CN112714691B

CN112714691B - Method for manufacturing metal-clad laminate

Info

Publication number: CN112714691B
Application number: CN201980061206.6A
Authority: CN
Inventors: 中岛崇裕; 高桥健; 佐佐木翔真
Original assignee: Kuraray Co Ltd
Current assignee: Kuraray Co Ltd
Priority date: 2018-09-25
Filing date: 2019-09-20
Publication date: 2022-03-29
Anticipated expiration: 2039-09-20
Also published as: JP2020203495A; TWI821409B; JP6767602B2; WO2020066880A8; KR20210043710A; WO2020066880A1; JPWO2020066880A1; CN112714691A; TW202021789A; KR102324897B1

Abstract

The invention provides a method for efficiently manufacturing a metal-clad laminate. In the above manufacturing method, a pair of pressure rollers (r) is prepared₁，r₂) A pair of release material unwinding rollers (16, 16), and two or more unwinding rollers for unwinding constituent materials of the metal-clad laminate so that the constituent materials are at least formed in a state (M)/(M) in which metal foils are adjacent to each other, and a pair of release materials (C)₁，C₂) The unwinding rollers are disposed so as to sandwich the entire constituent material. A pair of release materials (C)₁，C₂) Heating in advance, and sandwiching the constituent material between the pair of pressure rollers (r)₁，r₂) The entire structure is thermocompression bonded, and then two or more metal-clad laminates are produced through a peeling step.

Description

Method for manufacturing metal-clad laminate

Related application

The present application claims priority based on japanese patent application 2018-178691 filed in japan on 25.9.2018, which is incorporated by reference in its entirety as part of the present application.

Technical Field

The present invention relates to a method for producing a metal-clad laminate in which a metal foil is laminated on at least one surface of a film (hereinafter, may be referred to as a thermoplastic liquid crystal polymer film) containing a thermoplastic polymer (hereinafter, may be referred to as a thermoplastic liquid crystal polymer) capable of forming an optically anisotropic melt phase (or a metal-clad laminate having a metal layer on at least one surface of a thermoplastic liquid crystal polymer film).

Background

Thermoplastic liquid crystal polymer films are known to be excellent materials in high heat resistance, low moisture absorption, high frequency characteristics, and the like, and have recently attracted attention as electronic circuit materials for high-speed transmission. When used for electronic circuit board applications, a laminate of a thermoplastic liquid crystal polymer film and a metal foil represented by a copper foil is used, and as a technique for producing such a laminate composed of a thermoplastic liquid crystal polymer film and a metal foil, the following methods are exemplified: a thermoplastic liquid crystal polymer film cut into a predetermined size and a metal foil are stacked between an upper hot plate and a lower hot plate by using a hot press apparatus, and are heated and pressed in a vacuum state. However, this method has a problem of poor production efficiency because it is a batch method.

On the other hand, a method of laminating the thermoplastic liquid crystal polymer film and the metal foil by roll-to-roll (hereinafter, referred to as a roll) and continuously thermocompression bonding the laminated films is advantageous in terms of production efficiency. In particular, as a method for industrially producing a metal laminate with good productivity when the metal laminate is produced by a roll method, patent document 1 (international publication No. 2011/093427) discloses a method for producing a single-sided metal-clad laminate, in which a separator (C) having surface roughness (Rz) of both the front surface and the back surface of 2.0 μm or less is used by a roll method, and a pair of pressure rollers (r) are pressed against each other₁，r₂) In the recipe (r)₁)/(B)/(A)/(C)/(A)/(B)/(r₂) The insulating film (a), the metal foil (B) and the separator (C) were stacked in this order, thermocompression bonded, and peeled off from the separator (C) to obtain 2 single-sided metal-clad laminates.

Further, patent document 2 (jp 2014-128913 a) discloses a method for producing a double-sided metal-clad laminate in which a metal is bonded to both sides of an insulating film (a)A method for forming a metal-clad laminate on both sides of a foil (B, B'), wherein a heat capacity of 50 to 150J/m is used²A separating film (C) in the range between the pair of pressure rollers (r)₁，r₂) In the recipe (r)₁)/(B)/(A)/(B′)/(C)/(B′)/(A)/(B)/(r₂) The insulating film (a), the metal foil (B, B'), and the separator (C) were stacked in this order and thermocompression bonded, and then the double-sided metal-clad laminate was separated or peeled from the separator (C), thereby obtaining 2 double-sided metal-clad laminates.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2011/093427

Patent document 2: japanese patent laid-open No. 2014-128913

Disclosure of Invention

Problems to be solved by the invention

These patent documents are each characterized in that 2 metal-clad laminates are arranged so as to be vertically symmetrical about a separator and to be in contact with each other, and are thermocompression bonded by a roll. However, in these documents, the separator disposed at the center is directly contacted with the metal-clad laminate while being introduced into the heating roller.

Since the thermal compression bonding is generally performed in a temperature range in which the thermal compression bonding temperature of the thermoplastic liquid crystal polymer film exceeds 200 ℃, if the separator film having a high water absorption rate is introduced into the pressure roller in a normal temperature state and rapidly heated by the pressure roller, the separator film is heated from the normal temperature to a high temperature exceeding 200 ℃ at a burst, and thus the moisture of the separator film rapidly volatilizes.

At this time, the separator is brought into contact with the constituent material of the metal-clad laminate while being introduced into the heating roller, and therefore, moisture rapidly evaporated from the separator directly acts on the constituent material of the metal-clad laminate, and as a result, defects such as appearance defects such as bubble marks and lamination defects are generated in the metal-clad laminate. Further, due to thermal expansion caused by a rapid temperature rise during thermocompression bonding, the metal-clad laminate has poor appearance such as wrinkles and poor lamination due to a difference in thermal expansion coefficient between the separator and another material. When moisture is present in the separator, the thermoplastic polymer is hydrolyzed by water vapor generated by sudden temperature rise, and as a result, the low-molecular-weight thermoplastic liquid crystal polymer of the metal-clad laminate adheres to the surface of the separator, and the separator cannot be reused.

The present invention has been made to solve these problems, and an object of the present invention is to provide a method for efficiently producing a metal-clad laminate by a roll method.

Means for solving the problems

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that, even when 2 or more metal-clad laminates are simultaneously thermocompression bonded as a multiaxial laminate, by heating a release material before a constituent material of the metal-clad laminate (hereinafter, sometimes simply referred to as a constituent material) comes into contact with the release material, (i) moisture of the release material can be removed to suppress occurrence of defects due to moisture in the metal-clad laminate, (ii) a difference in thermal expansion coefficient between the release material and the constituent material can be reduced to prevent occurrence of wrinkles and the like in the metal-clad laminate, (iii) and that such a production method can prevent contamination of the release material, enables reuse of the release material, is excellent in economy, and, when such release material is used to thermocompression bond the constituent materials in a state in which metal foils are adjacent to each other, as a result, the metal foils can be efficiently peeled from each other in the peeling step to produce a metal-clad laminate, and the present invention has been completed.

That is, the present invention can be configured as follows.

[ mode 1]

A method for manufacturing a metal-clad laminate, comprising at least:

a pair of pressure rollers (r) are prepared₁，r₂) Releasing the release material (C)₁，C₂) A step of forming two or more metal-clad laminates each composed of a thermoplastic liquid crystal polymer film (F) and a metal foil (M);

with the above-mentioned constituent materials toThe two or more unwinding rollers are arranged so as to reduce the number of (M)/(M) metal foils adjacent to each other, and the pair of release materials (C) is used₁，C₂) A configuration step of configuring a release material unwinding roller so as to sandwich the entire constituent material;

the pair of release materials (C)₁，C₂) A heating step of discharging the release material from the unwinding roll and heating the release material;

a pair of release materials (C) after the heating process₁，C₂) The constituent material is sandwiched and the whole is guided into the pair of pressure rollers (r)₁，r₂) Hot press bonding step (2); and

after the thermal compression bonding step, the release material (C) is removed by at least 1 removing roller₁，C₂) With the release material (C)₁，C₂) And a peeling step of peeling off the thermoplastic liquid crystal polymer film (F) and/or the metal foil (M) in contact with each other and peeling off the adjacent metal foil (M) from the metal foil (M).

[ mode 2]

The method for producing a metal-clad laminate according to mode 1, wherein the thermoplastic liquid crystal polymer film (F) and the release material (C)₁，C₂) Either or both of which are in contact.

[ mode 3]

The method for producing a metal-clad laminate according to mode 1, wherein the metal foil (M) and the release material (C)₁，C₂) Either or both of which are in contact.

[ mode 4]

The method for producing a metal-clad laminate according to mode 1 or 2, wherein,

in the thermocompression bonding step, the pair of pressure rollers (r) are pressed₁，r₂) In the recipe (r)₁)/(C₁)/(F)/(M)/(M)/(F)/(C₂)/(r₂) Are overlapped in sequence and are subjected to hot-press bonding,

in the above peeling step, in (C)₁) between/((F)), (F)/(C)₂) And (M)/(M) in the presence of a solvent,2 metal-clad laminates were obtained.

[ means 5]

in the thermocompression bonding step, the pair of pressure rollers (r) are pressed₁，r₂) In the recipe (r)₁)/(C₁)/(F)/(M)/(M)/(F)/(M)/(M)/(F)/(C₂)/(r₂) Are overlapped in sequence and are subjected to hot-press bonding,

in the above peeling step, in (C)₁) between/((F)), (F)/(C)₂) And (M)/(M) to obtain 3 metal-clad laminates.

[ mode 6]

The method for producing a metal-clad laminate according to mode 1 or 3, wherein,

in the thermocompression bonding step, the pair of pressure rollers (r) are pressed₁，r₂) In the recipe (r)₁)/(C₁)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂)/(r₂) Are overlapped in sequence and are subjected to hot-press bonding,

in the above peeling step, in (C)₁) Between (M), (M)/(C)₂) And (M)/(M) to obtain 2 metal-clad laminates.

[ mode 7 ]

in the thermocompression bonding step, the pair of pressure rollers (r)₁，r₂) In the recipe (r)₁)/(C₁)/(M)/(F)/(M)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂)/(r₂) Are overlapped in sequence and are subjected to hot-press bonding,

in the above peeling step, in (C)₁) Between (M), (M)/(C)₂) And (M)/(M) to obtain 3 metal-clad laminates.

[ mode 8 ]

The method for producing a metal-clad laminate according to any one of aspects 1 to 7, wherein the release material (C)₁) And/or a release material (C)₂) To selectA release material selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film and a heat-resistant nonwoven fabric.

[ means 9 ]

The method for producing a metal-clad laminate according to any one of aspects 1 to 8, wherein the pair of release materials (C) is applied to the pair of mold release materials in the heating step₁，C₂) Is discharged from a release material unwinding roll and is externally connected to the pair of pressing rolls (r)₁，r₂) Thereby heating the respective release materials.

[ mode 10 ]

The method for producing a metal-clad laminate according to mode 9, wherein the pair of release materials (C) is heated in the heating step₁，C₂) And the pair of pressure rollers (r)₁，r₂) The contact time by external connection is 1.0 second or more.

[ mode 11 ]

The method for producing a metal-clad laminate according to mode 9 or 10, further comprising a step of applying the pair of release materials (C)₁，C₂) Is externally connected with the pair of pressure rollers (r)₁，r₂) A pair of guide rollers (g)₁，g₂)。

[ means 12 ]

The method for manufacturing a metal-clad laminate according to any one of aspects 1 to 11, further comprising a step for passing the metal-clad laminate through the pair of pressure rollers (r)₁，r₂) And a cooling roller for cooling the subsequent laminate.

[ means 13 ]

The method for producing a metal-clad laminate according to any one of aspects 1 to 5 and 8 to 12, wherein the thermoplastic liquid crystal polymer film (F) and the release material (C) are thermally compression bonded₁) Or a release material (C)₂) The peel strength of (A) is 0.6kN/m or less (more preferably 0.4kN/m or less, 0.3kN/m or less).

[ mode 14 ]

The method for manufacturing a metal-clad laminate according to any one of aspects 1 to 3 and 6 to 13, wherein the metal foil (M) and the release material (C) after thermocompression bonding₁) Or a release material (C)₂) The peel strength of (A) is 0.3kN/m or less (more preferably 0.2kN/m or less, 0.1kN/m or less).

[ means 15 ]

The method for producing a metal-clad laminate according to any one of aspects 1 to 14, wherein the peel strength between the metal foil (M) and the metal foil (M) after the thermocompression bonding is 0.3kN/M or less (more preferably 0.2kN/M or less, 0.1kN/M or less).

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

Effects of the invention

According to the present invention, since the release material can be brought into contact with the constituent material and thermocompression bonded in a state in which the moisture content is reduced, a metal-clad laminate in which appearance defects such as bubble marks and wrinkles do not occur can be efficiently produced. Further, since the release material is preheated in the heating step, the difference in thermal expansion coefficient between the release material and the constituent material at the time of lamination is reduced, and the occurrence of wrinkles and the like in the metal-clad laminate can be prevented. Therefore, the manufacturing method can prevent the release material from being polluted, enables the release material to be repeatedly used and has excellent economical efficiency. Further, by using a release material (C) after a heating process₁，C₂) The entire constituent material is sandwiched and thermocompression bonded in a state in which the metal foils are adjacent to each other, so that sudden heat release to the metal foils can be prevented, the laminate can be rapidly separated in the peeling step, and the production efficiency can be improved.

Drawings

The invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiments and the drawings are only for illustration and description and should not be used to define the scope of the invention. The scope of the invention is to be determined from the following claims. In the drawings, like reference numerals designate like parts throughout the several views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.

Fig. 1 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to embodiment 1 of the present invention.

Fig. 2 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to embodiment 2 of the present invention.

Fig. 3 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to embodiment 3 of the present invention.

Fig. 4 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to embodiment 4 of the present invention.

Fig. 5 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to embodiment 5 of the present invention.

Fig. 6 is a schematic side view for explaining a modification of the method of manufacturing a metal-clad laminate according to embodiment 1 of the present invention.

Fig. 7 is a schematic side view for explaining another modification of the method for producing a metal-clad laminate according to embodiment 1 of the present invention.

Detailed Description

The method for producing a metal-clad laminate of the present invention can continuously produce a plurality of sets of metal-clad laminates each having a metal foil laminated on at least one surface of a thermoplastic liquid crystal polymer film.

(thermoplastic liquid Crystal Polymer film)

The thermoplastic liquid crystal polymer film used in the production method of the present invention is formed of a melt-moldable liquid crystal polymer. The thermoplastic liquid crystal polymer is a polymer capable of forming a melt phase having optical anisotropy, and the chemical constitution thereof is not particularly limited as long as it is a melt-moldable liquid crystal polymer, and examples thereof include a thermoplastic liquid crystal polyester, and a thermoplastic liquid crystal polyesteramide having an amide bond introduced thereinto.

The thermoplastic liquid crystal polymer may be a polymer obtained by further introducing an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond to 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 polyester amides derived from compounds classified into the following exemplary compounds (1) to (4) and derivatives thereof. Of these, it goes without saying that there is an appropriate range of combination of the respective raw material compounds in order to form the polymer capable of forming an optically anisotropic melt phase.

(1) Aromatic or aliphatic dihydroxy Compound (see Table 1 for representative examples)

[ Table 1]

(2) Aromatic or aliphatic dicarboxylic acid (see Table 2 for representative examples)

[ Table 2]

(3) Aromatic hydroxycarboxylic acids (see Table 3 for representative examples)

[ Table 3]

(4) Aromatic diamine, aromatic hydroxylamine or aromatic aminocarboxylic acid (see Table 4 for representative examples)

[ Table 4]

Representative examples of the thermoplastic liquid-crystalline polymers obtained from these raw material compounds include copolymers having the structural units shown in tables 5 and 6.

[ Table 5]

[ Table 6]

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

For example, in the case of the polymer (i), when the thermoplastic liquid crystal polymer contains at least a repeating unit of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the molar ratio (a)/(B) of the p-hydroxybenzoic acid of the repeating unit (a) to the 6-hydroxy-2-naphthoic acid of the repeating unit (B) is preferably (a)/(B) about 10/90 to 90/10, more preferably (a)/(B) about 15/85 to 85/15, and still more preferably (a)/(B) about 20/80 to 80/20 in the thermoplastic liquid crystal polymer.

In the case of the polymer of (ii), the molar ratio of each repeating unit of at least one aromatic hydroxycarboxylic acid (C) selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, at least one aromatic diol (D) selected from the group consisting of 4, 4 '-dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4, 4' -dihydroxydiphenyl ether, and at least one aromatic dicarboxylic acid (E) selected from the group consisting of terephthalic acid, isophthalic acid, and 2, 6-naphthalenedicarboxylic acid may be the aromatic hydroxycarboxylic acid (C): the above aromatic diol (D): the aromatic dicarboxylic acid (E) is (30 to 80): (35-10): (35-10), more preferably (C): (D) the method comprises the following steps (E) (35-75): (32.5-12.5): (32.5 to 12.5), and more preferably (C): (D) the method comprises the following steps (E) (40-70): (30-15): (30-15) or so.

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

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

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

The melt phase capable of forming optical anisotropy in the present invention can be identified, for example, by placing a sample on a heating stage, heating the sample at an elevated temperature in a nitrogen atmosphere, and observing the transmitted light of the sample.

As a preferable thermoplastic liquid crystal polymer, a melting point (hereinafter referred to as Tm)₀) May be in the range of 200 to 360 ℃, preferably 240 to 360 ℃, more preferably 260 to 360 ℃, and further preferably Tm₀Is 270 to 350 ℃. Note that Tm is₀It can be determined by measuring the temperature at which the main endothermic peak appears by a differential scanning calorimeter (DSC, Shimadzu corporation). That is, after the thermoplastic liquid crystal polymer sample was heated at a rate of 10 ℃/min to be completely melted, the melt was cooled at a rate of 10 ℃/min to 50 ℃, and the temperature was again heated at a rate of 10 ℃/min, and then the position of the occurrence of the endothermic peak was defined as the melting point of the thermoplastic liquid crystal polymer sample.

The thermoplastic liquid crystal polymer may contain thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyether ether ketone, and fluorine resin, various additives, fillers, and the like, as long as the effects of the present invention are not impaired.

The thermoplastic liquid crystal polymer film used in the production method of the present invention can be obtained by, for example, extrusion molding of a melt-kneaded product of the thermoplastic liquid crystal polymer. As the extrusion molding method, any method can be used, but a known T die method, inflation method, or the like is industrially advantageous. In particular, the inflation method applies stress not only in the machine axis direction (hereinafter abbreviated as MD direction) but also in the direction orthogonal thereto (hereinafter abbreviated as TD direction) to the thermoplastic liquid crystal polymer film, and can uniformly stretch the film in the MD direction and the TD direction, and thus a thermoplastic liquid crystal polymer film in which molecular orientation, dielectric characteristics, and the like in the MD direction and the TD direction are controlled can be obtained.

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

In extrusion molding by the inflation method, a cylindrical sheet melt-extruded from an annular die is stretched at a predetermined stretch ratio (corresponding to a stretching ratio in the MD direction) and a predetermined blow ratio (corresponding to a stretching ratio in the TD direction) to form a film.

The stretch ratio of such extrusion molding may be, for example, about 1.0 to 10, preferably about 1.2 to 7, and more preferably about 1.3 to 7 as the stretch ratio (or stretch ratio) in the MD direction. The stretch 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, as で.

Further, the heat treatment may be performed by a known or conventional heat treatment to adjust the heat as requiredMelting point and/or coefficient of thermal expansion of the plastic liquid crystal polymer film. The heat treatment conditions may be appropriately set according to the purpose, and for example, the melting point (Tm) of the thermoplastic liquid crystal polymer₀) Above-10 ℃ (e.g., Tm)₀-10℃～Tm₀About +30 ℃, preferably Tm₀℃～Tm₀About +20 ℃) for several hours, thereby increasing the melting point (Tm) of the thermoplastic liquid crystal polymer film.

The thermoplastic liquid crystal polymer film may have a melting point (Tm) of 270 to 380 ℃ and preferably 280 to 370 ℃.

The melting point (Tm) of the thermoplastic liquid crystal polymer film can be obtained by observing the thermal behavior of a sample of the thermoplastic liquid crystal polymer film using a differential scanning calorimeter. That is, the position of the endothermic peak occurring when the temperature of the thermoplastic liquid crystal polymer film sample was raised at a rate of 10 ℃/min was determined as the melting point (Tm) of the thermoplastic liquid crystal polymer film.

(Metal foil)

The metal foil used in the production method of the present invention is not particularly limited, and may be, for example, gold, silver, copper, iron, nickel, aluminum, or an alloy metal thereof, and is preferably a copper foil or a stainless steel foil from the viewpoint of conductivity, handling properties, cost, and the like. As the copper foil, a copper foil produced by a rolling method or an electrolytic method can be used.

The thickness of the metal foil may be appropriately set as needed, and may be, for example, about 5 to 50 μm, and more preferably 8 to 35 μm. The metal foil may be subjected to a surface treatment such as roughening treatment which is usually performed.

(Release Material)

The release material used in the production method of the present invention is not particularly limited as long as it can be easily peeled from an adjacent adherend after thermocompression bonding and has heat resistance, and examples thereof include: heat-resistant resin films such as non-thermoplastic polyimide films, aramid films, and teflon (registered trademark) films; heat-resistant composite films (e.g., composite films composed of two or more heat-resistant resin films, composite films composed of a metal foil and a heat-resistant resin film); metal foils such as aluminum foil and stainless steel foil; and heat-resistant nonwoven fabrics made of heat-resistant fibers (e.g., heat-resistant resin fibers and metal fibers). These release materials may be used alone or in combination of two or more.

Among these release materials, heat-resistant resin films, heat-resistant composite films, and heat-resistant nonwoven fabrics are preferable from the viewpoint of excellent heat resistance and rebound properties.

The thickness of the release material can be appropriately set as needed, and can be, for example, about 10 to 300 μm, preferably 15 to 150 μm, and more preferably 15 to 45 μm. In addition, in order to improve the releasability from the adherend after thermocompression bonding, a releasing treatment may be applied to one surface or both surfaces of the release material. Examples of the method of the release treatment include a method of providing a heat-resistant release resin coating such as a silicone resin or a fluororesin on at least one surface of a release material.

(method for producing Metal-clad laminate)

The method for manufacturing a metal-clad laminate of the present invention includes at least:

the two or more unwinding rollers are arranged so that the constituent materials form at least a state (M)/(M) in which the metal foils are adjacent to each other, and the pair of release materials (C)₁，C₂) A configuration step of configuring a release material unwinding roller so as to sandwich the entire constituent material;

the pair of release materials (C)₁，C₂) A heating step of discharging the release materials from the release material unwinding roll and heating the release materials respectively;

a pair of release materials (C) after the heating process₁，C₂) The pair of pressure rollers (b) are integrally introduced while sandwiching the constituent material (c)r₁，r₂) Hot press bonding step (2); and

Here, the thermoplastic liquid crystal polymer film (F) in the constituent material for forming 1 metal-clad laminate may be one sheet or two or more sheets. The metal foil (M) may be one sheet or two or more sheets. When two or more sheets are contained, they may be the same or different.

The metal-clad laminate discharged from the unwinding roll may be composed of the thermoplastic liquid crystal polymer film (F) and the metal foil (M) alone, or may be composed of the thermoplastic liquid crystal polymer film (F) and the metal foil (M) in a metal-clad laminate (M)/(F) on one side. Therefore, the two or more unwinding rolls for unwinding the constituent material for forming the two or more metal-clad laminates composed of the thermoplastic liquid crystal polymer film (F) and the metal foil (M) may include (i) an unwinding roll for unwinding the thermoplastic liquid crystal polymer film (F), (ii) an unwinding roll for unwinding the metal foil (M), and/or (iii) an unwinding roll for unwinding the one-side metal-clad laminate (M)/(F).

The metal-clad laminates obtained may be the same or different.

Each pay-off roll is disposed so as to satisfy the following conditions, for example.

(i) Two or more metal-clad laminates (single-sided metal-clad laminates and/or double-sided metal-clad laminates) are formed from constituent materials of the two or more metal-clad laminates, and adjacent metal-clad laminates are adjacent to each other with respective metal foils interposed therebetween.

(ii) A release material (C) discharged from a pair of release material unwinding rolls₁，C₂) Sandwiching the whole of the constituting material, i.e. release material (C)₁) And a release material (C)₂) Respectively forming the outermost layers.

Release material (C)C₁，C₂) So long as the heating step (C) can heat the release material₁，C₂) The release material (C) may be heated by an external heating means such as a heater, without particular limitation₁，C₂) Alternatively, a pressure roller (r) may be used₁，r₂) Heating the release material (C) by a separately provided heating roller₁，C₂). Alternatively, the release material (C) may be used₁，C₂) Is externally connected to the pressure roller (r)₁，r₂) To heat the release material (C)₁，C₂)。

By preheating the release material (C) in the heating step₁，C₂) The moisture of the release material can be removed, and the difference in thermal expansion coefficient between the release material and the constituent material can be reduced. And, by using the release material (C) after the heating process₁，C₂) The entire constituent material is sandwiched and thermocompression bonded in a state in which the metal foils are adjacent to each other, and heat is prevented from being suddenly released to the metal foils, thereby facilitating peeling between the metal foils.

The heating step can be determined based on the thermocompression bonding temperature, and when the thermocompression bonding temperature is T ℃, the temperature of the heating step may be, for example, T-10 ℃ or more, T-5 ℃ or more, and preferably lower than the thermocompression bonding temperature, and the upper limit may be lower than T ℃.

In the heating step, the heating time may be appropriately set according to the heating means, and for example, it is preferable to heat the release material in a range in which the moisture content of the release material is within a predetermined range (for example, 1100ppm or less, 900ppm or less, 700ppm or less, or 400ppm or less).

The following describes specific embodiments with reference to the drawings. Fig. 1 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to embodiment 1.

In the manufacturing method of the present invention, a pair of pressure rollers (r)₁，r₂) Upstream side of (2) preparing to release the release material (C)₁，C₂) A pair of release material unwinding rolls 11, two or more thermoplastic liquid crystal films (F) from which the thermoplastic liquid crystal polymer film (F) is dischargedPolymer film unwinding rollers 12, and two or more metal

foil unwinding rollers

13, 13 that unwind the metal foil (M).

Here, as shown in fig. 1, in embodiment 1, a thermoplastic liquid crystal polymer film (F), a metal foil (M), and a release material (C) are used₁) And a release material (C)₂) At a pair of pressure rollers (r)₁，r₂) The sequence between is (r)₁)/(C₁)/(F)/(M)/(M)/(F)/(C₂)/(r₂) The unwinding rollers are arranged in such a manner.

Specifically, a pair of pressure rollers (r)₁，r₂) So as to let out the release material (C)₁，C₂) The pair of release

material unwinding rollers

11, 11 are disposed so as to form the outermost layers, and two or more thermoplastic liquid crystal polymer

film unwinding rollers

12, 12 for unwinding the thermoplastic liquid crystal polymer film (F) are disposed inside the pair of release material unwinding rollers, and two or more metal

foil unwinding rollers

13, 13 for unwinding the metal foil (M) are disposed inside the pair of release material unwinding rollers.

As shown in fig. 1, the pair of pressure rollers (r) are opposed to each other₁，r₂) After each unwinding roll was disposed, a thermoplastic liquid crystal polymer film (F), a metal foil (M), and a release material (C) were placed₁，C₂) Is fed from each unwinding roll as shown by the arrow direction, and is opposed to a pair of pressure rolls (r) in the MD direction (or laminating direction) as shown by the arrow₁，r₂) The introduction is performed.

Herein, a pair of release materials (C) paid out from release material unwinding rolls 11, 11 are wound up₁，C₂) The pair of pressure rollers (r) are respectively contacted with the constituent material before the constituent material is introduced into the pair of pressure rollers₁，r₂) And externally connecting for a specified time.

In the external connection process, a release material (C) is used₁，C₂) And a pressure roller (r)₁，r₂) Can be contacted with the release material (C)₁，C₂) Removing water. And by lowering the release material (C) before contacting the thermoplastic liquid crystal polymer film (F) and the metal foil (M)₁，C₂) The water content of (2) can inhibit the generation of bubble marks on the surface of the laminateAnd defects such as lamination defects. In the circumscribed step, a starting point of contact with the outer periphery of the pressure roller may be appropriately set according to the size of the pressure roller and the rotation speed of the pressure roller, and the release material (C) may be used₁，C₂) The external connection process is performed so as to follow the pressure roller from a predetermined starting point. In the present invention, the term "external connection" means: the release material is brought into contact with and conveyed so as to follow the outer periphery of the pressure roller from a predetermined starting point.

The release material unwinding roller is positioned so that a pair of release materials (C) can be wound₁，C₂) And a pair of pressure rollers (r)₁，r₂) The contact is not particularly limited, and the release material discharged from the release material unwinding roll may be directly introduced into the pressure roll, or the release material discharged from the release material unwinding roll may be introduced into the pressure roll after passing through one or more than two guide rolls. Therefore, it is preferable to provide a pair of guide rollers (g) for externally connecting the pair of release materials to the pair of pressure rollers₁，g₂)。

For example, as shown in FIG. 1, a pair of release materials (C)₁，C₂) After being discharged from the release material unwinding rollers 11, the release material may not be directly introduced into the pressure roller (r)₁，r₂) But by being arranged at the pressure roller (r)₁，r₂) The

adjacent guide rollers

14, 14 are guided into a pair of pressure rollers (r) from the

guide rollers

14, 14₁，r₂). The pair of release materials (C) can be guided by the

guide rollers

14, 14₁，C₂) Is externally connected with a pair of pressure rollers (r)₁，r₂) The desired position of the device.

The guide roller is arranged at a position where a pair of release materials (C) can be arranged₁，C₂) Is externally connected with a pair of pressure rollers (r)₁，r₂) Although the guide roller is not particularly limited and is disposed in the vicinity of the pressure roller in fig. 1, it may be in contact with the pressure roller.

For example, in FIG. 1, a release material (C) is applied prior to thermocompression bonding₁) Is externally connected to the pressure roller (r)₁) And a release material (C)₂) Is externally connected to the pressure roller (r)₂). By thus externally connecting (or surrounding) the release material to the pressure roller, the release material can be removedMoisture contained in the molding material, and the release material can be preheated in advance to the vicinity of the thermal compression bonding temperature. The distance between the release material and the outer periphery of the pressure roller may be set as appropriate, and may be, for example, 1/8 or more, 1/4 or more, and 1/2 or more of the circumference of the pressure roller.

The time for externally connecting the release member and the pressure roller may be appropriately set according to various conditions such as the type of the release member, the state of the release member, and the heating temperature of the pressure roller, and from the viewpoint of removing moisture from the release member, the time for externally connecting the release member and the pressure roller is preferably, for example, 1.0 second or more, for example, 1.0 to 200 seconds, and for example, 3.0 to 125 seconds.

The time for the external connection can be set as appropriate by predicting the time at which the moisture content of the release material reaches a predetermined range (for example, 1100ppm or less, 900ppm or less, 700ppm or less, or 400ppm or less).

Preferably, a release material (C)₁，C₂) Before the pressure roller is pressed, the temperature of the pressure roller is externally increased so that the heating temperature T DEG C of the pressure roller reaches a temperature of T-15 DEG or more. The temperature of the release material before pressing by the pressing roller may be T-10 ℃ or higher, T-5 ℃ or higher, and may be lower than the heating temperature.

A pair of release materials (C)₁，C₂) After the external connection process, the constituent material of the metal-clad laminate composed of the thermoplastic liquid crystal polymer film (F) and the metal foil (M) is sandwiched as the outermost layer, and the whole is introduced into a pair of press rollers (r)₁，r₂)。

For example, in FIG. 1, a pair of release materials (C)₁，C₂) Is integrally guided to a pair of pressure rollers (r) by sandwiching (F)/(M)/(M)/(F)₁，r₂)。

The pair of pressure rollers comprises a pair of release materials (C) at a predetermined heating temperature₁，C₂) (C) a laminate comprising a thermoplastic liquid crystal polymer film (F) and a metal foil (M) as the outermost layer₁)/(F)/(M)/(M)/(F)/(C₂) Pressure is applied.

As the pressure roller, a known heating and pressing device can be used. Further, the thermocompression bonding temperature and the pressure condition of the pressure roller are not particularly limited, but for good adhesion of the thermoplastic liquid crystal polymer film and the metal foil, for example, the thermocompression bonding temperature may be in the range of, for example, (Tm-20) to (Tm +20) DEG C, and preferably (Tm-15) to (Tm +5) DEG C, with respect to the melting point (Tm) of the thermoplastic liquid crystal polymer film.

The pressing pressure may be in the range of 10t/m (98kN/m) to 1.5t/m (14.7kN/m), and preferably in the range of 5t/m (49kN/m) to 1.0t/m (9.8 kN/m). The pressing pressure is a value obtained by dividing a force (pressing load) applied to the pressing roller by the effective width of the pressing roller.

In the method for producing a metal-clad laminate of the present invention, the release material (C) is separated by at least 1 separation roller₁，C₂) With the release material (C)₁，C₂) The thermoplastic liquid crystal polymer film (F) and/or the metal foil (M) in contact with each other are peeled off, and the adjacent metal foil (M) and the metal foil (M) are peeled off.

In the peeling step, peeling between the release material and the thermoplastic liquid crystal polymer film and/or the metal foil in contact with the release material and peeling between the adjacent metal foil (M) and the metal foil (M) may be performed simultaneously or in stages.

The peeling step may be carried out by a known or conventional method, and for example, in the peeling step, (i) the release material (C) may be carried out by using at least 1 peeling roller₁，C₂Either of) peeling from the thermoplastic liquid crystal polymer film (F) in contact with the release material, (ii) the release material (C)₁，C₂Any one of) peeling from the metal foil (M) in contact with the release material, and (iii) peeling from the metal foil (M) adjacent to the release material. The order of the above (i), (ii) and (iii) is not particularly limited, and two or more of these may be performed simultaneously or may be performed in stages.

The at least 1 peeling roller may be a pair of peeling rollers, two or more peeling rollers provided individually, or a combination thereof. The order of the peeling rollers may be set as appropriate, and either may be on the upstream side.

For example, the above (i), (ii) and (iii) may be performed at once by passing between a pair of peeling rollers.

Alternatively, any two of (i), (ii), and (iii) may be performed at once by passing between a pair of peeling rollers, the remaining peeling may be performed in stages by a single peeling roller, or the peeling may be performed in stages by a single peeling roller and then the remaining peeling may be performed by passing between a pair of peeling rollers.

For example, when the peeling is performed in stages, the peeling between (M)/(M) as the metal foil may be performed as the first peeling step, and the peeling may be performed subsequently or simultaneously with the step selected from (C)₁) between/((F)), (F)/(C)₂) A (C) is₁) Between (M) and (M)/(C)₂) At least 1 stripping step in between. When the peeling step between the metal foils is first performed, heat can be quickly released from the metal foils, and as a result, the cooling rate of the laminate in the peeling step can be increased.

Alternatively, when the peeling is performed in stages, the release material (C) may be used₁，C₂) With the release material (C)₁，C₂) A step of peeling the thermoplastic liquid crystal polymer film (F) and/or the metal foil (M) in contact with each other, namely, a step selected from (C)₁) between/((F)), (F)/(C)₂) A (C) is₁) Between (M) and (M)/(C)₂) At least 1 kind of peeling between the two steps is performed as an initial peeling step. The remaining peeling step may be performed subsequently or simultaneously as necessary.

In the present invention, since the release material is disposed on the outermost layer, the release material can be very easily released. As a result, the formation of wrinkles that are likely to occur when peeling is difficult can be suppressed, and a high-quality metal-clad laminate can be produced with high productivity.

For example, in embodiment 1 shown in fig. 1, a laminate (C)₁)/(F)/(M)/(M)/(F)/(C₂) Passing through the stripping

rollers

15, 15 at (C)₁) between/((F)), (F)/(C)₂) And (M)/(M), thereby producing 2 single-sided metal-clad laminates (MF). Peeled off release material (C)₁，C₂) Are wound by release material winding rolls 16, respectively. The peeled release material (C) is suppressed in contamination by the low molecular weight thermoplastic liquid crystal polymer₁，C₂) Can be reused as required. The obtained metal-clad laminate is wound by the metal

laminate winding rollers

17, 17.

In addition, as shown in FIG. 2, in embodiment 2, a thermoplastic liquid crystal polymer film (F), a metal foil (M), and a release material (C) are used₁) And a release material (C)₂) At a pair of pressure rollers (r)₁，r₂) The sequence between is (r)₁)/(C₁)/(F)/(M)/(M)/(F)/(M)/(M)/(F)/(C₂)/(r₂) The unwinding rollers are arranged in such a manner. Here, members having the same functions as those in fig. 1 are given the same reference numerals and are not described.

In embodiment 2 shown in fig. 2, a pair of pressure rollers (r)₁，r₂) To (C)₁)/(F)/(M)/(M)/(F)/(M)/(M)/(F)/(C₂) The laminated body having the above-mentioned mode is described in (C)₁) between/((F)), (F)/(C)₂) And (M)/(M) were peeled off, thereby producing 2 single-sided metal-clad laminates (M)/(F) (hereinafter sometimes abbreviated as MF or FM) and 1 double-sided metal-clad laminate (M)/(F)/(M) (hereinafter sometimes abbreviated as MFM).

In addition, as shown in FIG. 3, in embodiment 3, a thermoplastic liquid crystal polymer film (F), a metal foil (M), and a release material (C) are used₁) And a release material (C)₂) At a pair of pressure rollers (r)₁，r₂) The sequence between is (r)₁)/(C₁)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂)/(r₂) The unwinding rollers are arranged in such a manner. Here, members having the same functions as those in fig. 1 are given the same reference numerals and are not described.

In embodiment 3 shown in fig. 3, a pair of pressure rollers (r)₁，r₂) To (C)₁)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂) In overlapping mannerA laminate of (C)₁) Between (M), (M)/(C)₂) And (M)/(M), thereby manufacturing 2 double-sided metal-clad laminates (MFM).

In addition, as shown in FIG. 4, in embodiment 4, a thermoplastic liquid crystal polymer film (F), a metal foil (M), and a release material (C) are used₁) And a release material (C)₂) At a pair of pressure rollers (r)₁，r₂) The sequence between is (r)₁)/(C₁)/(M)/(F)/(M)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂)/(r₂) The unwinding rollers are arranged in such a manner. Here, members having the same functions as those in fig. 1 are given the same reference numerals and are not described.

In the 4 th embodiment shown in fig. 4, a pair of pressure rollers (r)₁，r₂) To (C)₁)/(M)/(F)/(M)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂) The laminated body having the above-mentioned mode is described in (C)₁) Between (M), (M)/(C)₂) And (M)/(M), thereby manufacturing 3 double-sided metal-clad laminates (MFM).

In embodiment 5, as shown in fig. 5, a metal foil (M), and a release material (C) are laminated on one surface of a metal foil (M) and a thermoplastic liquid crystal polymer film (F) in a metal-clad laminate (MF) (FM)₁) And a release material (C)₂) In the thermocompression bonding, a pair of pressure rollers (r)₁，r₂) The sequence between is (r)₁)/(C₁)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂)/(r₂) The unwinding rollers are arranged in such a manner. Here, the metal-clad laminate (MF) is paid out from the pay-off roll 18. In addition, members having the same functions as those in fig. 1 are given the same reference numerals and are not described.

In embodiment 5 shown in fig. 5, a pair of pressure rollers (r)₁，r₂) To (C)₁)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂) The laminated body having the above-mentioned mode is described in (C)₁) Between (M), (F)/(C)₂) And (M)/(M), thereby manufacturing 2 double-sided metal-clad laminates (MFM).

In addition, a cooling roller for cooling the pressure roller may be provided on the downstream side of the pressure roller as neededWill be transmitted from a pair of pressure rollers (r)₁，r₂) The passed laminate was cooled. For example, since wrinkles and undulations are likely to occur due to tension when a laminate having a high temperature is conveyed, the laminate after lamination can be cooled to Tg or less (80 ℃ or less) of the thermoplastic liquid crystal polymer film by slowly cooling the laminate with a cooling roll of 30 ℃. The cooling roller is preferably disposed between the pressure roller and the peeling roller. The cooling roll may be constituted by a pair of rolls or 1 single roll.

For example, fig. 6 is a schematic side view for explaining a modification example in which the peeling step in embodiment 1 is changed. As shown in fig. 6, the cooling

rollers

19, 19 are provided on a pair of pressure rollers (r)₁，r₂) And two or more peeling rollers 25, 25' are provided at different positions in the lamination traveling direction. By means of a pair of pressure rollers (r)₁，r₂) The thermally pressed laminate is then gradually cooled by passing through the cooling

rollers

19, 19. Then is stripped off at (F)/(C) by a stripping roll 25₂) And (M)/(M) to produce a single-sided metal-clad laminate (MF), followed by peeling at (C) with a peeling roller 25₁) And (M) to produce a single-sided metal-clad laminate (MF).

As another example, fig. 7 is a schematic side view for explaining a modification example in which the peeling step in embodiment 1 is changed. As shown in fig. 7, a pair of pressure rollers (r) are used₁，r₂) The thermally bonded laminate is first separated between (M)/(M) by passing through the

separation rollers

15 and 15, and then divided into laminates (MFCs)₁) And (MFC)₂) Then, each laminate passes through the 2 nd peeling rollers 25 and 25' at the ratio of (F)/(C)₁) And (F)/(C)₂) Is peeled off, thereby finally manufacturing 2 single-sided metal clad laminates (MF).

The peeling strength between the release material and the thermoplastic liquid crystal polymer film after thermocompression bonding, the peeling strength between the release material and the metal foil, and the peeling strength between the metal foil and the metal foil can be appropriately set as long as the peeling step can be performed. Here, the peel strength is a peel strength (peel strength) measured in accordance with JIS C5016-1994(90 ℃ peeling).

For example, the peel strength between the release material and the thermoplastic liquid crystal polymer film after thermocompression bonding is preferably 0.6kN/m or less, more preferably 0.4kN/m or less, and still more preferably 0.3kN/m or less.

For example, the peel strength between the release material and the metal foil after thermocompression bonding is preferably 0.3kN/m or less, more preferably 0.2kN/m or less, and still more preferably 0.1kN/m or less.

For example, the peel strength between the metal foil and the metal foil after thermocompression bonding is preferably 0.3kN/m or less, more preferably 0.2kN/m or less, and still more preferably 0.1kN/m or less.

Industrial applicability

According to the manufacturing method of the present invention, a metal-clad laminate can be efficiently manufactured, and the obtained metal-clad laminate can be effectively used as a component used in the electric/electronic field, the office equipment/precision equipment field, the power semiconductor field, or the like, for example, a circuit board (particularly, a board for millimeter wave radar).

As described above, the preferred embodiments of the present invention have been described with reference to the drawings, but those skilled in the art can easily conceive various changes and modifications within the obvious scope when viewing the present specification. Therefore, such changes and modifications are to be construed as being within the scope of the invention as defined by the appended claims.

Description of the symbols

11 … release material unwinding roller

12 … thermoplastic liquid crystal polymer film decoiling roll

13 … metal foil decoiling roll

14 … guide roller

15, 25, 25' … peel roll

16 … stripper take-up roll

17 … Metal clad laminate take-up roll

18 … metal clad laminate unwind roll

19 … chill roll

Claims

1. A method for manufacturing a metal-clad laminate, comprising at least:

a pair of release materials (C) after the heating process₁，C₂) The constituent material is sandwiched and the whole is guided into the pair of press rollers (r)₁，r₂) Hot press bonding step (2); and

the release material (C) is removed by at least 1 removing roller after the thermal compression bonding process₁，C₂) With the release material (C)₁，C₂) And a peeling step of peeling off the thermoplastic liquid crystal polymer film (F) and/or the metal foil (M) in contact with each other and peeling off the adjacent metal foil (M) from the metal foil (M).

2. The method for producing a metal-clad laminate according to claim 1, wherein a thermoplastic liquid crystal polymer film (F) and the release material (C)₁，C₂) Either or both of which are in contact.

3. The method for manufacturing a metal-clad laminate according to claim 1, wherein a metal foil (M) and the release material (C)₁，C₂) Either or both of which are in contact.

4. The method for producing a metal-clad laminate according to claim 1 or 2, wherein,

in the thermal compression bonding step, the pair of pressure rollers (r) are provided₁，r₂) In the recipe (r)₁)/(C₁)/(F)/(M)/(M)/(F)/(C₂)/(r₂) Are overlapped in sequence and are subjected to hot-press bonding,

in the peeling step, the step (C) is₁) between/((F)), (F)/(C)₂) And (M)/(M) to obtain 2 metal-clad laminates.

5. The method for producing a metal-clad laminate according to claim 1 or 2, wherein,

in the thermal compression bonding step, the pair of pressure rollers (r) are provided₁，r₂) In the recipe (r)₁)/(C₁)/(F)/(M)/(M)/(F)/(M)/(M)/(F)/(C₂)/(r₂) Are overlapped in sequence and are subjected to hot-press bonding,

in the peeling step, the step (C) is₁) between/((F)), (F)/(C)₂) And (M)/(M) to obtain 3 metal-clad laminates.

6. The method for producing a metal-clad laminate according to claim 1 or 3,

in the thermal compression bonding step, the pair of pressure rollers (r) are provided₁，r₂) In the recipe (r)₁)/(C₁)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂)/(r₂) Are overlapped in sequence and are subjected to hot-press bonding,

in the peeling step, the step (C) is₁) Between (M), (M)/(C)₂) And (M)/(M) to obtain 2 metal-clad laminates.

7. The method for producing a metal-clad laminate according to claim 1 or 3,

in the thermal compression bonding step, the pair of pressure rollers (r) are provided₁，r₂) In the recipe (r)₁)/(C₁)/(M)/(F)/(M)/(M)/(F)/(M)/(M)/(F)/(M)/(C₂)/(r₂) Are overlapped in sequence and are subjected to hot-press bonding,

in the peeling step, the step (C) is₁) Between (M), (M)/(C)₂) And (M)/(M) to obtain 3 metal-clad laminates.

8. The method for producing a metal-clad laminate according to any one of claims 1 to 3, wherein the release material (C)₁) And/or a release material (C)₂) Is a release material selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film and a heat-resistant non-woven fabric.

9. The method for producing a metal-clad laminate according to any one of claims 1 to 3, wherein the pair of release materials (C) is applied in the heating step₁，C₂) Is discharged from a release material unwinding roll and is externally connected to the pair of pressing rolls (r)₁，r₂) Thereby heating the respective release materials.

10. The method for manufacturing a metal-clad laminate according to claim 9, wherein in the heating step, the pair of release materials (C) is heated₁，C₂) And the pair of pressure rollers (r)₁，r₂) The contact time by external connection is 1.0 second or more.

11. The method for manufacturing a metal-clad laminate according to claim 9, further comprising a step for applying the pair of release materials (C)₁，C₂) Is externally connected with the pair of pressure rollers (r)₁，r₂) A pair of guide rollers (g)₁，g₂)。

12. The method for manufacturing a metal-clad laminate according to claim 10, further comprising a step for applying the pair of release materials (C)₁，C₂) Is externally connected with the pair of pressure rollers (r)₁，r₂) A pair of guide rollers (g)₁，g₂)。

13. The method for producing a metal-clad laminate according to any one of claims 1 to 3, further comprising a step for passing the metal-clad laminate through the pair of pressure rollers (r)₁，r₂) And a cooling roller for cooling the subsequent laminate.

14. The method for manufacturing a metal-clad laminate according to claim 11, further comprising a step for passing the metal-clad laminate through the pair of pressure rollers (r)₁，r₂) And a cooling roller for cooling the subsequent laminate.

15. The method for producing a metal-clad laminate according to any one of claims 1 to 3, wherein the thermoplastic liquid crystal polymer film (F) and the release material (C) are thermally compression bonded₁) Or a release material (C)₂) The peel strength of (A) is 0.6kN/m or less.

16. The method for producing a metal-clad laminate according to claim 14, wherein the thermoplastic liquid crystal polymer film (F) and the release material (C) after thermocompression bonding₁) Or a release material (C)₂) The peel strength of (A) is 0.6kN/m or less.

17. The method for producing a metal-clad laminate according to any one of claims 1 to 3, wherein the metal foil (M) and the release material (C) after thermocompression bonding₁) Or a release material (C)₂) The peel strength of (A) is 0.3kN/m or less.

18. The method for manufacturing a metal-clad laminate according to claim 14, wherein the metal foil (M) and the release material (C) after thermocompression bonding₁) Or a release material (C)₂) The peel strength of (A) is 0.3kN/m or less.

19. The method for producing a metal-clad laminate according to any one of claims 1 to 3, wherein the peel strength between the metal foil (M) and the metal foil (M) after thermocompression bonding is 0.3kN/M or less.

20. The method for producing a metal-clad laminate according to claim 14, wherein the peel strength between the metal foil (M) and the metal foil (M) after the thermocompression bonding is 0.3kN/M or less.