temperature than the pressure roll (r ₁ ). Method.
[Aspect 12]
The method for producing a metal-clad laminate according to any one of aspects 1 to 11, wherein a plurality of long single-sided metal-clad laminates (A) and elongated metal shaping sheets (B) are provided. A method for manufacturing a metal-clad laminate, which prepares and manufactures a plurality of metal-clad laminates.
[Aspect 13]
The method for manufacturing a metal-clad laminate according to aspect 11, which is subordinate to any one of aspects 6 to 9, wherein a plurality of sets of single-sided metal-clad laminate (A) and metal addition are formed in the thermocompression bonding step. A method for manufacturing a metal-clad laminate, in which a release cushioning material (C) is laminated and introduced between laminates including a shape sheet (B).
[Aspect 14]
A method for producing a metal-clad laminate according to aspect 13, wherein (r ₁ ) / (B) / (A) is formed between a pair of pressure rolls (r ₁ , r ₂ ) in the thermocompression bonding step. The single-sided metal-clad laminate (A), the metal shaping sheet (B), and the release cushion material (C) are stacked in the order of / (C) / (A) / (B) / (r ₂ ). A method for manufacturing a metal-clad laminate to be introduced.
[Aspect 15]
The method for producing a metal-clad laminate according to aspect 11 or 12, which is subordinate to any one of aspects 6 to 9, wherein in the thermocompression bonding step, a pair of pressure rolls (r ₁ , r _2). ), A method for manufacturing a metal-clad laminate, in which the release cushion material (C) is laminated and introduced so as to be in contact with at least one of the pressure rolls.
[Aspect 16]
The method for producing a metal-clad laminate according to aspect 15, wherein in the thermocompression bonding step, (r ₁ ) / (C) / (B) are placed between a pair of pressure rolls (r ₁ , r ₂ ). / (A) / (A) / (B) / (C) / (r ₂ ) or (r ₁ ) / (C) / (A) / (B) / (B) / (A) / (C) ) / (R ₂ ), a method for manufacturing a metal-clad laminate, in which a single-sided metal-clad laminate (A), a metal shaping sheet (B), and a release cushioning material (C) are stacked and introduced. ..

It should be noted that any combination of at least two components disclosed in the claims and / or the specification and / or the drawings is included in the present invention. In particular, any combination of two or more of the claims described in the claims is included in the present invention.

According to the present invention, a single-sided metal-clad laminate and a metal shaping sheet are prepared and arranged so that the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate and the shaping surface of the metal shaping sheet are in contact with each other. By introducing the film into a pair of pressure rolls and thermocompression bonding, the shaping process can be continuously performed, so that a metal-clad laminate in which dimensional changes are suppressed can be efficiently manufactured.

The present invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, embodiments and drawings are for illustration and illustration purposes only and should not be used to define the scope of the invention. The scope of the present invention is determined by the appended claims. The drawings are not necessarily shown at a constant scale and are exaggerated to show the principles of the present invention.
It is a side schematic diagram for demonstrating the manufacturing method of the metal-clad laminate by 1st Embodiment of this invention. It is a side schematic diagram for demonstrating the manufacturing method of the metal-clad laminate according to the 2nd Embodiment of this invention. It is a side schematic diagram for demonstrating the manufacturing method of the metal-clad laminate according to the 3rd Embodiment of this invention. It is a side schematic diagram for demonstrating the manufacturing method of the metal-clad laminate according to the 4th Embodiment of this invention. It is a side schematic diagram for demonstrating the manufacturing method of the metal-clad laminate according to the 5th Embodiment of this invention. It is a side schematic diagram for demonstrating the manufacturing method of the metal-clad laminate according to the 6th Embodiment of this invention.

In the method for producing a metal-clad laminate of the present invention, a metal-clad laminate in which a metal shaping sheet is laminated on a thermoplastic liquid crystal polymer film surface of a single-sided metal-clad laminate, or a metal-clad laminate that has been shaped-treated is continuously connected. Can be manufactured as a target.
In the present invention, the metal-clad laminate is a metal-clad laminate having a metal layer on one surface of a thermoplastic liquid crystal polymer film and a metal shaping sheet on the other surface, or a thermoplastic liquid crystal polymer film. It may be a metal-clad laminate having a metal layer on one surface and the other surface being shaped, and may be appropriately provided with other accessories (for example, a release cushioning material).

(Thermoplastic liquid crystal polymer film)
The thermoplastic liquid crystal polymer film used in the production method of the present invention is formed from a liquid crystal polymer that can be melt-molded. The thermoplastic liquid crystal polymer is a polymer capable of forming an optically anisotropic molten phase, and the chemical composition thereof is not particularly limited as long as it is a liquid crystal polymer that can be melt-molded. , Thermoplastic liquid crystal polyester, or thermoplastic liquid crystal polyester amide in which an amide bond is introduced therein.

Further, the thermoplastic liquid crystal polymer may be a polymer in which an imide bond, a carbonate bond, an isocyanate-derived bond such as a carbodiimide bond or an isocyanurate bond is further introduced into an aromatic polyester or an aromatic polyester amide.

Specific examples of the thermoplastic liquid crystal polymer used in the present invention include known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyesteramides derived from the compounds classified into (1) to (4) and derivatives thereof exemplified below. Can be mentioned. However, it goes without saying that the combination of various raw material compounds has an appropriate range in order to form a polymer capable of forming an optically anisotropic molten phase.

(1) Aromatic or aliphatic diols (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)

Typical examples of thermoplastic liquid crystal polymers obtained from these raw material compounds include copolymers having structural units shown in Tables 5 and 6.

Among these copolymers, a copolymer containing p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid as at least a repeating unit is preferable, and (i) p-hydroxybenzoic acid and 6-hydroxy- A copolymer containing a repeating unit with 2-naphthoic acid, or at least one aromatic hydroxycarboxylic acid selected from the group consisting of (ii) p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and at least one. A copolymer containing a repeating unit of the aromatic diol of the above and at least one aromatic dicarboxylic acid is preferable.

For example, in the copolymer of (i), if the thermoplastic liquid crystal polymer contains at least a repeating unit of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the p-hydroxybenzoic acid of the repeating unit (A). The molar ratio (A) / (B) of the acid to the 6-hydroxy-2-naphthoic acid of the repeating unit (B) is (A) / (B) = 10/90 to 90 / in the thermoplastic liquid crystal polymer. It is preferably about 10, more preferably (A) / (B) = about 15/85 to 85/15, and even more preferably (A) / (B) = 20/80 to. It may be about 80/20.

Further, in the case of the copolymer of (ii), at least one aromatic hydroxycarboxylic acid (C) selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid and 4,4'-. From the group consisting of at least one aromatic diol (D) selected from the group consisting of dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, and the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. The molar ratio of each repeating unit of at least one selected aromatic dicarboxylic acid (E) in the thermoplastic liquid crystal polymer is as follows: aromatic hydroxycarboxylic acid (C): said aromatic diol (D): said aromatic dicarboxylic acid ( E) = (30 to 80) :( 35 to 10) :( 35 to 10), more preferably (C) :( D) :( E) = (35 to 75) :( It may be about 32.5 to 12.5): (32.5 to 12.5), and more preferably (C) :( D) :( E) = (40 to 70) :( 30 to 12.5). 15): It may be about (30 to 15).

The molar ratio of the repeating unit derived from 6-hydroshiki-2-naphthoic acid in the aromatic hydroxycarboxylic acid (C) may be, for example, 85 mol% or more, preferably 90 mol% or more. It may be preferably 95 mol% or more. The molar ratio of the repeating unit derived from 2,6-naphthalenedicarboxylic acid in the aromatic dicarboxylic acid (E) may be, for example, 85 mol% or more, preferably 90 mol% or more, and more preferably 95 mol%. It may be% or more.

The aromatic diol (D) is a repeating unit derived from two different aromatic diols selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether. It may be (D1) and (D2), in which case the molar ratio of the two aromatic diols may be (D1) / (D2) = 23/77 to 77/23, more preferably. May be 25/75 to 75/25, more preferably 30/70 to 70/30.

Further, the molar ratio of the repeating structural unit derived from the aromatic diol to the repeating structural unit derived from the aromatic dicarboxylic acid is preferably (D) / (E) = 95/100 to 100/95. If it is out of this range, the degree of polymerization does not increase and the mechanical strength tends to decrease.

The fact that the optically anisotropic molten phase referred to in the present invention can be formed can be determined by, for example, placing the sample on a hot stage, heating the sample in a nitrogen atmosphere, and observing the transmitted light of the sample. ..

A preferred thermoplastic liquid crystal polymer has a melting point (hereinafter referred to as Tm ₀ ) having, for example, a melting point in the range of 200 to 360 ° C., preferably in the range of 240 to 350 ° C., and more preferably Tm _0. The temperature is 260 to 330 ° C. The melting point can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer sample using a differential scanning calorimeter. That is, after the thermoplastic liquid crystal polymer sample was heated at a rate of 10 ° C./min to completely melt it, the melt was cooled to 50 ° C. at a rate of 10 ° C./min and again at a rate of 10 ° C./min. The position of the endothermic peak that appears after the temperature is raised is determined as the melting point of the thermoplastic liquid crystal polymer sample.

Further, from the viewpoint of melt moldability, the thermoplastic liquid crystal polymer may have a melt viscosity of 30 to 120 Pa · s at a shear rate of 1000 / s at (Tm ₀ + 20) ° C., preferably a melt viscosity of 50. It may have ~ 100 Pa · s.

The thermoplastic liquid crystal polymer includes thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyetheretherketone, and fluororesin, as long as the effects of the present invention are not impaired. , Various additives, fillers and the like may be added.

The thermoplastic liquid crystal polymer film used in the production method of the present invention is obtained, for example, by extrusion molding the melt-kneaded product of the thermoplastic liquid crystal polymer. Any method is used as the extrusion molding method, but the well-known T-die method, inflation method and the like are industrially advantageous. In particular, in the inflation method, stress is applied not only in the mechanical axis direction (hereinafter abbreviated as MD direction) of the thermoplastic liquid crystal polymer film but also in the direction orthogonal to this (hereinafter abbreviated as TD direction), and the MD direction and TD direction are applied. Since it can be uniformly stretched in the direction, a thermoplastic liquid crystal polymer film having controlled molecular orientation, dielectric properties, etc. in the MD direction and the TD direction can be obtained.

For example, in the extrusion molding by the T-die method, the melt sheet extruded from the T-die may be stretched not only in the MD direction of the thermoplastic liquid crystal polymer film but also in both the MD direction and the TD direction at the same time to form a film. Alternatively, the melt sheet extruded from the T die may be once stretched in the MD direction and then stretched in the TD direction to form a film.

Further, in the extrusion molding by the inflation method, a predetermined draw ratio (corresponding to the stretching ratio in the MD direction) and a blow ratio (corresponding to the stretching ratio in the TD direction) with respect to the cylindrical sheet melt-extruded from the ring die. It may be stretched with and formed into a film.

The draw ratio of such extrusion molding may be, for example, about 1.0 to 10 as the draw ratio (or draw ratio) in the MD direction, preferably about 1.2 to 7, and more preferably 1. It may be about 3 to 7. Further, the stretching ratio (or blow ratio) in the TD direction may be, for example, about 1.5 to 20, preferably about 2 to 15, and more preferably about 2.5 to 14.

Further, if necessary, a known or conventional heat treatment may be performed to adjust the melting point and / or the coefficient of thermal expansion of the thermoplastic liquid crystal polymer film. The heat treatment conditions can be set appropriately according to the object, for example, the thermoplastic liquid crystal polymer relative to the melting point _{(Tm 0), (Tm 0} -10) ℃ or higher _{(e.g., (Tm 0 -10) ~ (} Tm 0 +30) The melting point (Tm) of the thermoplastic liquid crystal polymer film may be raised by heating at about ° C., preferably (Tm ₀ ) to (Tm ₀ +20) ° C.) for several hours. The melting point (Tm) of the thermoplastic liquid crystal polymer film can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer film sample using a differential scanning calorimeter. That is, the position of the endothermic peak that appears when the temperature of the thermoplastic liquid crystal polymer film sample is raised at a rate of 10 ° C./min can be determined as the melting point (Tm) of the thermoplastic liquid crystal polymer film.

(Single-sided metal-clad laminate)
The single-sided metal-clad laminate used in the production method of the present invention is one in which a metal layer is arranged on one surface of the thermoplastic liquid crystal polymer film. A commercially available product may be used as the single-sided metal-clad laminate. For example, in the method for producing a single-sided metal-clad laminate, a metal foil is bonded to a thermoplastic liquid crystal polymer film by thermocompression bonding as a metal layer. Alternatively, the metal layer may be formed by sputtering, vapor deposition, electroless plating or the like. From the viewpoint of production efficiency and convenience, a method of adhering a metal foil to a thermoplastic liquid crystal polymer film by thermocompression bonding is preferable.

A long one-sided metal-clad laminate is used. In that case, the long object may have a roll shape wound on a roll, or may have a non-roll shape not wound on a roll. The length of the long object is not particularly limited as long as it can be continuously conveyed, but it may be 100 m or more (for example, 100 to 500 m). As a method of adhering the metal foil to the thermoplastic liquid crystal polymer film, a method of superimposing the thermoplastic liquid crystal polymer film and the metal leaf and continuously thermocompression bonding by a roll press or a double belt press by a roll-to-roll method is preferable. ..

The peel strength between the thermoplastic liquid crystal polymer film and the metal layer of the single-sided metal-clad laminate may be 0.6 N / mm or more, preferably 0.8 N / mm or more, and more preferably 1.0 N / mm or more. It may be. Further, the upper limit of the peel strength between the thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate and the metal layer is not particularly limited, but may be, for example, 2.0 N / mm or less. Here, the peel strength is the peel strength (peeling strength) measured with reference to JIS C 5016-1994 (peeling in the 90 ° direction).

In the production method of the present invention, preparation of a single-sided metal-clad laminate (for example, production of a single-sided metal-clad laminate by thermocompression bonding of a thermoplastic liquid crystal polymer film and metal leaf) and shaping treatment of the single-sided metal-clad laminate (that is, Thermocompression bonding with the metal shaping sheet) is performed independently. Therefore, it is possible to avoid heating and pressurizing at a high temperature during the shaping process, and as a result, it is possible to suppress the dimensional change of the metal-clad laminate and to generate wrinkles due to the difference in thermal expansion of each material. It can be suppressed.

The metal forming the metal layer is not particularly limited, and may be, for example, gold, silver, copper, iron, tin, nickel, aluminum, chromium, or an alloy metal thereof. When the metal foil is adhered as the metal layer, for example, the metal foil formed of the metal may be used, and a copper foil or a stainless steel foil is preferable from the viewpoint of conductivity, handleability, cost and the like. As the copper foil, those produced by a rolling method or an electrolytic method can be used. Further, the metal foil may be subjected to surface treatment such as roughening treatment, which is usually performed, as long as the high frequency characteristics of the metal-clad laminate of the present invention are not impaired.

The thickness of the metal layer can be appropriately set as needed, and may be, for example, about 1 to 50 μm, more preferably in the range of 9 to 35 μm.

(Metal shaping sheet)
The metal shaping sheet used in the production method of the present invention is a sheet made of metal, and at least one surface is a shaping surface. A long metal shaping sheet is used. The elongated object may have a roll shape wound on a roll, or may have a non-roll shape not wound on a roll. The length of the long object is not particularly limited as long as it can be continuously conveyed, but it may be 100 m or more (for example, 100 to 500 m).

The metal shaping sheet is preferably a metal foil having at least one surface having a shaping surface. The metal forming the metal shaping sheet is not particularly limited, and may be, for example, gold, silver, copper, iron, tin, nickel, aluminum, chromium or an alloy metal thereof, and when a metal foil is used. For example, a metal foil formed of the metal may be used, and a copper foil or a stainless steel foil is preferable from the viewpoint of handleability, cost, and the like. As these metal foils, those produced by a rolling method or an electrolytic method can be used, and surface treatment such as roughening treatment may be performed in order to obtain a desired shaped surface.

Further, from the viewpoint of suppressing warpage due to thermal expansion during thermocompression bonding, the metal forming the metal shaping sheet is a material having a coefficient of thermal expansion similar to that of the metal forming the metal layer of the single-sided metal-clad laminate (for example). , The same type of metal). In particular, it is preferable that both the metal layer and the metal shaping sheet are copper foils.

The shaped surface of the metal shaped sheet may have, for example, a surface roughness (Rz) of 1.0 to 7.0 μm from the viewpoint of improving the interlayer adhesiveness with the bonding sheet in circuit processing. In the production method of the present invention, the surface roughness (Rz) of the shaped surface of the metal shaping sheet is transferred, and the surface roughness (Rz) of the surface roughness (Rz) similar to that of the metal shaping sheet is transferred to the surface of the thermoplastic liquid crystal polymer film. Can be formed. Further, the surface roughness (Rz) of the shaping surface of the metal shaping sheet may be preferably 1.5 to 5.5 μm, more preferably 2.0 to 4.5 μm. Here, in the present invention, the surface roughness (Rz) indicates the ten-point average roughness measured with reference to JIS B 0601-1994 using a contact-type surface roughness meter, and is the roughness of the reference length. In the curve, it represents the sum of the average of the mountain heights from the highest peak to the fifth in the highest order and the average of the valley depths from the deepest valley bottom to the fifth.

The shaping surface of the metal shaping sheet may be subjected to a mold release treatment from the viewpoint of facilitating peeling of the metal shaping sheet after thermocompression bonding. As a method of the mold release treatment, for example, a method of applying a mold release agent to the shape surface of the metal shape sheet to provide a mold release layer may be used. Examples of the release agent include silicone-based resins and fluororesins.

The thickness of the metal shaping sheet can be appropriately set as needed, and may be, for example, about 5 to 50 μm, more preferably in the range of 9 to 35 μm.

(Release cushion material)
A release cushion material may be used in the production method of the present invention, if necessary. A long material may be used as the release cushion material. The elongated object may have a roll shape wound on a roll, or may have a non-roll shape not wound on a roll. The length of the long object is not particularly limited as long as it can be continuously conveyed, but it may be 100 m or more (for example, 100 to 500 m).

The release cushioning material is not particularly limited as long as it can be peeled off from the adjacent adherend after thermal pressure bonding, has heat resistance, and has cushioning properties, and is a non-thermoplastic polyimide film, aramid film, or Teflon ( Heat-resistant resin film such as a film (registered trademark); heat-resistant composite film (for example, composite film composed of a plurality of heat-resistant resin films, composite film composed of metal foil and heat-resistant resin film); heat-resistant fiber (for example, heat resistance) A heat-resistant non-woven film composed of resin fibers (resin fibers, metal fibers); and a metal foil (for example, a coating layer of a release agent such as a silicone-based resin or a fluorine-based resin) on at least one surface. For example, aluminum film, stainless film, etc.) and the like. These release cushioning materials may be used alone or in combination of two or more. The release cushion material (for example, a heat-resistant resin film, a heat-resistant composite film, or a heat-resistant non-woven fabric) is subjected to a mold release treatment from the viewpoint of facilitating peeling from the adherend after thermocompression bonding. May be. Examples of the mold release processing method include the above-mentioned methods.
Among these release cushioning materials, a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant non-woven fabric are preferable from the viewpoint of excellent heat resistance and cushioning property (repulsive elasticity).

The thickness of the release cushion material can be appropriately set as needed, and may be, for example, about 5 to 300 μm, preferably 10 to 150 μm, and more preferably 25 to 75 μm. ..

The surface roughness (Rz) of at least one surface of the release cushion material is 2.0 μm from the viewpoint of facilitating peeling from the adherend (single-sided metal-clad laminate or metal shaping sheet) after thermocompression bonding. It may be less than or equal to, preferably 1.8 μm or less, and more preferably 1.5 μm or less. Further, the lower limit of the surface roughness (Rz) of at least one surface of the release cushion material is not particularly limited, but may be, for example, 0.05 μm or more, preferably 0.10 μm or more, and more preferably 0. It may be 15 μm or more.

(Manufacturing method of metal-clad laminate)
The method for producing a metal-clad laminate of the present invention is:
A long single-sided metal-clad laminate (A) in which a metal layer is adhered to one surface of a thermoplastic liquid crystal polymer film, and a long metal shaping sheet (B) in which at least one surface is a shaping surface. ) And the process of preparing
A pair of pressure rolls (r ₁ , r ₂ ) are arranged so that the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the shaping surface of the metal shaping sheet (B) are in contact with each other. The thermocompression bonding process to be introduced into
At least prepare.

The single-sided metal-clad laminate (A) and the metal shaping sheet (B) are not particularly limited as long as they can be introduced into the pressure roll as a long product, and for example, a long product manufactured upstream of the thermocompression bonding step can be used. It may be transported as it is and used, or an unwinding roll may be prepared.
When a long product manufactured upstream is used as it is, for example, a single-sided metal-clad laminate (A) is manufactured by superimposing a thermoplastic liquid crystal polymer film and a metal foil and continuously thermocompression bonding, and winding the product. Instead, it may be overlapped with the separately prepared metal shaping sheet (B) downstream of the transport direction as it is. In this case, the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the shaping surface of the metal shaping sheet (B) are arranged and overlapped so as to be in contact with each other.
When preparing unwinding rolls, each unwinding roll is a thermoplastic liquid crystal polymer film in which the single-sided metal-clad laminate (A) and the metal shaping sheet (B) are adjacent to each other and the single-sided metal-clad laminate (A) is adjacent to each other. It is arranged so that the surface and the shaping surface of the metal shaping sheet (B) are in contact with each other.

The method for producing a metal-clad laminate of the present invention is:
In the preparatory process, a longer release cushion material (C) is prepared,
In the thermocompression bonding step, the release cushion material (C) is arranged on at least one of the non-contact side of the single-sided metal-clad laminate (A) and the metal shaping sheet (B), and a pair of pressure rolls (r). _1, it may be introduced to _{r 2).}

By using the release cushion material (C), the release cushion material (C) acts as a cushion, so that pressure is applied in thermocompression bonding between the single-sided metal-clad laminate (A) and the metal shaping sheet (B). The pressure from the roll can be dispersed, and the transferability of the shaped surface of the metal shaping sheet (B) to the surface of the thermoplastic liquid crystal polymer film can be improved. For example, if the heating temperature in the pressure roll (r _{1, r 2)} is high, pressure if pressure pressure is low, when the short pressing time is uniform pressure due to the presence of the releasing cushion material (C) Highly effective in improving sex.

When the release cushion material (C) is used, the release cushion material (C) is a single-sided metal-clad laminate (A) on the non-contact surfaces of the single-sided metal-clad laminate (A) and the metal shaping sheet (B). ) And / or may be arranged adjacent to the metal shaping sheet (B).

For example, the release cushion material (C) is arranged adjacent to the metal layer of the single-sided metal-clad laminate (A), and the metal-clad laminate is formed in the order of at least (C) / (A) / (B). It may be thermocompression bonded as described above. By adjoining the release cushion material (C) to the metal layer side of the single-sided metal-clad laminate (A), heat is suppressed from the release cushion material (C) being transferred from the single-sided metal-clad laminate (A) side. Since it acts as a heat insulating material, it is possible to prevent the thermoplastic liquid crystal polymer film from being heated more than necessary from the metal layer side, and to prevent the liquid crystal polymer molecules from being easily oriented.

Further, in the thermocompression bonding step, at least one of the pressure rolls (r ₁ , r ₂ ) is a heated pressure roll (hr), and the heated pressure roll (hr) is changed to (hr) / (B). ) / (A), or when the release cushion material (C) is used, (hr) / (B) / (A) / (C) or (hr) / (C) / (B) It may be introduced in the order of / (A). By heating the single-sided metal-clad laminate (A) from the metal shaping sheet (B) side, heat is efficiently transferred to the surface of the thermoplastic liquid crystal polymer film to which the single-sided metal-clad laminate (A) is shaped. Therefore, the heating and pressurizing conditions can be adjusted so as to prevent the thermoplastic liquid crystal polymer film from being heated more than necessary, and the shaping process can be performed efficiently.

In the method for producing a metal-clad laminate of the present invention, a plurality of long single-sided metal-clad laminates (A) and a plurality of elongated metal shaping sheets (B) are prepared, and a plurality of metal-clad laminates are prepared. It may be manufactured.

When manufacturing a plurality of metal-clad laminates, a release cushion material (C) is provided between a plurality of sets of single-sided metal-clad laminates (A) and laminates including a metal shaping sheet (B) in a thermocompression bonding step. It may be introduced in layers.

Also, superimposed when manufacturing a plurality of metal-clad laminate, in the thermocompression bonding step, a pair of pressure rolls (r _{1, r 2)} at least one release cushion material in contact with the pressure roll of the (C) May be introduced.

Here, the plurality of single-sided metal-clad laminates (A) may be the same or different. Further, the plurality of metal shaping sheets (B) may be the same or different.

Furthermore, the obtained plurality of metal-clad laminates may be the same or different.

The obtained metal-clad laminate (a metal-clad laminate in which a metal layer is laminated on one surface of a thermoplastic liquid crystal polymer film and a metal shaping sheet is provided on the other surface) is a thermoplastic liquid crystal polymer film and metal shaping. The peel strength (P1) between the sheet and the sheet may be 0.5 N / mm or less, preferably 0.2 N / mm or less, and more preferably 0.1 N / mm or less.
Further, in the obtained metal-clad laminate, the peel strength (P2) between the thermoplastic liquid crystal polymer film and the metal layer may be, for example, 0.6 N / mm or more, preferably 0.8 N / mm. It may be mm or more, more preferably 1.0 N / mm or more. Further, the upper limit of the peel strength between the thermoplastic liquid crystal polymer film and the metal layer is not particularly limited, but may be 2.0 N / mm or less.
Further, the obtained metal-clad laminate has a peel strength (P1) between the thermoplastic liquid crystal polymer film and the metal shaping sheet, and a peel strength (P2) between the thermoplastic liquid crystal polymer film and the metal layer. The divided value (P1 / P2) may be 0.6 or less, preferably 0.4 or less, and more preferably 0.2 or less.

Further, in the obtained metal-clad laminate, the orientation degree f (f1) on the metal layer side in the thickness direction of the thermoplastic liquid crystal polymer film is set to the orientation degree f (or the shaping treatment surface side) on the metal shaping sheet side (or shaping treatment surface side). The value (f1 / f2) divided by f2) may be 1.05 to 1.40, preferably 1.10 to 1.35, and more preferably 1.15 to 1.30. In the present invention, in the thermocompression bonding step between the single-sided metal-clad laminate (A) and the metal shaping sheet (B), it is avoided to heat and pressurize at a higher temperature than necessary (for example, above the melting point of the thermoplastic liquid crystal polymer film). By being able to do so, it is possible to suppress the change in the molecular orientation on the metal shaping sheet side, or the degree of orientation in the thickness direction of the thermoplastic liquid crystal polymer film can be set to a specific relationship. Here, the degree of orientation on the metal layer side in the thickness direction of the thermoplastic liquid crystal polymer film is the degree of orientation on the side in contact with the metal layer when the thermoplastic liquid crystal polymer film is divided into two equal parts in the thickness direction. The degree of orientation on the metal shaping sheet side (shape processing surface side) in the thickness direction of the thermoplastic liquid crystal polymer film is the same as the metal shaping sheet when the thermoplastic liquid crystal polymer film is divided into two equal parts in the thickness direction. The degree of orientation of the part on the contact side (the surface side that has been shaped).

Here, the degree of orientation f is an index that gives the degree of orientation of the crystal region of the polymer, and is calculated as follows. The degree of orientation f is measured using a rotary anti-cathode X-ray diffractometer Ru-200 manufactured by Rigaku Denki, and the X-ray output is measured as follows using a voltage of 40 kV, a current of 100 mA, and a target CuKα (λ = 1.5405 A). be able to. The change in crystal orientation can be obtained from a wide-angle X-ray photograph. First, the metal shaping sheet of the metal-clad laminate is peeled off, the metal layer is etched and removed, and the obtained film is cut out in the MD direction, attached to the sample holder, and X-rays are incident from the Edge direction for imaging. The diffraction image is exposed on the plate. Then, the obtained diffraction image can be converted into an orientation distribution curve, and a simple orientation degree f can be calculated from the following equation (1) from the half-value width H of the peak of the curve of the diffraction intensity with respect to the β angle in the circumferential direction. it can.
f = (180-H) / 180 (1)
In the formula, H is the half price range.
The degree of orientation f is measured on both the metal layer side and the metal shaping sheet side (shape processing surface side) of the thermoplastic liquid crystal polymer film.
The half-value width H is the peak of the intensity distribution obtained by ring-integrating the diffraction angle 2θ = 15 ° to 30 ° (for example, around about 20 ° ((110) plane)) by wide-angle X-ray diffraction measurement. It may be a half price range.

Hereinafter, specific embodiments will be described with reference to the drawings. FIG. 1 is a schematic side view for explaining a method for manufacturing a metal-clad laminate according to the first embodiment.
As shown in FIG. 1, in the first embodiment, on the upstream side of the pair of pressure rolls (r _{1, r 2),} unwinding sided metal-clad laminate unwound sided metal-clad laminate (A) roll 11 and the metal shaping sheet unwinding roll 12 for unwinding the metal shaping sheet (B) are prepared.

Here, in the first embodiment, the single-sided metal-clad laminate (A) and the metal shaping sheet (B) are placed between the pair of pressure rolls (r ₁ , r ₂ ) (r ₁ ) / (A). ) / (B) / (r ₂ ), each unwinding roll is arranged in this order.

Specifically, the upstream side of the pair of pressure rolls _{(r 1,} r _2), the thermoplastic liquid crystal polymer film surface and the vehicle surface of the metal shaped sheet (B) of the single-sided metal-clad laminate (A) The single-sided metal-clad laminate unwinding roll 11 and the metal shaping sheet unwinding roll 12 are arranged so as to be in contact with each other.

As shown in FIG. 1, after each unwinding roll is arranged on the pair of pressure rolls (r ₁ , r ₂ ), a single-sided metal-clad laminate is shown from each unwinding roll in the direction of the arrow. (a), and a metal shaped sheet (B) is unwound, the pair of pressure rolls (r _{1, r 2),} is introduced in the MD direction (or laminate direction) indicated by arrows, a pair is thermocompression bonding in the pressure roll _(r 1, r _2), the metal-clad laminate (D) ((A) / (B)) is formed.

In a pair of pressure rolls _{(r 1,} r _2), single-sided metal-clad laminate (A), and a metal shaped sheet (B) is introduced stacked in this order, at a predetermined heating temperature, application of pressure. In the manufacturing method of the present invention, since the prepared single-sided metal-clad laminate (A) is directly used for manufacturing, the temperature is higher than necessary (for example, in the thermocompression bonding step with the metal shaping sheet (B)). It is possible to avoid heating and pressurizing at (above the melting point of the thermoplastic liquid crystal polymer film). As a result, it is possible to suppress the dimensional change of the metal-clad laminate, the occurrence of wrinkles due to the difference in thermal expansion of each material, and further, the thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate (A). The peelability between the surface and the shaped surface of the metal shaping sheet (B) can be improved.

As the pressurizing roll, a known heating and pressurizing device can be used, and examples thereof include a metal roll, a rubber roll, and a resin-coated metal roll. A pair of pressure rolls (r _{1, r 2),} even using the same one another, may use different ones. For example, the pressure roll (r ₁ ) may be a metal roll from the viewpoint of increasing the heating efficiency, and the pressure roll (r ₂ ) is a metal roll like the pressure roll (r ₁ ). It may be a rubber roll or a resin-coated metal roll.

The pair of pressure rolls (r _{1, r 2)} is to be heated only one may be heated both. When heating both, the heating temperature of the pressure roll (r _{1, r 2)} may be identical to one another or may be different. For example, it is preferable that the pressure roll disposed on the metal shaping sheet (B) side has a higher temperature, and in the case of the first embodiment as shown in FIG. 1, the metal shaping sheet (B) side. The heating temperature of the pressure roll (r ₂ ) disposed in may be higher than that of the pressure roll (r ₁ ). In that case, for example, by higher in heating temperature of the pressure roll metal shaped sheet (B) is in contact (r _2), thermoplastic sided metal-clad laminate of metal shaped sheet (B) (A) Since heat can be transferred to the liquid crystal polymer film surface (the surface to be subjected to the shaping treatment), the shaping treatment can be efficiently performed and the dimensional change of the metal-clad laminate can be suppressed. .. When the heating temperature is from the pressure roll (r ₁₎ towards the pressure roll (r ₂₎ is high, for example, the temperature difference between the heating temperature of the heating temperature and the pressure roller (r ₁₎ of the pressure roll (r ₂₎ May be 20 to 200 ° C., preferably 25 to 150 ° C., and more preferably 30 to 100 ° C.

Further, the thermocompression bonding temperature and the pressure condition of the pressure roll are not particularly limited, but from the viewpoint of improving the transferability of the unevenness of the shaping surface of the metal shaping sheet (B), for example, a thermoplastic liquid crystal polymer film. The thermocompression bonding temperature may be, for example, (Tm-150) ° C. or higher, preferably (Tm-130) ° C. or higher (for example, (Tm-100) ° C. or higher) with respect to the melting point (Tm). It may be preferably (Tm-110) ° C. or higher (for example, (Tm-90) ° C. or higher). Further, from the viewpoint of improving the peelability of the metal shaping sheet (B) and suppressing the occurrence of dimensional changes and wrinkles, the temperature may be lower than (Tm) ° C., preferably (Tm-5) ° C. or lower. It may be preferably (Tm-10) ° C. or lower. The thermocompression bonding temperature may be the heating temperature of the pressurizing rolls (r ₁ , r ₂ ), and when the heating temperatures of the pair of pressurizing rolls (r ₁ , r ₂ ) are different from each other, pressurization is performed. The thermocompression bonding temperature may be the higher of the heating temperatures of the rolls (r ₁ , r ₂ ).
The pressurizing pressure may be in the range of 16.0 t / m (156.8 kN / m) or less, preferably 8.0 t / m (78.4 kN / m) or less. The lower limit of the pressurizing pressure is not particularly limited, but may be 0.5 t / m (4.9 kN / m) or more. The pressurizing pressure is a value obtained by dividing the force applied to the pressurizing roll (crimping load) by the maximum width of the material passing between the pressurizing rolls.

In the manufacturing method of the present invention, a cooling roll may be provided on the downstream side of the pressure roll, if necessary. The cooling roll is preferably provided between the pressure roll and the first release roll. The cooling roll may be composed of a pair of rolls or one single roll.

The manufacturing method of the present invention may further include a peeling step of peeling the metal shaping sheet (B) from the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) after the thermocompression bonding step. The stripping step, for example, after passing through the pair of pressure rolls (r _{1, r 2),} by using the pair of pressure rolls (r _{1, r 2)} as a release roll immediately sided metal-clad laminate (A The metal shaping sheet (B) may be peeled from (), or the metal shaping sheet (A) may be peeled from the single-sided metal-clad laminate (A) by using at least one peeling roll arranged separately from the pressure roll. B) may be peeled off.

For example, in the first embodiment shown in FIG. 1, the metal-clad laminates (D) ((A) / (B)) obtained by the thermocompression bonding step are passed through the release rolls 21 and 21. The metal-clad laminate (E) is produced by being peeled off between (A) and (B), and is wound on the metal-clad laminate take-up roll 31. The metal-clad laminate (E) obtained by peeling the metal shaping sheet (B) is laminated in the order of metal layer / thermoplastic liquid crystal polymer film, and the metal layer of the thermoplastic liquid crystal polymer film is not adhered. The unevenness of the shaping surface of the metal shaping sheet (B) is transferred to the surface on the side. That is, the surface roughness (Rz) of the metal-clad laminate (E) on the side where the metal layer of the thermoplastic liquid crystal polymer film is not adhered may be 1.0 to 7.0 μm, preferably 1.5. It may be ~ 5.5 μm, more preferably 2.0 ~ 4.5 μm.

In the production method of the present invention, the peel strength between the single-sided metal-clad laminate (A) and the metal shaping sheet (B) may be appropriately set as long as the peeling step can be performed. For example, the peel strength between the single-sided metal-clad laminate (A) and the metal shaping sheet (B) is preferably 0.5 N / mm or less, and more preferably 0.2 N / mm or less. , 0.1 N / mm or less, more preferably. The lower limit is not particularly limited, but may be 0 N / mm. In the manufacturing method of the present invention, in the thermocompression bonding step, a shaping process is performed by heating and pressurizing at a lower temperature while maintaining a low interlayer adhesiveness between the single-sided metal-clad laminate (A) and the metal shaping sheet (B). Can be applied.

The peeled metal shaping sheet (B) is wound by the metal shaping sheet winding roll 32. In the production method of the present invention, the peeled metal shaping sheet (B) may be reused if necessary.

Further, FIG. 2 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the second embodiment. Members having the same role as those in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted. As shown in FIG. 2, in the second embodiment, on the upstream side of the pair of pressure rolls (r _{1, r 2),} unwinding sided metal-clad laminate unwound sided metal-clad laminate (A) roll 11. Prepare a metal shaping sheet unwinding roll 12 for unwinding the metal shaping sheet (B) and a release cushion material unwinding roll 13 for unwinding the release cushion material (C).

In the second embodiment, single-sided metal-clad laminate (A), a metal shaped sheet (B) and release the cushion material (C) is a pair of pressure rolls (r _{1, r 2)} between at , (R ₁ ) / (C) / (A) / (B) / (r ₂ ), and each unwinding roll is arranged in this order.

Specifically, the upstream side of the pair of pressure rolls _{(r 1,} r _2), the thermoplastic liquid crystal polymer film surface and the vehicle surface of the metal shaped sheet (B) of the single-sided metal-clad laminate (A) The single-sided metal-clad laminate unwinding roll 11 and the metal shaping sheet unwinding roll 12 are arranged so as to be in contact with each other, and the metal layer surface of the single-sided metal-clad laminate (A) and the release cushion material (C) are further arranged. The release cushion material unwinding roll 13 is arranged so as to come into contact with each other.

As shown in FIG. 2, after each unwinding roll is arranged on a pair of pressure rolls (r ₁ , r ₂ ), a single-sided metal-clad laminate is shown from each unwinding roll in the direction of the arrow. (a), a metal shaped sheet (B), and release the cushion material (C) is unwound, the pair of pressure rolls _{(r 1, r 2),} MD direction (or laminate indicated by arrow is introduced in the direction), _(thermally bonding at r 1, _{r 2),} the metal-clad laminate (F) ((C) a pair of pressure rolls / (a) / (B)) is formed.

As shown in FIG. 2, in the second embodiment, the use of release packing cushion (C), dispersing the pressure from the pair of pressure rolls (r _{1, r 2)} by the cushioning It is possible to improve the transferability of the metal shaping sheet (B) to the thermoplastic liquid crystal polymer film having the uneven shape of the shaping surface. Further, since the overlapping release cushion material and (C) the metal layer side of the single-sided metal-clad laminate (A), the role of releasing the cushion material (C) is to insulate the heat from the pressure roll (r ₁₎ Further, it is possible to suppress heat transfer more than necessary to the surface of the thermoplastic liquid crystal polymer film on the metal layer side, and it is possible to suppress dimensional change. Particularly, when the heating temperature in the pressure roll (r _{1, r 2)} is high, pressure if pressure pressure is low, when the short pressing time, since unevenness such pressure is likely to occur, the release cushion material By using (C), the effect of improving the pressure uniformity is high.

In the production method of the present invention, a metal-clad laminate obtained by a thermal pressure bonding step using at least one peeling roll (a metal-clad laminate comprising a single-sided metal-clad laminate (A) and a metal shaping sheet (B)). Alternatively, the single-sided metal-clad laminate (A) is a metal-clad laminate in which the surface of the thermoplastic liquid crystal polymer film is shaped, and the metal-clad laminate is provided with the release cushion material (C). The cushion material (C) may be peeled off. For example, after passing through the pair of pressure rolls (r _{1, r 2),} the pair of pressure rolls (r _{1, r 2)} is used as the peeling rolls, the release cushion material immediately from the metal-clad laminate (C ) May be peeled off, or the release cushion material (C) may be peeled off from the metal-clad laminate by using at least one peeling roll arranged separately from the pressure roll.

In the manufacturing method of the present invention, the order of peeling of the metal shaping sheet (B) and peeling of the release cushion material (C) can be appropriately set according to the mode of the metal-clad laminate.

For example, in the second embodiment shown in FIG. 2, the metal-clad laminate (F) ((C) / (A) / (B)) obtained by the thermocompression bonding step is the first peeling roll 21, By passing through 21, the metal-clad laminate (D) is produced by peeling between (C) / (A). The metal-clad laminate (D) obtained by peeling the release cushion material (C) is the metal layer of the single-sided metal-clad laminate (A) / the thermoplastic liquid crystal polymer film / metal of the single-sided metal-clad laminate (A). The shaping sheets (B) are laminated in this order.

In the manufacturing method of the present invention, the peel strength between the release cushion material (C) and the single-sided metal-clad laminate (A) or the metal shaping sheet (B) is appropriately set as long as the peeling step can be performed. May be done.

For example, the peel strength between the release cushion material (C) and the single-sided metal-clad laminate (A) or the metal shaping sheet (B) is preferably 0.1 N / mm or less, preferably 0.05 N / mm. It is more preferably mm or less, and further preferably 0.03 N / mm or less. The lower limit is not particularly limited, but may be 0 N / mm.

The release cushion material (C) that has been peeled off is wound by the release cushion material winding roll 33. In the manufacturing method of the present invention, the peeled release cushion material (C) can be reused as needed.

The metal-clad laminate (D) from which the release cushion material (C) has been peeled off is peeled between (A) / (B) by passing through the second peeling rolls 22 and 22, and the metal-clad laminate (D) is peeled off. (E) is manufactured and wound on a metal-clad laminate winding roll 31.

Further, FIG. 3 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the third embodiment. As shown in FIG. 3, in the third embodiment, the single-sided metal-clad laminate (A), the metal shaping sheet (B) and the release cushion material (C) are made of a pair of pressure rolls (r ₁ , r). ₂ ), each unwinding roll is arranged in the order of (r ₁ ) / (C) / (A) / (B) / (C) / (r ₂ ). Here, the members having the same role as those in FIG. 2 are designated by the same reference numerals, and the description thereof will be omitted.

In the third embodiment shown in FIG. 3, metal tensioning is performed between the pair of pressure rolls (r ₁ , r ₂ ) so as to form (C) / (A) / (B) / (C). In the laminated body (F), the release cushion material (C) is peeled off between (C) / (A) and (B) / (C) to produce a metal-clad laminate (D), and then the laminated body (D) is manufactured. The metal shaping sheet (B) is peeled off from the metal-clad laminate (D) to produce the metal-clad laminate (E).

Further, in the third embodiment shown in FIG. 3, the heating temperature of the pair of pressure rolls (r _{1, r 2),} which may be the same as each other or different, for example, the first As in the embodiment, the heating temperature of the pressure roll (r ₂ ) on the metal shaping sheet (B) side may be higher than that of the pressure roll (r ₁ ). By higher in heating temperature of the metal shaped sheet (B) and the adjacent release cushion material (C) in contact with pressure roll (r _2), single-sided metal-clad laminate of metal shaped sheet (B) ( Heat can be efficiently transferred to the thermoplastic liquid crystal polymer film surface (surface to be subjected to the shaping treatment) side of A).

Further, FIG. 4 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the fourth embodiment. As shown in FIG. 4, in the fourth embodiment, the single-sided metal-clad laminate (A), the metal shaping sheet (B), and the release cushion material (C) are made of a pair of pressure rolls (r ₁ , r). ₂ ), each unwinding roll is arranged in the order of (r ₁ ) / (B) / (A) / (C) / (A) / (B) / (r ₂ ). Here, the members having the same role as those in FIG. 2 are designated by the same reference numerals, and the description thereof will be omitted.

In the fourth embodiment shown in FIG. 4, the pair of pressure rolls (r ₁ , r ₂ ) are overlapped so as to be (B) / (A) / (C) / (A) / (B). The release cushion material (C) is peeled off from the metal-clad laminate (F) to produce two metal-clad laminates (D), and then a metal shaping sheet (a metal shaping sheet (D) is produced from the metal-clad laminate (D). B) is peeled off to produce two metal-clad laminates (E).

In the fourth embodiment shown in FIG. 4, a plurality of metal-clad laminates can be manufactured, and the production efficiency is high. The two metal-clad laminates (D) may be the same or different from each other. Similarly, the two metal-clad laminates (E) may be the same as or different from each other.

In the fourth embodiment shown in FIG. 4, the release cushion material (C) is overlapped with the single-sided metal-clad laminate (A) on both sides, so that the release layers are arranged on both sides. preferable.

Further, in the fourth embodiment shown in FIG. 4, when the same metal-clad laminate is obtained, a pair of pressure rolls (r ₁ , ₁ ,) are used from the viewpoint of suppressing the occurrence of wrinkles due to the difference in thermal expansion in the thermocompression bonding step. r ₂ ) may be the same, and the heating temperature may be the same.

Further, FIG. 5 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the fifth embodiment. As shown in FIG. 5, in the fifth embodiment, the single-sided metal-clad laminate (A), the metal shaping sheet (B) and the release cushion material (C) are made of a pair of pressure rolls (r ₁ , r). _{Between 2} ), each unwinding roll is in the order of (r ₁ ) / (C) / (B) / (A) / (A) / (B) / (C) / (r ₂ ). Be placed. Here, the members having the same role as those in FIG. 2 are designated by the same reference numerals, and the description thereof will be omitted.

In the fifth embodiment shown in FIG. 5, between a pair of pressure rolls _(r 1, r _2), and (C) / (B) / (A) / (A) / (B) / (C) The release cushioning material (C) is peeled off from the metal-clad laminate (F) stacked so as to form two metal-clad laminates (D), and then the metal is metallized from the metal-clad laminate (D). The shaping sheet (B) is peeled off to produce two metal-clad laminates (E).

In the fifth embodiment shown in FIG. 5, a plurality of metal-clad laminates can be manufactured, and the production efficiency is high. The two metal-clad laminates (D) may be the same or different from each other. Similarly, the two metal-clad laminates (E) may be the same as or different from each other.

Further, FIG. 6 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the sixth embodiment. As shown in FIG. 6, in the sixth embodiment, the single-sided metal-clad laminate (A), the metal shaping sheet (B) and the release cushion material (C) are made of a pair of pressure rolls (r ₁ , r). _{Between 2} ), each unwinding roll is in the order of (r ₁ ) / (C) / (A) / (B) / (B) / (A) / (C) / (r ₂ ). Be placed. Here, the members having the same role as those in FIG. 2 are designated by the same reference numerals, and the description thereof will be omitted.

In the sixth embodiment shown in FIG. 6, between a pair of pressure rolls _(r 1, r _2), and (C) / (A) / (B) / (B) / (A) / (C) The release cushioning material (C) is peeled off from the metal-clad laminate (F) stacked so as to form two metal-clad laminates (D), and then the metal is metallized from the metal-clad laminate (D). The shaping sheet (B) is peeled off to produce two metal-clad laminates (E).

In the sixth embodiment shown in FIG. 6, a plurality of metal-clad laminates can be manufactured, and the production efficiency is high. The two metal-clad laminates (D) may be the same or different from each other. Similarly, the two metal-clad laminates (E) may be the same as or different from each other.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the present Examples. In the following examples and comparative examples, the peelability and warpage were evaluated by the following methods.

[Peeling strength]
In Examples 1 and 2, a metal-clad laminate before peeling the polyimide film (C) and the metal shaping sheet (B) after thermal crimping was separately obtained, and a peeling test piece having a width of 3 mm from the metal-clad laminate was obtained. The interface between the single-sided metal-clad laminate (E) and the metal shaping sheet (B) and the single-sided metal-clad laminate (B) at a speed of 50 mm / min by the 90 ° method according to JIS C 6471. The strength (N / mm) when peeled off at the interface between E) and the polyimide film (C) was measured.

[Evaluation of peelability]
The single-sided metal-clad laminate and the metal shaping sheet were continuously peeled off, and those in which no wrinkles, deformation, poor peeling, or material destruction were observed at a length of 20 m or more were evaluated as A, and those observed were evaluated as B.

[Warp measurement]
A sample with a width of 250 mm and a length of 250 mm is taken from a single-sided metal-clad laminate, the sample is placed on a horizontal table, and the height of the part of the four corners of the sample that floats most from the table is measured on a scale. , This was a warp. Those with a warp of less than 5 mm were evaluated as A, and those with a warp of 5 mm or more were evaluated as B.

(Manufacturing Example 1)
Copper foil (Fukuda Metal Foil Powder Industry Co., Ltd., "CF-H9A-DS-HD2") on one side of a thermoplastic liquid crystal polymer film ("Vexter" (registered trademark) manufactured by Kuraray Co., Ltd., melting point 310 ° C., thickness 50 μm) , Thickness 12 μm), and using a metal roll with a diameter of 300 mm, set the surface temperature of the metal roll to 260 ° C. and the pressurizing pressure to 8 t / m, pass it at a speed of 3.0 m / min, and thermocompression bond it. , A single-sided metal-clad laminate (A) having a thermoplastic liquid crystal polymer film / copper foil structure was prepared.

(Example 1)
Single-sided metal-clad laminate (A) obtained in Production Example 1, electrolytic copper foil as metal shaping sheet (B) ("JX-EFL-V2" manufactured by JX Nippon Mining & Metals Co., Ltd., thickness 12 μm, surface roughness of shaped surface is (Rz) 2.0 .mu.m), and the protective material (C) as a polyimide film (manufactured by Kaneka Corporation, "apical NPI", prepared as a roll unwinding thickness 75 [mu] m), respectively, a pair of pressure rolls _{(r 1,} r Introduced in the order of r ₁ / C / A / B / r ₂ between ₂ ). Using metal rolls with a diameter of 300 mm as a pair of pressure rolls (r ₁ , r ₂ ), the surface temperature of the metal rolls is set to 200 ° C., the pressure pressure is set to 8 t / m, and the speed is 3.0 m / min. by passing through a pair of pressure rolls (r _1, r ₂₎ were thermocompression bonding.

After thermocompression bonding, as shown in FIG. 2, after passing through a pair of pressure rolls (r _{1, r 2),} using a pair of peeling rolls (21), separating the polyimide film (C), followed by a pair The single-sided metal-clad laminate (E) and the metal shaping sheet (B) are separated by the peeling roll (22) of the above, and the surface shape of the metal shaping sheet (B) is transferred to the surface of the thermoplastic liquid crystal polymer film. A metal-clad laminate (E) was obtained. Table 7 shows the peelability of the metal shaping sheet (B) and the warp measurement results of the obtained single-sided metal-clad laminate (E). The peel strength between the single-sided metal-clad laminate (E) and the metal shaping sheet (B) was 0.05 N / mm or less. Further, the peel strength between the single-sided metal-clad laminate (E) and the polyimide film (C) was not adhered at all and could not be measured.

(Example 2)
A single-sided metal-clad laminate (E) was produced in the same manner as in Example 1 except that the surface temperature of the metal roll was set to 240 ° C. Table 7 shows the peelability of the metal shaping sheet (B) and the warp measurement results of the obtained single-sided metal-clad laminate (E). The peel strength between the single-sided metal-clad laminate (E) and the metal shaping sheet (B) was 0.08 N / mm or less. Further, the peel strength between the single-sided metal-clad laminate (E) and the polyimide film (C) was not adhered at all and could not be measured.

(Comparative Example 1)
Instead of the single-sided metal-clad laminate (A), a thermoplastic liquid crystal polymer film (L) ("Vexter" (registered trademark) manufactured by Kuraray Co., Ltd., melting point 310 ° C., thickness 50 μm) and copper foil (M) (Fukuda metal foil) A pair of pressure rolls together with the metal shaping sheet (B) and the protective material (C) in the same manner as in Example 1 except that "CF-H9A-DS-HD2" manufactured by Powder Industry Co., Ltd., thickness 12 μm) is used. When the single-sided metal-clad laminate (E) is produced by introducing in the order of r ₁ / C / M / L / B / r ₂ between (r ₁ , r ₂ ), a thermoplastic liquid crystal polymer film ( The peeling strength between the L) and the copper foil (M) is low, and when the metal shaping sheet (B) is peeled off, the peeling occurs partially between the thermoplastic liquid crystal polymer film (L) and the copper foil (M). It is thought that.

(Comparative Example 2)
When the single-sided metal-clad laminate (E) is produced in the same manner as in Comparative Example 1 except that the surface temperature of the metal roll is 320 ° C., the peel strength between the thermoplastic liquid crystal polymer film (L) and the copper foil (M) is sufficient. Although it is high, the peel strength between the thermoplastic liquid crystal polymer film (L) and the metal shaping sheet (B) is also high, so that the thermoplastic liquid crystal polymer film (L) and the metal shaping sheet (B) are peeled off. At that time, it is considered that any of continuous wrinkles, deformation, poor peeling, and material destruction of the film occurs, and the warp tends to be large.

As shown in Table 7, in Examples 1 and 2, since the single-sided metal-clad laminate (A) was manufactured in advance, the surface temperature of the metal roll can be set to a relatively low temperature, whereby the single-sided metal-clad laminate (A) can be set to a relatively low temperature. The body and the metal shaping sheet did not adhere firmly to each other, and the molecular orientation of the thermoplastic liquid crystal polymer film did not change, resulting in good peelability and warpage.

According to the manufacturing method of the present invention, the shape-treated metal-clad laminate can be efficiently produced, and the obtained metal-clad laminate has irregularities transferred to it, so that the metal-clad laminate is bonded to the bonding sheet. It has excellent properties and good circuit workability. Therefore, the obtained metal-clad laminate can be effectively used as a component used in the fields of electricity / electronics, office equipment / precision equipment, power semiconductors, etc., for example, a circuit board (particularly a substrate for millimeter-wave radar). Can be done.

As described above, a preferred embodiment of the present invention has been described with reference to the drawings, but those skilled in the art can easily assume various changes and modifications within a self-evident range by looking at the present specification. There will be. Therefore, such changes and amendments are construed as being within the scope of the invention as defined by the claims.

11 ... Single-sided metal-clad laminate unwinding roll 12 ... Metal shaping sheet unwinding roll 13 ... Detachable cushion material unwinding roll 21 and 22 ... Peeling roll 31 ... Metal-clad laminate Winding roll 32 ... Metal shaping sheet Winding roll 33 ... Release cushion material Winding roll r ₁ , r ₂ ... Pressurized roll A ... Single-sided metal-clad laminate B ... Metal Shaped sheet C ... Release cushion material D, E, F ... Metal-clad laminate

Claims (16)

1. A long single-sided metal-clad laminate (A) in which a metal layer is adhered to one surface of a thermoplastic liquid crystal polymer film, and a long metal shaping sheet (B) in which at least one surface is a shaping surface. ) And the process of preparing
   A pair of pressure rolls (r ₁ , r ₂ ) are arranged so that the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the shaping surface of the metal shaping sheet (B) are in contact with each other. The thermocompression bonding process to be introduced into
   A method for manufacturing a metal-clad laminate, which comprises at least.
2. The method for manufacturing a metal-clad laminate according to claim 1.
   A method for producing a metal-clad laminate, further comprising a peeling step of peeling the metal shaping sheet (B) from the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) after the thermocompression bonding step.
3. The method for producing a metal-clad laminate according to claim 1 or 2, when the thermocompression bonding temperature is the melting point (Tm) of the thermoplastic liquid crystal polymer film, (Tm-150) ° C. or higher (Tm). A method for producing a metal-clad laminate that is below ° C.
4. The method for manufacturing a metal-clad laminate according to any one of claims 1 to 3, wherein the peel strength between the single-sided metal-clad laminate (A) and the metal shaping sheet (B) is 0.5 N. A method for manufacturing a metal-clad laminate of / mm or less.
5. The method for producing a metal-clad laminate according to any one of claims 1 to 4, wherein the surface roughness (Rz) of the shaped surface of the metal shaped sheet (B) is 1.0 to 7. A method for producing a metal-clad laminate having a thickness of 0 μm.
6. The method for producing a metal-clad laminate according to any one of claims 1 to 5.
   In the preparatory process, a longer release cushion material (C) is prepared,
   In the thermocompression bonding step, the release cushion material (C) is arranged on at least one of the non-contact side of the single-sided metal-clad laminate (A) and the metal shaping sheet (B), and a pair of pressure rolls (r). _1, is introduced into the _{r 2),} method for producing a metal clad laminate.
7. The method for manufacturing a metal-clad laminate according to claim 6, wherein the peel strength between the release cushion material (C) and the single-sided metal-clad laminate (A) or the metal shaping sheet (B) is 0. A method for producing a metal-clad laminate having a thickness of 1 N / mm or less.
8. The method for producing a metal-clad laminate according to claim 6 or 7, wherein the release cushion material (C) is separated from a heat-resistant resin film, a heat-resistant composite film, a heat-resistant non-woven fabric, and at least one surface. A method for producing a metal-clad laminate selected from the group consisting of a metal foil having a mold layer.
9. The method for producing a metal-clad laminate according to any one of claims 6 to 8, wherein the surface roughness (Rz) of at least one surface of the release cushion material (C) is 2.0 μm or less. A method for manufacturing a metal-clad laminate.
10. The method for manufacturing a metal-clad laminate according to any one of claims 6 to 9, wherein in the thermocompression bonding step, between a pair of pressure rolls (r ₁ , r ₂ ), (r ₁ ). The single-sided metal-clad laminate (A), the metal shaping sheet (B), and the release cushion material (C) are stacked in the order of / (C) / (A) / (B) / (r ₂ ). A method for manufacturing a metal-clad laminate to be introduced.
11. The method for manufacturing a metal-clad laminate according to claim 10, wherein in the thermocompression bonding step, the pressure roll (r ₂ ) has a higher heating temperature than the pressure roll (r ₁ ). Production method.
12. The method for manufacturing a metal-clad laminate according to any one of claims 1 to 11, wherein a long single-sided metal-clad laminate (A) and a long metal shaping sheet (B) are respectively used. A method for manufacturing a metal-clad laminate, in which a plurality of metal-clad laminates are prepared to produce a plurality of metal-clad laminates.
13. The method for manufacturing a metal-clad laminate according to claim 11, which is subordinate to any one of claims 6 to 9, wherein a plurality of sets of single-sided metal-clad laminates (A) and A method for manufacturing a metal-clad laminate, in which a release cushion material (C) is laminated and introduced between laminates containing a metal shaping sheet (B).
14. The method for manufacturing a metal-clad laminate according to claim 13, wherein in the thermocompression bonding step, (r ₁ ) / (B) / (A) are sandwiched between a pair of pressure rolls (r ₁ , r ₂ ). ) / (C) / (a ) / (B) / ( so that the order of _{r 2),} single-sided metal-clad laminate (a), a metal shaped sheet (B) and release the cushion material (C) A method for manufacturing a metal-clad laminate that is introduced in layers.
15. The method for manufacturing a metal-clad laminate according to claim 11 or 12, which is subordinate to any one of claims 6 to 9, wherein in the thermocompression bonding step, a pair of pressure rolls (r _1). , R ₂ ) A method for manufacturing a metal-clad laminate in which a release cushion material (C) is laminated and introduced so as to be in contact with at least one of the pressure rolls.
16. The method for producing a metal-clad laminate according to claim 15, wherein in the thermocompression bonding step, (r ₁ ) / (C) / (B) are sandwiched between a pair of pressure rolls (r ₁ , r ₂ ). ) / (A) / (A) / (B) / (C) / (r ₂ ) or (r ₁ ) / (C) / (A) / (B) / (B) / (A) / ( Manufacture of a metal-clad laminate in which a single-sided metal-clad laminate (A), a metal shaping sheet (B), and a release cushion material (C) are stacked and introduced in the order of C) / (r ₂ ). Method.

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