JP7458396B2 - Manufacturing method of metal clad laminate - Google Patents

Description

Related applications

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

The present invention provides a film (hereinafter referred to as a thermoplastic liquid crystal polymer film) made of a thermoplastic polymer (hereinafter sometimes referred to as a thermoplastic liquid crystal polymer) capable of forming an optically anisotropic melt phase. A metal clad laminate (or The present invention relates to a method for producing a metal-clad laminate (a metal-clad laminate in which the metal-shaped sheet on the other side is peeled off).

Thermoplastic liquid crystal polymer films are known as materials with excellent properties such as high heat resistance, low moisture absorption, and high frequency characteristics, and have recently attracted attention as materials for electronic circuits for high-speed transmission. When used for electronic circuit board applications, a metal-clad laminate consisting of a thermoplastic liquid crystal polymer film and metal foil is used, but in the bonding process in the circuit processing process, the thermoplastic liquid crystal polymer film included in the metal-clad laminate is used. The interlayer adhesion between the bonding sheet and the bonding sheet may not be sufficient. Conventionally, in order to improve the interlayer adhesion with the bonding sheet, in a single-sided metal-clad laminate that has a metal layer on one side of a thermoplastic liquid crystal polymer film, an uneven shape is formed on the surface of the thermoplastic liquid crystal polymer film on the other side. The imprinting process was being performed.

Patent Document 1 (JP 2016-10967 A) discloses a method for producing a liquid crystal polymer film with metal foil, which 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 pressing them, in which the surface of the second metal foil that is stacked on the liquid crystal polymer film is a matte surface, and the matte surface is subjected to a release treatment.

Further, in Patent Document 2 (Japanese Patent Application Laid-open No. 2006-179609), at least one surface of each thermoplastic resin layer is subjected to a chemical roughening treatment using an alkaline mixed solution as a chemical solution, and the surface subjected to the treatment is Disclosed is a method for manufacturing a laminated wiring board, characterized in that a laminated board having two or more layers is formed by stacking a thermoplastic resin on the surface of another unit board, and the laminated board is heated and pressurized. is disclosed to be a liquid crystal polymer.

Unexamined Japanese Patent Publication No. 2016-10967 Japanese Patent Application Publication No. 2006-179609

Furthermore, when a metal-clad laminate is used in an electronic circuit for high-speed transmission, a skin effect occurs in the metal layer that serves as a transmission line, so the high frequency characteristics of the metal layer, that is, the transmission loss, depend on its surface roughness. Therefore, it is preferable to use a low-roughness metal layer with a small surface roughness because the transmission loss is reduced, and in other words, the high-frequency characteristics are improved.

However, as in Patent Document 1, when a first metal foil, a liquid crystal polymer film, and a second metal foil that is to be peeled off later for shaping treatment are stacked and heated and pressurized, they are laminated and integrated all at once. If a first metal foil with low roughness is used, it will be necessary to heat it to near (or above) the melting point of the liquid crystal polymer film in order to improve the interlayer adhesion between the first metal foil and the liquid crystal polymer film. . In that case, high-temperature heat is also applied to the interface between the second metal foil and the liquid crystal polymer film, which is to be peeled off later, and even if the second metal foil has been subjected to a release treatment, interlayer adhesion occurs due to the anchor effect caused by the surface irregularities. Since the properties become higher, it becomes difficult to peel off the second metal foil.

Furthermore, since the liquid crystal polymer molecules of a thermoplastic liquid crystal polymer film easily become oriented when heated and pressurized, heating and pressurizing at the above-mentioned high temperatures significantly changes the orientation, causing warping of the resulting metal-clad laminate. Since the dimensional change becomes large and the dimensional change becomes large, it becomes difficult to form a circuit board.

Further, when performing chemical roughening treatment as in Patent Document 2, fine irregularities can be imparted to the surface of the thermoplastic resin layer, but the chemical treatment increases the number of treatment steps and reduces production efficiency. Furthermore, since it is difficult to completely remove the chemical adhering to the chemically treated surface, the presence of impurities may cause problems in the resulting circuit board.

Therefore, an object of the present invention is to provide a method for manufacturing a metal-clad laminate that has small dimensional changes and is efficiently shaped.

As a result of intensive studies to achieve the above object, the inventors of the present invention have discovered that by independently performing the manufacturing of a single-sided metal-clad laminate and the shaping treatment of a single-sided metal-clad laminate, the shaping process can be improved. It has been found that dimensional changes in the metal-clad laminate can be suppressed because heating and pressurization at high temperatures can be avoided. Then, a single-sided metal-clad laminate in which a metal layer is adhered to one side of a thermoplastic liquid crystal polymer film is prepared, and the single-sided metal-clad laminate and a metal-shaped sheet are continuously bonded by thermocompression to achieve efficient imprinting. It was discovered that shape processing can be performed, leading to the completion of the present invention.

That is, the present invention may 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 side of a thermoplastic liquid crystal polymer film, and a long metal-formed sheet (B) in which at least one surface is a formed surface. ),
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 introduced into
A method for manufacturing a metal clad laminate, comprising at least the following.
[Aspect 2]
A method for manufacturing a metal clad laminate according to aspect 1, comprising:
A method for manufacturing a metal-clad laminate, further comprising a peeling step of peeling off the metal-shaped 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]
The method for producing a metal-clad laminate according to aspect 1 or 2, wherein the thermocompression bonding temperature is (Tm-150)°C or higher (Tm)°C, where the melting point (Tm) of the thermoplastic liquid crystal polymer film is taken as the melting point (Tm) of the thermoplastic liquid crystal polymer film. (preferably (Tm-130) °C or more and (Tm-5) °C or less, more preferably (Tm-110) °C or more and (Tm-10) °C or less).
[Aspect 4]
A 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-shaped sheet (B) is 0.5 N/3. A method for producing a metal clad laminate, which has a resistance of 0.2 N/mm or less (preferably 0.2 N/mm or less, more preferably 0.1 N/mm or less).
[Aspect 5]
A method for producing a metal-clad laminate according to any one of aspects 1 to 4, wherein the shaped surface of the metal shaped sheet (B) has a surface roughness (Rz) of 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]
A method for manufacturing a metal-clad laminate according to any one of aspects 1 to 5, comprising:
In the preparation process, a long release cushion material (C) is further prepared,
In the thermocompression bonding process, the release cushion material (C) is placed on at least one of the non-contact sides of the single-sided metal-clad laminate (A) and the metal-shaped sheet (B), and a pair of pressure rolls (r ₁ , _r2 ), a method for manufacturing a metal-clad laminate.
[Aspect 7]
A method for manufacturing a metal-clad laminate according to aspect 6, wherein the peel strength between the release cushion material (C) and the single-sided metal-clad laminate (A) or the metal-shaped 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 cushion material (C) includes a heat-resistant resin film, a heat-resistant composite film, a heat-resistant nonwoven fabric, and a release material on at least one surface. A method for manufacturing a metal clad laminate selected from the group consisting of metal foils comprising layers.
[Aspect 9]
A 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).
[Aspect 10]
A method for manufacturing a metal-clad laminate according to any one of aspects 6 to 9, wherein in the thermocompression bonding step, between a pair of pressure rolls (r ₁ , r ₂ ), (r ₁ )/ Layer the single-sided metal-clad laminate (A), metal-shaped sheet (B), and release cushion material (C) in the order of (C)/(A)/(B)/(r ₂ ). A method for manufacturing metal-clad laminates will be introduced.
[Aspect 11]
A method for producing a metal-clad laminate according to aspect 10, wherein in the thermocompression bonding step, the heating temperature of the pressure roll (r ₂ ) is higher than that of the pressure roll (r ₁ ). Method.
[Aspect 12]
A method for producing a metal-clad laminate according to any one of aspects 1 to 11, wherein a plurality of elongated single-sided metal-clad laminates (A) and a plurality of elongated metal-shaped sheets (B) are each produced. A method for manufacturing a metal-clad laminate, which comprises preparing and manufacturing a plurality of metal-clad laminates.
[Aspect 13]
The method for producing a metal-clad laminate according to aspect 12 , which is dependent on any one of aspects 6 to 9, wherein in the thermocompression bonding step, a plurality of sets of single-sided metal-clad laminates (A) and metal additives are A method for manufacturing a metal-clad laminate, in which a release cushion material (C) is introduced in layers between the laminates containing shaped sheets (B).
[Aspect 14]
A method for manufacturing a metal-clad laminate according to aspect 13, in which in the thermocompression bonding step, between a pair of pressure rolls (r ₁ , r ₂ ), (r ₁ )/(B)/(A) Stack the single-sided metal-clad laminate (A), metal-shaped sheet (B), and release cushion material (C) in the order of /(C)/(A)/(B)/(r ₂ ). A method for manufacturing metal-clad laminates will be introduced.
[Aspect 15]
A method for producing a metal clad laminate according to aspect 12 or aspect 13 , when dependent on 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, comprising introducing the release cushioning material (C) in a stacked manner so as to be in contact with at least one pressure roll.
[Aspect 16]
A method for producing a metal-clad laminate according to aspect 15, in which in the thermocompression bonding step, between a pair of pressure rolls (r ₁ , r ₂ ), (r ₁ )/(C)/(B) /(A)/(A)/(B)/(C)/(r ₂ ) or (r ₁ )/(C)/(A)/(B)/(B)/(A)/(C ) / (r ₂ ) A method for producing a metal-clad laminate, in which a single-sided metal-clad laminate (A), a metal-formed sheet (B), and a release cushion material (C) are introduced in layers in the following order: .

Note 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 recited in the claims is included in the invention.

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

The invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiments and drawings are merely for illustration and explanation, and should not be used to define the scope of the invention. The scope of the invention is defined by the appended claims. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic side view for explaining a method for manufacturing a metal-clad laminate according to a first embodiment of the present invention. It is a side surface schematic diagram for demonstrating the manufacturing method of the metal clad laminate according to the 2nd Embodiment of this invention. It is a side surface schematic diagram for demonstrating the manufacturing method of the metal clad laminate according to the 3rd Embodiment of this invention. It is a side surface schematic diagram for demonstrating the manufacturing method of the metal-clad laminate according to the 4th Embodiment of this invention. It is a side surface schematic diagram for demonstrating the manufacturing method of the metal clad laminate according to the 5th Embodiment of this invention. It is a side surface schematic diagram for demonstrating the manufacturing method of the metal clad laminate according to the 6th Embodiment of this invention.

The method for manufacturing a metal clad laminate of the present invention can continuously produce a metal clad laminate in which a metal shaping sheet is laminated on the thermoplastic liquid crystal polymer film surface of a single-sided metal clad laminate, or a shaped metal clad laminate.
In the present invention, the metal-clad laminate may be a metal-clad laminate having a metal layer on one side of a thermoplastic liquid crystal polymer film and a metal shaping sheet on the other side, or a metal-clad laminate having a metal layer on one side of a thermoplastic liquid crystal polymer film and the other side is shaped, and may be appropriately provided with other accessories (e.g., 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. This thermoplastic liquid crystal polymer is a polymer that can form an optically anisotropic melt phase, and is not particularly limited in its chemical composition as long as it is a liquid crystal polymer that can be melt-molded. , thermoplastic liquid crystal polyester, or thermoplastic liquid crystal polyester amide into which an amide bond is introduced.

The thermoplastic liquid crystal polymer may also be a polymer in which an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond has been 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 compounds classified into categories (1) to (4) and their derivatives as exemplified below. can be mentioned. However, in order to form a polymer capable of forming an optically anisotropic melt phase, it goes without saying that there is an appropriate range of combinations of various raw material compounds.

(1) Aromatic or aliphatic diol (see Table 1 for typical examples)

(2) Aromatic or aliphatic dicarboxylic acids (see Table 2 for representative 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)

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

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

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

In the case of the copolymer (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'- 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-naphthalene dicarboxylic acid. The molar ratio of each repeating unit of the selected at least one aromatic dicarboxylic acid (E) in the thermoplastic liquid crystal polymer is aromatic hydroxycarboxylic acid (C): the aromatic diol (D): the aromatic dicarboxylic acid ( E)=(30-80):(35-10):(35-10) or so, more preferably (C):(D):(E)=(35-75):( 32.5 to 12.5): (32.5 to 12.5), more preferably (C): (D): (E) = (40 to 70): (30 to 15): It may be about (30 to 15).

Further, the molar ratio of repeating units 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, it may be 95 mol% or more. The molar ratio of repeating units derived from 2,6-naphthalene dicarboxylic acid in the aromatic dicarboxylic acid (E) may be, for example, 85 mol% or more, preferably 90 mol% or more, more preferably 95 mol%. % or more.

Further, 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. (D1) and (D2), and in that 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.

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

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

Preferred thermoplastic liquid crystal polymers have a melting point (hereinafter referred to as Tm ₀ ) of, for example, 200 to 360°C, preferably 240 to 350°C, and more preferably a Tm ₀ of It has a temperature of 260 to 330°C. Note that the melting point can be obtained by observing the thermal behavior of a thermoplastic liquid crystal polymer sample using a differential scanning calorimeter. That is, after heating the thermoplastic liquid crystal polymer sample at a rate of 10°C/min to completely melt it, the melt was cooled at a rate of 10°C/min to 50°C, and then 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 Pa·s. ~100 Pa·s.

The thermoplastic liquid crystal polymer may include thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyether ether ketone, and fluororesin, within a range that does not impair the effects of the present invention. , various additives, fillers, etc. may be added.

The thermoplastic liquid crystal polymer film used in the manufacturing method of the present invention is obtained, for example, by extrusion molding of a melt-kneaded product of the thermoplastic liquid crystal polymer. Any method can be used as the extrusion molding method, but the well-known T-die method, inflation method, etc. 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 perpendicular thereto (hereinafter abbreviated as TD direction), and the film can be uniformly stretched in the MD direction and TD direction, so that a thermoplastic liquid crystal polymer film with controlled molecular orientation, dielectric properties, etc. in the MD direction and TD direction can be obtained.

For example, in extrusion molding using 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 simultaneously. Alternatively, the melt sheet extruded from the T-die may be stretched once in the MD direction and then stretched in the TD direction to form a film.

In addition, in extrusion molding by the inflation method, a cylindrical sheet melt-extruded from a ring die is subjected to a predetermined draw ratio (corresponding to the stretching ratio in the MD direction) and blow ratio (corresponding to the stretching ratio in the TD direction). The film may be formed by stretching.

The stretching ratio in such extrusion molding may be, for example, about 1.0 to 10, preferably about 1.2 to 7, 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.

Furthermore, if necessary, a known or customary heat treatment may be performed to adjust the melting point and/or coefficient of thermal expansion of the thermoplastic liquid crystal polymer film. The heat treatment conditions can be set as appropriate depending on the purpose, for example, (Tm ₀ -10)°C or higher (for example, (Tm _{0 -10} ) to (Tm ₀ +30)) relative to the melting point (Tm 0 ) of the thermoplastic liquid crystal polymer. The melting point (Tm) of the thermoplastic liquid crystal polymer film may be raised by heating it for several hours at a temperature of approximately (Tm ₀ ) to (Tm ₀ +20)°C) for several hours. Note that 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 thermoplastic liquid crystal polymer film sample is heated 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 manufacturing method of the present invention is one in which a metal layer is provided on one side of the thermoplastic liquid crystal polymer film. Note that a commercially available product may be used for the single-sided metal-clad laminate, but for example, a method for producing a single-sided metal-clad laminate is to adhere a metal foil as a metal layer to a thermoplastic liquid crystal polymer film by thermocompression bonding. Alternatively, the metal layer may be formed by sputtering, vapor deposition, electroless plating, or the like. From the viewpoint of production efficiency and simplicity, it is preferable to adhere the metal foil to the thermoplastic liquid crystal polymer film by thermocompression bonding.

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

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, 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 and the metal layer of the single-sided metal-clad laminate is not particularly limited, but may be, for example, 2.0 N/mm or less. Here, the peel strength is a peel strength (peel strength) measured with reference to JIS C 5016-1994 (90° direction peel).

The manufacturing method of the present invention involves preparing a single-sided metal-clad laminate (e.g., manufacturing a single-sided metal-clad laminate by thermocompression bonding of a thermoplastic liquid crystal polymer film and metal foil) and shaping the single-sided metal-clad laminate (i.e., (Thermocompression bonding with a metal shaped sheet) is performed independently. Therefore, it is possible to avoid heating and pressurizing at high temperatures during the shaping process, and as a result, it is possible to suppress dimensional changes in the metal clad laminate, and to prevent wrinkles due to differences in thermal expansion of each material. 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 alloy metals thereof. When a metal foil is bonded as a metal layer, for example, a metal foil formed of the above-mentioned metal may be used, and copper foil or stainless steel foil is preferable from the viewpoints of conductivity, ease of handling, cost, and the like. As the copper foil, one manufactured by a rolling method or an electrolytic method can be used. Further, the metal foil may be subjected to a commonly used surface treatment such as roughening treatment within a range that does not impair the high frequency characteristics of the metal clad laminate of the present invention.

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

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

The metal shaping sheet is preferably a metal foil having a shaping surface on at least one 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. When a metal foil is used, it may be, for example, a metal foil formed from the above metal, and copper foil or stainless steel foil is preferable from the viewpoint of handling and cost. As these metal foils, those manufactured by a rolling method or an electrolytic method can be used, and surface treatment such as roughening treatment may be performed to obtain the desired shaping surface.

In addition, from the viewpoint of suppressing warping due to thermal expansion during thermocompression bonding, the metal forming the metal shaped sheet should be made of a material having a coefficient of thermal expansion comparable to that of the metal forming the metal layer of the single-sided metal-clad laminate (e.g. , the same type of metal). In particular, it is preferable that both the metal layer and the metal shaped sheet are copper foils.

From the viewpoint of improving the interlayer adhesion with the bonding sheet in circuit processing, the shaping surface of the metal shaping sheet may have a surface roughness (Rz) of, for example, 1.0 to 7.0 μm. In the manufacturing method of the present invention, the surface roughness (Rz) of the shaping surface of the metal shaping sheet is transferred to form unevenness with the same surface roughness (Rz) as that of the metal shaping sheet on the surface of the thermoplastic liquid crystal polymer film. 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) refers to the ten-point average roughness measured with a contact surface roughness meter with reference to JIS B 0601-1994, and represents the sum of the average of the peak heights from the highest peak to the fifth highest peak in the roughness curve of the reference length and the average of the valley depths from the deepest valley bottom to the fifth deepest valley bottom in the deepest valley bottom.

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 shaping surface of the metal shaping sheet to provide a mold release layer may be used. Examples of the mold release agent include silicone resins and fluorine resins.

The thickness of the metal shaped sheet can be appropriately set as required, and may be, for example, approximately 5 to 50 μm, more preferably 9 to 35 μm.

(Release cushioning material)
In the manufacturing method of the present invention, a release cushioning material may be used as necessary. A long-sized material may be used as the release cushioning material. The long-sized material may be in a roll shape wound around a roll, or in a non-roll shape not wound around a roll. The length of the long-sized material is not particularly limited as long as it can be continuously transported, but 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 thermocompression bonding, has heat resistance, and has cushioning properties, and non-thermoplastic polyimide films, aramid films, Teflon ( Heat-resistant resin films such as (registered trademark) films; heat-resistant composite films (e.g., composite films made of multiple heat-resistant resin films, composite films made of metal foil and heat-resistant resin films); heat-resistant fibers (e.g., heat-resistant A heat-resistant nonwoven fabric composed of resin fibers, metal fibers); and metal foils having a release layer (e.g., a layer coated with a release agent such as silicone resin or fluorine resin) on at least one surface. Examples include aluminum foil, stainless steel foil, etc.). These release cushion materials may be used alone or in combination of two or more. Note that the release cushion material (e.g., heat-resistant resin film, heat-resistant composite film, or heat-resistant nonwoven fabric) is subjected to a release treatment in order to facilitate peeling from the adherend after thermocompression bonding. You can leave it there. Examples of the mold release treatment method include the methods described above.
Among these release cushioning materials, heat-resistant resin films, heat-resistant composite films, and heat-resistant nonwoven fabrics are preferred from the viewpoint of excellent heat resistance and cushioning properties (repulsion resilience).

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

The surface roughness (Rz) of at least one side 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-shaped sheet) after thermocompression bonding. It may be below, preferably 1.8 μm or less, 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 0.05 μm or more. It may be 15 μm or more.

(Method for manufacturing metal clad laminate)
The method for manufacturing a metal clad laminate of the present invention includes:
A long single-sided metal-clad laminate (A) in which a metal layer is adhered to one side of a thermoplastic liquid crystal polymer film, and a long metal-formed sheet (B) in which at least one surface is a formed surface. ),
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 introduced into
have at least the following.

The single-sided metal-clad laminate (A) and the metal-shaped sheet (B) are not particularly limited as long as they can be introduced into the pressure roll as long objects; for example, long objects manufactured upstream of the thermocompression bonding process may be used. It may be used by being conveyed as it is, or it may be prepared by preparing an unwinding roll.
When using a long product produced upstream as is, for example, a single-sided metal-clad laminate (A) is produced by continuously thermocompressing a thermoplastic liquid crystal polymer film and a metal foil, and then winding it up. Alternatively, it may be overlapped with a separately prepared metal shaped sheet (B) downstream in the conveyance direction. In this case, the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the shaped surface of the metal shaped sheet (B) are arranged and overlapped so as to be in contact with each other.
When preparing an unwinding roll, each unwinding roll has a single-sided metal-clad laminate (A) and a metal-shaped sheet (B) adjacent to each other, and a thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate (A). It is arranged in such a direction that the surface and the shaped surface of the metal shaped sheet (B) are in contact with each other.

The method for manufacturing a metal clad laminate of the present invention includes:
In the preparation process, a long release cushion material (C) is further prepared,
In the thermocompression bonding process, the release cushion material (C) is placed on at least one of the non-contact sides of the single-sided metal-clad laminate (A) and the metal-shaped sheet (B), and a pair of pressure rolls (r ₁ , r ₂ ).

By using the release cushion material (C), since the release cushion material (C) plays the role of a cushion, pressure is not applied during thermocompression bonding between the single-sided metal-clad laminate (A) and the metal-shaped sheet (B). The pressure from the rolls can be dispersed, and the transferability of the shaped surface of the metal shaped sheet (B) to the surface of the thermoplastic liquid crystal polymer film can be improved. For example, when the heating temperature with the pressure rolls (r ₁ , r ₂ ) is high, when the pressure is low, or when the pressure time is short, the presence of the release cushion material (C) makes it possible to maintain uniform pressure. It is highly effective in improving sex.

When using the release cushion material (C), the release cushion material (C) is attached to the single-sided metal-clad laminate (A) on the non-contact surfaces of the single-sided metal-clad laminate (A) and the metal-shaped sheet (B). ) and/or may be arranged adjacent to the metal shaped 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 also be thermocompression bonded. By placing the release cushion material (C) adjacent to the metal layer side of the single-sided metal-clad laminate (A), the release cushion material (C) suppresses heat transfer from the single-sided metal-clad laminate (A) side. Since the thermoplastic liquid crystal polymer film plays the role of a heat insulating material, it can prevent the thermoplastic liquid crystal polymer film from being heated more than necessary from the metal layer side, and can suppress the liquid crystal polymer molecules from becoming easily aligned.

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

The method for manufacturing the metal clad laminate of the present invention may involve preparing a plurality of long single-sided metal clad laminates (A) and a plurality of long metal shaped sheets (B) to produce a plurality of metal clad laminates.

When manufacturing multiple metal clad laminates, a release cushion material (C) is placed between the laminates including multiple sets of single-sided metal clad laminates (A) and metal shaped sheets (B) in the thermocompression bonding process. They may be introduced multiple times.

In addition, when a plurality of metal clad laminates are manufactured, in the thermocompression bonding step, the release cushion material (C) may be introduced in a layered manner so as to be in contact with at least one of the pair of pressure rolls (r ₁ , r ₂ ).

Here, the multiple single-sided metal clad laminates (A) may be the same or different. Also, the multiple metal shaped sheets (B) may be the same or different.

Furthermore, the resulting multiple 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 side of a thermoplastic liquid crystal polymer film and a metal-formed sheet on the other side) is made of a thermoplastic liquid crystal polymer film and a metal-formed sheet. 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.
In addition, the obtained metal-clad laminate may have a peel strength (P2) between the thermoplastic liquid crystal polymer film and the metal layer of, for example, 0.6 N/mm or more, preferably 0.8 N/mm. It may be at least 1.0 N/mm, more preferably at least 1.0 N/mm. 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.
In addition, in the obtained metal-clad laminate, the peel strength (P1) between the thermoplastic liquid crystal polymer film and the metal excipient sheet is determined by the 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.

In addition, the obtained metal-clad laminate has an orientation degree f(f1) on the metal layer side in the thickness direction of the thermoplastic liquid crystal polymer film and an orientation degree f(f1) on the metal shaping sheet side (or shaping treatment side). The value divided by f2) (f1/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 process of the single-sided metal-clad laminate (A) and the metal-shaped sheet (B), heating and pressing at an unnecessarily high temperature (e.g., higher than the melting point of the thermoplastic liquid crystal polymer film) is avoided. By being able to do this, the degree of orientation in the thickness direction of the thermoplastic liquid crystal polymer film can be set in a specific relationship, probably because it is possible to suppress changes in the molecular orientation on the metal shaped sheet side. Here, the degree of orientation on the metal layer side in the thickness direction of the thermoplastic liquid crystal polymer film refers to the degree of orientation on the side that is in contact with the metal layer when the thermoplastic liquid crystal polymer film is divided into two equal parts in the thickness direction. Yes, the degree of orientation on the metal-formed sheet side (forming-treated side) in the thickness direction of a thermoplastic liquid crystal polymer film is the degree of orientation of the metal-formed sheet when the thermoplastic liquid crystal polymer film is divided into two equal parts in the thickness direction. This refers to the degree of orientation of the part that is in contact (the side that has been subjected to shaping treatment).

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

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

Here, in the first embodiment, the single-sided metal-clad laminate (A) and the metal-shaped sheet (B) are moved between a pair of pressure rolls (r ₁ , r ₂ ) at a rate of (r ₁ )/(A )/(B)/(r ₂ ). Each unwinding roll is arranged in the following order.

Specifically, 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 placed on the upstream side of the pair of pressure rolls (r ₁ , r 2 ). The single-sided metal-clad laminate unwinding roll 11 and the metal-shaped sheet unwinding roll 12 are arranged so that they are in contact with each other.

As shown in FIG. 1, after each unwinding roll is arranged with respect to a pair of pressure rolls (r ₁ , r ₂ ), from each unwinding roll, as shown in the arrow direction, a single-sided metal clad laminate is (A) and the metal shaped sheet (B) are unwound and introduced into a pair of pressure rolls (r ₁ , r ₂ ) in the MD direction (or lamination direction) shown by the arrow. The metal clad laminate (D) ((A)/(B)) is formed by thermocompression bonding using pressure rolls (r ₁ , r ₂ ).

In a pair of pressure rolls (r ₁ , r ₂ ), a single-sided metal-clad laminate (A) and a metal-shaped sheet (B) are introduced overlappingly in this order, and pressure is applied at a predetermined heating temperature. In the manufacturing method of the present invention, the prepared single-sided metal-clad laminate (A) is directly used for manufacturing. It is possible to avoid heating and pressurizing the film at temperatures higher than the melting point of the thermoplastic liquid crystal polymer film. As a result, it is possible to suppress dimensional changes in the metal-clad laminate, and also to suppress the occurrence of wrinkles due to differences in thermal expansion of each material. The peelability between the surface and the shaped surface of the metal shaped sheet (B) can be improved.

As the pressure roll, a known heating and pressing device can be used, for example, a metal roll, a rubber roll, a resin-coated metal roll, etc. The pair of pressure rolls (r ₁ , r ₂ ) may be the same or different. 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 ) may be a metal roll like the pressure roll (r ₁ ), or may be a rubber roll or a resin-coated metal roll.

Moreover, only one of the pair of pressure rolls (r ₁ , r ₂ ) may be heated, or both may be heated. When both are heated, the heating temperatures of the pressure rolls (r ₁ , r ₂ ) may be the same or different. For example, it is preferable that the pressure roll disposed on the metal-shaped sheet (B) side has a higher temperature, and in the case of the first embodiment shown in FIG. The heating temperature of the pressure roll (r ₂ ) disposed at may be higher than that of the pressure roll (r ₁ ). In that case, for example, because the heating temperature of the pressure roll (r ₂ ) in contact with the metal-shaped sheet (B) is higher, the thermoplasticity of the single-sided metal-clad laminate (A) from the metal-shaped sheet (B) Heat can be transferred to the liquid crystal polymer film side (the side to be subjected to shaping treatment), making it possible to perform shaping treatment efficiently and suppressing dimensional changes in metal-clad laminates. . If the heating temperature of the pressure roll (r ₂ ) is higher than that of the pressure roll (r ₁ ), for example, the temperature difference between the heating temperature of the pressure roll (r ₂ ) and the heating temperature of the pressure roll (r ₁ ) may be 20 to 200°C, preferably 25 to 150°C, more preferably 30 to 100°C.

Although there are no particular restrictions on the thermocompression bonding temperature or the pressure conditions of the pressure roll, from the viewpoint of improving the transferability of the unevenness on the shaped surface of the metal shaped sheet (B), for example, a thermoplastic liquid crystal polymer film may be used. With respect to the melting point (Tm), 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), or more. Preferably, the temperature may be (Tm-110)°C or higher (for example, (Tm-90)°C or higher). In addition, from the viewpoint of improving the releasability of the metal shaped sheet (B) and suppressing dimensional changes and wrinkles, the temperature may be less than (Tm)°C, preferably less than (Tm-5)°C, or more. Preferably, the temperature may be (Tm-10)°C or lower. Note that the thermocompression bonding temperature may be the heating temperature of the pressure rolls (r ₁ , r ₂ ), and when the heating temperatures of the pair of pressure rolls (r ₁ , r ₂ ) are different from each other, the pressure The higher heating temperature among the heating temperatures of the rolls (r ₁ , r ₂ ) may be the thermocompression bonding temperature.
Further, the pressurizing pressure may be in a 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. Note that the pressurizing pressure is a value obtained by dividing the force (pressing load) applied to the pressurizing rolls by the maximum width of the material passing between the pressurizing rolls.

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

In the manufacturing method of the present invention, after the thermocompression bonding step, a peeling step of peeling the metal shaped sheet (B) from the thermoplastic liquid crystal polymer film surface of the single-sided metal clad laminate (A) may be further provided. In the peeling step, for example, after passing through a pair of pressure rolls (r ₁ , r ₂ ), the pair of pressure rolls (r ₁ , r ₂ ) may be used as peeling rolls to immediately peel the metal shaped sheet (B) from the single-sided metal clad laminate (A), or at least one peeling roll disposed separately from the pressure roll may be used to peel the metal shaped sheet (B) from the single-sided metal clad laminate (A).

For example, in the first embodiment shown in FIG. A metal-clad laminate (E) is produced by peeling between (A) and (B), and the metal-clad laminate (E) is wound up on a metal-clad laminate winding roll 31. The metal-clad laminate (E) obtained by peeling off the metal shaped sheet (B) has the metal layer/thermoplastic liquid crystal polymer film laminated in this order, and the metal layer of the thermoplastic liquid crystal polymer film is not bonded. The unevenness of the shaped surface of the metal shaped sheet (B) is transferred to the side surface. That is, the surface roughness (Rz) of the thermoplastic liquid crystal polymer film of the metal clad laminate (E) on the side to which the metal layer is not bonded may be 1.0 to 7.0 μm, preferably 1.5 5.5 μm, more preferably 2.0 to 4.5 μm.

In the manufacturing method of the present invention, the peel strength between the single-sided metal-clad laminate (A) and the metal-shaped 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 shaped sheet (B) is preferably 0.5 N/mm or less, more preferably 0.2 N/mm or less. , more preferably 0.1 N/mm or less. 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 process, heating and pressing at a lower temperature is performed to form the single-sided metal-clad laminate (A) and the metal-formed sheet (B) while maintaining the interlayer adhesion in a low state. can be applied.

The peeled metal shaped sheet (B) is wound up by a metal shaped sheet winding roll 32. In the manufacturing method of the present invention, the peeled metal shaped sheet (B) may be reused as necessary.

Moreover, FIG. 2 is a schematic side view for explaining the manufacturing method of the metal-clad laminate according to the second embodiment. Components having the same role as those in FIG. 1 are given the same reference numerals and their explanations will be omitted. As shown in FIG. 2, in the second embodiment, a single-sided metal-clad laminate unwinding roll for unwinding the single-sided metal-clad laminate (A) is placed on the upstream side of a pair of pressure rolls (r ₁ , r ₂ ). 11. Prepare a metal shaped sheet unwinding roll 12 for unwinding the metal shaped sheet (B) and a release cushion material unwinding roll 13 for unwinding the release cushion material (C).

Here, in the second embodiment, the single-sided metal-clad laminate (A), the metal-formed sheet (B), and the release cushion material (C) are placed between a pair of pressure rolls (r ₁ , r ₂ ). , (r ₁ )/(C)/(A)/(B)/(r ₂ ).

Specifically, 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 placed on the upstream side of the pair of pressure rolls (r ₁ , r 2 ). The single-sided metal-clad laminate unwinding roll 11 and the metal-shaped sheet unwinding roll 12 are arranged so that the metal layer surface of the single-sided metal-clad laminate (A) and the release cushion material (C) are in contact with each other. A release cushion material unwinding roll 13 is arranged so as to be in contact with it.

As shown in FIG. 2, after each unwinding roll is arranged with respect to a pair of pressure rolls (r ₁ , r ₂ ), from each unwinding roll, as shown in the arrow direction, a single-sided metal clad laminate is (A), _the metal shaped sheet (B), and the release cushion material (C) are unwound, and the MD direction indicated by the arrow (or _lamination direction) and thermocompression bonded by a pair of pressure rolls (r ₁ , r ₂ ) to form a metal clad laminate (F) ((C)/(A)/(B)).

As shown in FIG. 2, in the second embodiment, since the release cushion material (C) is used, the pressure from the pair of pressure rolls (r ₁ , r ₂ ) can be dispersed due to its cushioning properties. This makes it possible to improve the transferability of the uneven shape of the shaped surface of the metal shaped sheet (B) to the thermoplastic liquid crystal polymer film. Furthermore, since the release cushion material (C) is stacked on the metal layer side of the single-sided metal-clad laminate (A), the release cushion material (C) plays a role of insulating heat from the pressure roll (r ₁ ). Also, it is possible to suppress excessive heat transfer to the surface of the thermoplastic liquid crystal polymer film on the metal layer side, and it is possible to suppress dimensional changes. In particular, when the heating temperature with the pressure rolls (r ₁ , r ₂ ) is high, when the pressure is low, or when the pressure time is short, the pressure tends to be uneven, so the release cushion material The use of (C) is highly effective in improving pressure uniformity.

In the manufacturing method of the present invention, at least one peeling roll is used to produce a metal-clad laminate (a metal-clad laminate comprising a single-sided metal-clad laminate (A) and a metal-shaped sheet (B)) obtained by a thermocompression bonding process; or a metal-clad laminate in which the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) has been subjected to shaping treatment, and the metal-clad laminate is mold-released from a metal-clad laminate provided with a release cushion material (C). The cushioning material (C) may be peeled off. For example, after passing through a pair of pressure rolls (r ₁ , _{r 2 )} , _the release cushion material (C ) may be peeled off, or the release cushion material (C) may be peeled off from the metal-clad laminate using at least one peeling roll provided separately from the pressure roll.

In the manufacturing method of the present invention, the order of peeling off the metal shaped sheet (B) and peeling off the release cushion material (C) can be appropriately set depending on the aspect 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 above-mentioned thermocompression bonding process is peeled between (C)/(A) by passing through the first peel rolls 21, 21 to produce the metal clad laminate (D). The metal clad laminate (D) obtained by peeling off the release cushion material (C) is laminated in the order of the metal layer of the single-sided metal clad laminate (A)/the thermoplastic liquid crystal polymer film of the single-sided metal clad laminate (A)/the metal shaped sheet (B).

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 shaped sheet (B) may be set appropriately, as long as the peeling process can be performed.

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

The peeled release cushion material (C) is wound up by a release cushion material winding roll 33. In the manufacturing method of the present invention, the peeled release cushion material (C) can be reused as necessary.

The metal clad laminate (D) from which the release cushion material (C) has been peeled off is passed through the second peeling rolls 22, 22, whereby it is peeled off between (A)/(B) to produce the metal clad laminate (E), which is then wound up onto the metal clad laminate take-up roll 31.

Also, Fig. 3 is a side schematic view for explaining a manufacturing method of a metal clad laminate according to a third embodiment. As shown in Fig. 3, in the third embodiment, the single-sided metal clad laminate (A), the metal shaped sheet (B) and the release cushion material (C) are arranged between a pair of pressure rolls ( _r1 , _r2 ) in the order of ( _r1 )/(C)/(A)/(B)/(C)/( _r2 ), and the respective unwinding rolls are arranged. Here, the members having the same roles as those in Fig. 2 are given the same reference numerals and the description thereof is omitted.

In the third embodiment shown in FIG. 3, metal sheets are stacked in the order of (C)/(A)/(B)/(C) between a pair of pressure rolls (r ₁ , r ₂ ). In the laminate (F), the release cushion material (C) is peeled off between (C)/(A) and between (B)/(C) to produce a metal-clad laminate (D), and then, The metal shaped sheet (B) is peeled off from the metal clad laminate (D) to produce a metal clad laminate (E).

Further, in the third embodiment shown in FIG. 3, the heating temperatures of the pair of pressure rolls (r ₁ , r ₂ ) may be the same or different. Similarly to the embodiment, the heating temperature of the pressure roll (r ₂ ) on the metal shaped sheet (B) side may be higher than that of the pressure roll (r ₁ ). Since the heating temperature of the pressure roll (r ₂ ) in contact with the metal-shaped sheet (B) and the adjacent release cushion material (C) is higher, the single-sided metal-clad laminate ( Heat can be efficiently transferred to the thermoplastic liquid crystal polymer film side (the side to be subjected to shaping treatment) in A).

Moreover, FIG. 4 is a schematic side view for explaining the manufacturing method of the metal-clad laminate according to the fourth embodiment. As shown in FIG. 4, in the fourth embodiment, a single-sided metal-clad laminate (A), a metal-formed sheet (B), and a release cushion material (C) are connected to 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, members having the same role as those in FIG. 2 are given the same reference numerals, and explanations thereof will be omitted.

In the fourth embodiment shown in FIG. 4, a pair of pressure rolls (r ₁ , r ₂ ) are stacked so that (B)/(A)/(C)/(A)/(B) is formed. The mold release cushioning material (C) is peeled off from the metal-clad laminate (F) to produce two metal-clad laminates (D), and then the metal-shaped sheet (D) is separated 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, resulting in good production efficiency. The two metal clad laminates (D) may be the same or different. Similarly, the two metal clad laminates (E) may be the same or different.

In the fourth embodiment shown in FIG. 4, since the release cushion material (C) is overlapped with the single-sided metal-clad laminate (A) on both sides, it is possible that the release layer is provided on both sides. preferable.

Furthermore, in the fourth embodiment shown in FIG. 4, when obtaining the same metal-clad laminate, a pair of pressure rolls (r ₁ , r ₂ ) may be the same, and the heating temperatures may be the same.

Furthermore, FIG. 5 is a schematic side view for explaining the method for manufacturing a metal-clad laminate according to the fifth embodiment. As shown in FIG. 5, in the fifth embodiment, a single-sided metal-clad laminate (A), a metal-shaped sheet (B), and a release cushion material (C) are connected to a pair of pressure rolls (r ₁ , r ₂ ), each unwinding roll is in the order of (r ₁ )/(C)/(B)/(A)/(A)/(B)/(C)/(r ₂ ). Placed. Here, members having the same role as those in FIG. 2 are given the same reference numerals, and explanations thereof will be omitted.

In the fifth embodiment shown in FIG. 5, a metal clad laminate (F) is stacked between a pair of pressure rolls ( _r1 , _r2 ) in the order (C)/(B)/(A)/(A)/(B)/(C), and the release cushion material (C) is peeled off to produce two metal clad laminates (D), and then the metal shaped sheet (B) is peeled off from the metal clad laminate (D) to produce two metal clad laminates (E).

In the fifth embodiment shown in FIG. 5, multiple metal clad laminates can be manufactured, resulting in good production efficiency. The two metal clad laminates (D) may be the same as each other or different from each other. Similarly, the two metal clad laminates (E) may be the same as each other or different from each other.

Furthermore, FIG. 6 is a schematic side view for explaining the method for manufacturing a metal-clad laminate according to the sixth embodiment. As shown in FIG. 6, in the sixth embodiment, a single-sided metal-clad laminate (A), a metal-shaped sheet (B), and a release cushion material (C) are connected to a pair of pressure rolls (r ₁ , r ₂ ), each unwinding roll is in the order of (r ₁ )/(C)/(A)/(B)/(B)/(A)/(C)/(r ₂ ). Placed. Here, members having the same role as those in FIG. 2 are given the same reference numerals, and explanations thereof will be omitted.

In the sixth embodiment shown in FIG. 6, between a pair of pressure rolls (r ₁ , r ₂ ), (C)/(A)/(B)/(B)/(A)/(C) The release cushioning material (C) is peeled off from the metal-clad laminates (F) stacked so that two metal-clad laminates (D) are produced. The shaped 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, resulting in good production efficiency. The two metal clad laminates (D) may be the same or different. Similarly, the two metal clad laminates (E) may be the same or different.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, in the following Examples and Comparative Examples, peelability and warpage were evaluated by the following methods.

[Peel strength]
In Examples 1 and 2, a metal clad laminate was obtained separately after thermocompression bonding and before the polyimide film (C) and the metal shaped sheet (B) were peeled off. A 3 mm wide peel test piece was prepared from the metal clad laminate. In accordance with JIS C 6471, the peel strength (N/mm) was measured at the interface between the single-sided metal clad laminate (E) and the metal shaped sheet (B) and at the interface between the single-sided metal clad laminate (E) and the polyimide film (C) at a speed of 50 mm/min using the 90° method.

[Evaluation of peelability]
The single-sided metal clad laminate and the metal shaped sheet were continuously peeled off, and those that did not observe wrinkles, deformation, poor peeling, or material destruction over a length of 20 m or more were rated as A, and those that did observe wrinkles, deformation, poor peeling, or material destruction were rated as B.

[Warp measurement]
Take a sample with a width of 250 mm and a length of 250 mm from the single-sided metal-clad laminate, place the sample on a horizontal table, and measure the height of the part that is most floating from the table among the four corners of the sample using a scale. , this was defined as warpage. Those with warpage of less than 5 mm were evaluated as A, and those with warp of 5 mm or more were evaluated as B.

(Manufacturing example 1)
Copper foil (manufactured by Fukuda Metal Foil & Powder Industries Co., Ltd., "CF-H9A-DS-HD2") was coated 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, the surface temperature of the metal roll was set to 260 ° C., the pressure was set to 8 t/m, and the sheets were passed through at a speed of 3.0 m/min to bond by thermocompression. A single-sided metal-clad laminate (A) having a configuration of thermoplastic liquid crystal polymer film/copper foil was produced.

(Example 1)
The single-sided metal-clad laminate (A) obtained in Production Example 1 and the metal-formed sheet (B) were made of electrolytic copper foil (“JX-EFL-V2” manufactured by JX Nippon Mining & Metals Co., Ltd., thickness 12 μm, surface roughness of the formed surface). (Rz) 2.0 μm) and a polyimide film (Apical NPI manufactured by Kaneka Corporation, thickness 75 μm) as a release cushion material (C) were prepared as unwinding rolls, and a pair of pressure rolls (r ₁ , r ₂ ) in the order of r ₁ /C/A/B/r ₂ . Metal rolls each having a diameter of 300 mm were used as a pair of pressure rolls (r ₁ , r ₂ ), the surface temperature of the metal rolls was set to 200°C, the pressure was set to 8 t/m, and the speed was 3.0 m/min. It was passed through a pair of pressure rolls (r ₁ , r ₂ ) for thermocompression bonding.

After thermocompression bonding, as shown in FIG. 2, after passing through a pair of pressure rolls (r ₁ , r ₂ ), the polyimide film (C) is separated using a pair of peeling rolls (21), and then a pair of The single-sided metal-clad laminate (E) and the metal-shaped sheet (B) are separated by a peeling roll (22), and the single-sided metal-clad laminate (E) and the metal-shaped sheet (B) are separated from each other by a peeling roll (22). A metal-clad laminate (E) was obtained. Table 7 shows the peelability of the metal-shaped sheet (B) and the warpage 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-shaped sheet (B) was 0.05 N/mm or less. Moreover, the peel strength between the single-sided metal-clad laminate (E) and the polyimide film (C) could not be measured because there was no adhesion at all.

(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 240°C. Table 7 shows the peelability of the metal-shaped sheet (B) and the warpage 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-shaped sheet (B) was 0.08 N/mm or less. Moreover, the peel strength between the single-sided metal-clad laminate (E) and the polyimide film (C) could not be measured because there was no adhesion at all.

(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) were used. In the same manner as in Example 1, except that "CF-H9A-DS-HD2" manufactured by Powder Industry Co., Ltd. (thickness 12 μm) was used, a pair of processed materials were used together with the metal shaped sheet (B) and the release cushion material (C). When introduced between pressure rolls (r ₁ , r ₂ ) in the order of r ₁ /C/M/L/B/r ₂ to produce a single-sided metal-clad laminate (E), the thermoplastic liquid crystal polymer The peel strength between the film (L) and the copper foil (M) is low, and when the metal excipient sheet (B) is peeled off, there is partial peeling between the thermoplastic liquid crystal polymer film (L) and the copper foil (M). is thought to occur.

(Comparative example 2)
When a single-sided metal-clad laminate (E) was produced in the same manner as Comparative Example 1 except that the surface temperature of the metal roll was 320°C, the peel strength between the thermoplastic liquid crystal polymer film (L) and the copper foil (M) was sufficient. However, the peel strength between the thermoplastic liquid crystal polymer film (L) and the metal shaped sheet (B) also increases, so it is difficult to separate the thermoplastic liquid crystal polymer film (L) and the metal shaped sheet (B). During this process, it is thought that any one of wrinkles, deformation, poor peeling, and material destruction of the film will occur continuously, and it is also thought that warpage tends to increase.

As shown in Table 7, in Examples 1 and 2, since the single-sided metal-clad laminate (A) was manufactured in advance, the metal roll surface temperature could be set to a relatively low temperature, and as a result, the single-sided metal-clad laminate (A) There was no strong adhesion between the body and the metal shaped sheet, and there was no change in the molecular orientation of the thermoplastic liquid crystal polymer film, giving good results in terms of both releasability and warpage.

According to the production method of the present invention, it is possible to efficiently produce a shaped metal clad laminate, and since the obtained metal clad laminate has the unevenness transferred thereto, the interlayer adhesion with the bonding sheet It has excellent properties and good circuit workability. Therefore, the obtained metal-clad laminate can be effectively used as parts used in the electric/electronic field, office equipment/precision equipment field, power semiconductor field, etc., such as circuit boards (particularly millimeter wave radar boards). Can be done.

As mentioned above, the preferred embodiments of the present invention have been described with reference to the drawings, but those skilled in the art will easily assume various changes and modifications within the obvious scope after viewing the present specification. Probably. It is therefore contemplated that such changes and modifications are within the scope of the invention as defined by the claims.

11... Single-sided metal clad laminate unwinding roll 12... Metal shaped sheet unwinding roll 13... Release cushion material unwinding rolls 21, 22... Peeling roll 31... Metal clad laminate Take-up roll 32...Metal shaped sheet take-up roll 33...Release cushion material take-up rolls _r1 , _r2 ...Pressure roll A...Single-sided metal-clad laminate B...Metal Shaped sheet C...Release cushion material D, E, F...Metal clad laminate

Claims (16)

A long single-sided metal-clad laminate (A) in which a metal layer is adhered to one side of a thermoplastic liquid crystal polymer film, and a long metal-formed sheet (B) in which at least one surface is a formed surface. ),
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 introduced into
A method for manufacturing a metal clad laminate, comprising at least the following. A method for manufacturing a metal clad laminate according to claim 1, comprising:
A method for manufacturing a metal-clad laminate, further comprising a peeling step of peeling off the metal-shaped 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, wherein the thermocompression bonding temperature is (Tm-150)° C. or higher (Tm) when the melting point (Tm) of the thermoplastic liquid crystal polymer film is taken as the melting point (Tm) of the thermoplastic liquid crystal polymer film. A method for producing a metal clad laminate, the temperature being less than ℃. The method for producing 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-shaped sheet (B) is 0.5N. /mm or less, a method for manufacturing a metal clad laminate. 5. The method for producing a metal-clad laminate according to any one of claims 1 to 4, wherein the shaped surface of the metal shaped sheet (B) has a surface roughness (Rz) of 1.0 to 7. A method for manufacturing a metal-clad laminate having a thickness of 0 μm. A method for producing the metal clad laminate according to any one of claims 1 to 5,
In the preparation step, a long release cushion material (C) is further prepared,
In a thermocompression bonding step, the release cushion material (C) is placed on at least one of the non-contacting sides of the single-sided metal clad laminate (A) and the metal shaped sheet (B), and the single-sided metal clad laminate (A) and the metal shaped sheet ( _B ) are introduced into a pair of pressure rolls ( _r1 , r2). The method for producing 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 shaped sheet (B) is 0.1 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) comprises a heat-resistant resin film, a heat-resistant composite film, a heat-resistant nonwoven fabric, and a release cushion material on at least one surface. A method for manufacturing a metal clad laminate selected from the group consisting of metal foils provided with a mold layer. The method for producing a metal-clad laminate according to any one of claims 6 to 8, wherein the release cushion material (C) has a surface roughness (Rz) of at least one surface of 2.0 μm or less. A method for manufacturing metal-clad laminates. The method for manufacturing a metal-clad laminate according to any one of claims 6 to 9, wherein in the thermocompression bonding step, (r ₁ ) is formed between a pair of pressure rolls (r ₁ , r ₂ ). Layer the single-sided metal-clad laminate (A), metal-shaped sheet (B), and release cushion material (C) in the order of /(C)/(A)/(B)/(r ₂ ). A method for manufacturing metal-clad laminates will be introduced. The method for producing a metal clad laminate according to claim 10, wherein in the thermocompression bonding step, the pressure roll ( _r2 ) has a higher heating temperature than the pressure roll ( _r1 ). A method for producing a metal-clad laminate according to any one of claims 1 to 11, wherein the elongated single-sided metal-clad laminate (A) and the elongated metal-shaped sheet (B) are each A method for manufacturing a metal-clad laminate, which comprises preparing a plurality of metal-clad laminates and manufacturing a plurality of metal-clad laminates. The method for producing a metal-clad laminate according to claim 12 when dependent on any one of claims 6 to 9, wherein in the thermocompression bonding step, a plurality of sets of single-sided metal-clad laminates (A) and A method for producing a metal-clad laminate, in which a release cushioning material (C) is introduced in layers between the laminates containing metal-shaped sheets (B). The method for producing a metal clad laminate according to claim 13, wherein in the thermocompression bonding step, a single-sided metal clad laminate ( _A ), a metal shaped sheet (B) and a release cushion material (C) are stacked and introduced between _a pair of pressure rolls ( _r1 , _r2 ) in the order of (r1)/(B)/(A)/(C)/(A)/(B)/(r2). The method for producing a metal clad laminate according to claim 12 or 13 when dependent on any one of claims 6 to 9, wherein in the thermocompression bonding step, a pair of pressure rolls (r _{1 .} A method for producing a metal clad laminate as described in claim 15, wherein in the thermocompression bonding process, a single-sided metal clad laminate ( _A ), a metal shaped sheet (B) and a release cushion material (C) are introduced in _a stacked manner between a pair of pressure rolls ( _r1 , _r2 ) in the order of ( _r1 )/(C)/(B)/(A)/(A)/(B)/(C)/( _r2 ), or (r1)/(C)/(A)/(B)/(B)/(A)/(C)/(r2).

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