JP7182747B2 - METHOD FOR MANUFACTURING METAL-CLAD LAMINATED BODY - Google Patents

Description

Related application

This application claims priority from Japanese Patent Application No. 2020-053323 filed on March 24, 2020 in Japan, the entirety of which is incorporated herein by reference.

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

Thermoplastic liquid crystal polymer films are known as materials with excellent heat resistance, low hygroscopicity, high-frequency characteristics, etc., and have been attracting attention in recent years as electronic circuit materials for high-speed transmission. When used for electronic circuit boards, a laminate of a thermoplastic liquid crystal polymer film and a metal foil typified by copper foil is used. Techniques include a method in which a thermoplastic liquid crystal polymer film cut to a predetermined size and a metal foil are placed on top of each other between upper and lower hot plates using a hot press device, and heat-pressed in a vacuum state. However, since this system is a batch system, there is a problem of poor production efficiency.

On the other hand, a roll-to-roll method in which a thermoplastic liquid crystal polymer film and a metal foil are laminated and continuously thermocompressed is advantageous in terms of production efficiency. In particular, in manufacturing by the roll-to-roll method, as a method for manufacturing a metal-clad laminate with good industrial productivity, Patent Document 1 (Patent No. 5661051) discloses a roll-to-roll method in which both front and back surfaces are (r ₁ )/( _B )/(A)/ ₍ The insulating film (A), the metal foil (B), and the spacing film (C) are superimposed and thermocompressed in the order of C)/(A)/(B)/(r ₂ ) to form the spacing film. A method for manufacturing a single-sided metal-clad laminate is disclosed in which two single-sided metal-clad laminates are obtained by peeling from (C).

Japanese Patent No. 5661051

Patent Document 1 is characterized in that two metal-clad laminates are arranged vertically symmetrically around the spacing film so as to abut against the spacing film, and are thermocompression bonded by a roll-to-roll method. , comes into direct contact with the insulating film as it is introduced into the pressure roll.

However, when a thermoplastic liquid crystal polymer film is used as the insulating film, since the thermoplastic liquid crystal polymer film is a thermoplastic resin, the thermoplastic liquid crystal polymer film is softened by heat immediately before it is introduced between the pressure rolls. As a result, partial contact with the separation film having a different coefficient of thermal expansion and elastic modulus causes appearance defects such as wrinkles in that portion.

In addition, as described in Patent Document 1, when the separation film is not used, the appearance defect occurs due to heat fusion between the liquid crystal polymer films. There was a problem that they adhered when introduced into the pressure roll.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for efficiently manufacturing a metal-clad laminate while suppressing appearance defects such as wrinkles.

The inventors of the present invention have made intensive studies to achieve the above object, and as a result, in producing a plurality of metal-clad laminates, a laminate material in which thermoplastic liquid crystal polymer films are arranged in contact with each other is used. Even in the case of continuous thermocompression bonding, if a thermoplastic liquid crystal polymer film having a crystal orientation degree fp in the plane direction smaller than a crystal orientation degree fv in the thickness direction is used as at least one of the thermoplastic liquid crystal polymer films, the thermal Surprisingly, even if the thermoplastic liquid crystal polymer films are in contact with each other without using a separation film during pressure bonding, the adhesiveness between the thermoplastic liquid crystal polymer films can be suppressed and the films can be easily separated. Furthermore, the obtained metal-clad laminate can be prevented from having poor appearance such as wrinkles, and the present invention has been completed.

That is, the present invention can be configured in the following aspects.
[Aspect 1]
A method for manufacturing a plurality of metal-clad laminates,
A step of continuously thermocompressing a laminate material, wherein the laminate material comprises at least a pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other, and the pair of thermoplastic liquid crystal polymer films (F, F ) and at least a pair of metal foils (M, M) respectively arranged in contact with the outer surface of the
a thermocompression bonding step of thermocompression bonding the laminate material with the at least one pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other in the laminate material;
a thermoplastic liquid crystal polymer film separation step of separating the at least one pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other after the thermocompression bonding step;
with at least
At least one of the pair of separated thermoplastic liquid crystal polymer films (F, F) is a thermoplastic liquid crystal polymer film in which the crystal orientation degree fp in the planar direction is smaller than the crystal orientation degree fv in the thickness direction. A method for producing a tension laminate.
[Aspect 2]
The method for producing a metal-clad laminate according to aspect 1, wherein the degree of crystal orientation fp in the planar direction of the thermoplastic liquid crystal polymer film is 0.4 to 0.7 (preferably 0.5 to 0.6). A method for manufacturing a metal-clad laminate, which is within the scope.
[Aspect 3]
In the method for producing a metal-clad laminate according to aspect 1 or 2, the degree of crystal orientation fv in the thickness direction of the thermoplastic liquid crystal polymer film is 0.7 to 0.9 (preferably 0.7 to 0.9). 8) A method for producing a metal-clad laminate, which falls within the range of 8).
[Aspect 4]
A method for manufacturing a metal-clad laminate according to any one of aspects 1 to 3, wherein the thermocompression bonding step is continuous isostatic pressing or hot roll pressing using a pair of pressure rolls (r ₁ , r ₂ ). A method for manufacturing a metal-clad laminate, performed in.
[Aspect 5]
A method for producing a metal-clad laminate according to any one of aspects 1 to 4,
In the thermocompression bonding step, the laminate material is thermocompressed with at least a pair of metal foils (M, M) in contact with each other in the laminate material,
A metal foil separation step of separating the at least one pair of metal foils (M, M) in contact with each other after the thermocompression bonding step,
A method for producing a metal-clad laminate.
[Aspect 6]
A method for producing a metal-clad laminate according to any one of aspects 1 to 5, wherein the laminate material has outermost metal foils (M ₁ , M ₂ ).
[Aspect 7]
A method for producing a metal-clad laminate according to aspect 6,
A method for producing a metal-clad laminate, wherein the laminate material is arranged in any one of the following order of (i) to (vi).
(i) _M1 /F/F/ _M2
(ii) _M1 /F/F/M/M/F/ _M2
(iii) _M1 /F/M/M/F/F/M/M/F/ _M2
(iv) _M1 /F/F/M/M/F/F/ _M2
(v) _M1 /F/F/M/M/F/F/M/M/F/ _M2
(vi) _M1 /F/M/M/F/F/M/M/F/F/M/M/F/ _M2
(Here, M ₁ , M ₂ : outermost layer metal foil, F: thermoplastic liquid crystal polymer film, M: metal foil)
[Aspect 8]
The manufacturing method according to any one of aspects 1 to 7, wherein the laminate material is thermocompression bonded via a pair of protective materials (C ₁ , C ₂ ) during thermocompression bonding. A method for manufacturing a laminate.
[Aspect 9]
The production method according to aspect 8, wherein the protective material (C ₁ ) and/or the protective material (C ₂ ) is selected from the group consisting of heat-resistant resin films, heat-resistant composite films, and heat-resistant nonwoven fabrics. material (preferably, the protective material (C ₁ ) and the protective material (C ₂ ) are each a protective material selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant nonwoven fabric), A method for producing a metal-clad laminate.
[Aspect 10]
The production method according to any one of aspects 1 to 9, wherein the thermocompression bonding temperature is the melting point (Tm _L ) to (Tm _L −120)° C. to (Tm _L )° C. (preferably (Tm _L −100)° C. to (Tm _L )° C.).
[Aspect 11]
The production method according to any one of aspects 1 to 10, wherein the peel strength between the thermoplastic liquid crystal polymer film (F) and the thermoplastic liquid crystal polymer film (F) after thermocompression bonding is 0.3 kN/m or less. (preferably 0.2 kN/m or less, more preferably 0.1 kN/m or less).
[Aspect 12]
The production method according to any one of aspects 1 to 11, wherein the difference in melting points of the thermoplastic liquid crystal polymer films in contact with each other in the laminate material is 0 to 70°C (preferably 0 to 60°C, more preferably is in the range of 0 to 50° C.), a method for producing a metal-clad laminate.

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 claimed claims is included in the invention.

According to the present invention, by using a thermoplastic liquid crystal polymer film having a specific degree of crystal orientation, the thermoplastic liquid crystal polymer films can be easily separated from each other even after thermocompression bonding, so the occurrence of poor appearance is suppressed. The metal-clad laminate can be produced efficiently.

The present 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 for illustration and description only and should not be used to define the scope of the invention. The scope of the invention is defined by the appended claims. In the accompanying drawings, the same reference numbers in different drawings indicate the same parts. The drawings are not necessarily drawn to scale and are exaggerated to illustrate the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS It is a side view schematic diagram for demonstrating the manufacturing method of the metal clad laminated body by the 1st Embodiment of this invention. It is a side view for explaining the manufacturing method of the metal-clad laminate according to the second embodiment of the present invention. It is a schematic side view for explaining a method for manufacturing a metal-clad laminate according to a third embodiment of the present invention. It is a schematic side view for explaining a method for manufacturing a metal-clad laminate according to a fourth embodiment of the present invention.

In the method for producing a metal-clad laminate of the present invention, it is possible to continuously produce a plurality of sets of metal-clad laminates in which a metal foil is 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 manufacturing method of the present invention is formed from a melt moldable liquid crystal polymer. The thermoplastic liquid crystal polymer is a polymer capable of forming an optically anisotropic melt phase, and is not particularly limited in terms of its chemical constitution as long as it is a liquid crystalline polymer that can be melt-molded. , a thermoplastic liquid crystal polyester, or a thermoplastic liquid crystal polyester amide into which an amide bond is introduced.

Further, the thermoplastic liquid crystal polymer may be a polymer obtained by introducing an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond or an isocyanurate bond into an aromatic polyester or an aromatic polyester amide.

Specific examples of the thermoplastic liquid crystalline polymer used in the present invention include known thermoplastic liquid crystalline polyesters and thermoplastic liquid crystalline polyester amides derived from compounds classified into the following examples (1) to (4) and derivatives thereof. can be mentioned. However, it goes without saying that there is an appropriate range of combinations of various raw material compounds in order to form a polymer capable of forming an optically anisotropic molten phase.

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

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

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

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

Copolymers having repeating units shown in Tables 5 and 6 are typical examples of thermoplastic liquid crystal polymers obtained from these raw material compounds.

Among these copolymers, preferred are polymers containing at least p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid as repeating units, particularly (i) p-hydroxybenzoic acid and 6-hydroxy- A copolymer containing repeating units 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 repeating units of aromatic diols and/or aromatic hydroxylamines and at least one aromatic dicarboxylic acid is preferred.

For example, in the copolymer (i), when the thermoplastic liquid crystal polymer contains at least repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the repeating unit (A) of p-hydroxybenzoic acid The molar ratio (A)/(B) between the acid and 6-hydroxy-2-naphthoic acid in the repeating unit (B) is (A)/(B) = 10/90 to 90/ in the thermoplastic liquid crystal polymer. It is desirable to be about 10, more preferably (A) / (B) = about 15/85 to 85/15, more preferably (A) / (B) = 20/80 to 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'- from the group consisting of at least one aromatic diol (D) selected from the group consisting of dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, and terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; The molar ratio of each repeating unit in the thermoplastic liquid crystal polymer of at least one selected aromatic dicarboxylic acid (E) is: the aromatic hydroxycarboxylic acid (C): the aromatic diol (D): the aromatic dicarboxylic acid (E) = (30 to 80): (35 to 10): (35 to 10), more preferably (C): (D): (E) = (35 to 75): (32.5 to 12.5): It may be about (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-naphthalenedicarboxylic 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.

In addition, 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) may be used, in which case the molar ratio of the two aromatic diols may be (D1)/(D2)=23/77 to 77/23, more preferably may be 25/75 to 75/25, more preferably 30/70 to 70/30.

Further, the molar ratio of the repeating unit derived from the aromatic diol (D) and the repeating unit derived from the aromatic dicarboxylic acid (E) is (D)/(E) = 95/100 to 100/95. is preferred. Outside this range, the degree of polymerization tends to be low and the mechanical strength tends to be low.

The ability to form an optically anisotropic molten phase as referred to in the present invention can be identified by, for example, placing a sample on a hot stage, heating the sample at an elevated temperature in a nitrogen atmosphere, and observing light transmitted through the sample. .

Preferred thermoplastic liquid crystal polymers have a melting point (hereinafter referred to as Tm ₀ ) in the range of, for example, 200 to 360° C., preferably 240 to 350° C., more preferably Tm ₀ 260 to 330°C. The melting point can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer sample using a differential scanning calorimeter. That is, after heating a thermoplastic liquid crystal polymer sample from room temperature (for example, 25° C.) at a rate of 10° C./min to completely melt it, the melt was cooled to 50° C. at a rate of 10° C./min, The position of the endothermic peak that appears after the temperature is again raised at a rate of 10° C./min 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, for example, 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 It may have 50 to 100 Pa·s.

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

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

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

Further, in extrusion molding by the inflation method, a predetermined draw ratio (corresponding to the draw ratio in the MD direction) and blow ratio (corresponding to the draw ratio in the TD direction) are applied to the cylindrical sheet melt-extruded from the ring die. The crystal orientation degree f, which will be described later, can be controlled by stretching and forming the film.

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

The specific relationship between the draw ratio and the blow ratio cannot be shown because the thermophysical properties of the thermoplastic liquid crystal polymer, the desired thickness of the thermoplastic liquid crystal polymer film, and other manufacturing conditions affect the above draw ratio and blow ratio. Within the range of the ratio, the crystal orientation degree fp in the plane direction and the crystal orientation degree fv in the thickness direction can be controlled to have a specific relationship by adjusting the blow ratio to be larger than the draw ratio.

In addition, if necessary, a known or conventional heat treatment may be performed to adjust the melting point and/or thermal expansion coefficient of the thermoplastic liquid crystal polymer film. The heat treatment conditions can be appropriately set according to the purpose. For example, the melting point ₍ Tm ₀ ) of the thermoplastic liquid crystal polymer is (Tm _{0 -10} ) ° C. C., preferably from ( _Tm.sub.0 ) to ( _Tm.sub.0 +20).degree. C.) for several hours to raise the melting point (Tm) of the thermoplastic liquid crystal polymer film.

The melting point (Tm) of the thermoplastic liquid crystal polymer film may be, for example, 270-380°C, preferably in the range of 280-370°C. 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 melting point (Tm) of the thermoplastic liquid crystal polymer film can be determined by the position of the endothermic peak that appears when the temperature of the thermoplastic liquid crystal polymer film sample is increased from room temperature (e.g., 25°C) at a rate of 10°C/min. can.

The thickness of the thermoplastic liquid crystal polymer film can be appropriately set according to the application. For example, considering that it is used as a material for the insulating layer of a multilayer circuit board, it may be 10 to 500 μm, preferably 15 to 500 μm. It may be 250 μm, more preferably 25-180 μm.

(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 alloy metals thereof. Copper foil and stainless steel foil are preferable from the viewpoint of cost and the like. In addition, as a copper foil, what is manufactured by a rolling method or an electrolysis method can be used.

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

(Protective layer)
A protective material may be used in the manufacturing method of the present invention, if necessary. The protective material is not particularly limited as long as it can be easily peeled off from the adjacent metal foil after thermocompression bonding and has heat resistance. heat-resistant resin film; heat-resistant composite film (e.g., composite film composed of multiple heat-resistant resin films, composite film composed of metal foil and heat-resistant resin film); metal foil such as aluminum foil and stainless steel foil; and heat-resistant fiber (for example, heat-resistant resin fibers, metal fibers), heat-resistant nonwoven fabrics, and the like. These protective materials may be used alone or in combination of two or more.
Among these protective materials, heat-resistant resin films, heat-resistant composite films, and heat-resistant nonwoven fabrics are preferable from the viewpoint of excellent heat resistance and impact resilience.

The thickness of the protective material can be appropriately set as required, and may be, for example, about 10 to 300 μm, preferably 15 to 150 μm, more preferably 15 to 130 μm. In addition, the protective material may be subjected to release treatment on one side or both sides for the purpose of improving releasability from the metal foil after thermocompression bonding. Examples of the method of the release treatment include a method of providing a heat-resistant release resin film such as silicone resin or fluororesin on at least one surface of the protective material.

(Method for manufacturing metal-clad laminate)
The method for producing a metal-clad laminate of the present invention comprises:
A step of continuously thermocompressing a laminate material, wherein the laminate material comprises at least a pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other, and the pair of thermoplastic liquid crystal polymer films (F, F ) and at least a pair of metal foils (M, M) respectively disposed in contact with the outer surface of the laminate material, and at least a pair of thermoplastic liquid crystal polymer films (F, F) are in contact with each other in the laminate material a thermocompression step of thermocompression bonding the laminate material in a state of
a thermoplastic liquid crystal polymer film separation step for separating at least a pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other after the thermocompression bonding step;
at least.

The thermoplastic liquid crystal polymer film and the metal foil are not particularly limited as long as they form a laminate material and can be continuously thermocompressed. For example, an unwinding roll of each material constituting the laminate material is prepared. However, the unwind rolls may be arranged so as to form the laminate material of the desired configuration. In addition, the method for producing a metal-clad laminate of the present invention is performed by a roll-to-roll method in which each material unwound from an unwinding roll is superimposed, passed through at least a thermocompression bonding step and a separation step, and wound up with a winding roll. may In the present invention, the term "laminate material" refers to a material that is laminated in a predetermined arrangement to produce a plurality of desired metal-clad laminates.

Here, the thermoplastic liquid crystal polymer film (F) as a constituent material for forming one metal-clad laminate in the laminate material may be singular or plural. Also, the number of metal foils (M) may be singular or plural. In addition, when two or more are included, each may be the same or different.

Furthermore, each constituent material of the laminate material may be a single piece of the thermoplastic liquid crystal polymer film (F) or a single piece of the metal foil (M), or may be a single piece of the thermoplastic liquid crystal polymer film (F). It may be a single-sided metal-clad laminate (M/F) in which a metal foil (M) is arranged. Therefore, when using a plurality of unwinding rolls for unwinding constituent materials for forming a plurality of metal-clad laminates composed of a thermoplastic liquid crystal polymer film (F) and a metal foil (M), (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) a single-sided metal-clad laminate (M/F) An unwind roll may be included for unwinding the. Each of these constituent materials may be the same or different. A single-sided metal-clad laminate (M/F) as a constituent material of the laminate material can be used as a material for manufacturing a double-sided metal-clad laminate (M/F/M).

The laminate material comprises at least a pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other, and at least a pair of metal foils disposed in contact with the outer surfaces of the pair of thermoplastic liquid crystal polymer films (F, F). (M, M) may be used as long as the arrangement is composed of at least It may be arranged to include an arrangement in the order M/F/F/M.

In the method for producing a metal-clad laminate of the present invention, at least one of the pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other in the laminate material has a crystal orientation degree fp in the plane direction in the thickness direction. It is a thermoplastic liquid crystal polymer film having a degree of orientation smaller than fv. In the present invention, by using a thermoplastic liquid crystal polymer film having a specific degree of crystal orientation for at least one of the pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other, crystals are oriented in the thickness direction. It was found that the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other can be suppressed from adhering to each other after thermocompression bonding, and can be easily separated, probably because the cage layer structure is developed.
Both of the pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other in the laminate material are thermoplastic liquid crystal polymer films in which the crystal orientation degree fp in the plane direction is smaller than the crystal orientation degree fv in the thickness direction. Preferably.

Here, the degree of crystal orientation f is an index that gives the degree of orientation of the crystal region of the polymer, and the closer the degree of crystal orientation fp in the plane direction is to 0.5, the more the orientation of crystals in the biaxial directions of the plane of the film. It means that the crystal orientation in the thickness direction is close to isotropic, and the larger the crystal orientation degree fv in the thickness direction (for example, the closer it is to 1.0), the higher the crystal orientation in the film thickness direction. The degree of crystal orientation f was measured using a rotating anticathode X-ray diffractometer Ru-200 manufactured by Rigaku Denki Co., Ltd., and the X-ray output was measured using a voltage of 40 kV, a current of 100 mA, and a target CuKα (λ = 1.5405 A) as follows. can be measured to A change in crystal orientation can be determined from a wide-angle X-ray photograph. First, a thermoplastic liquid crystal polymer film is cut out in the MD direction and attached to a sample holder. A line is incident and a diffraction pattern is exposed on the imaging plate. Then, for the obtained diffraction image, each of the thickness direction and the plane direction (MD direction) is converted into an orientation distribution curve, and the degree of crystal orientation is calculated from the half width H of the peak of the diffraction intensity curve with respect to the circumferential direction β angle. f (degree of crystal orientation fp in the planar direction and degree of crystal orientation fv in the thickness direction) can be calculated from the following equation (1).
f=(180−H)/180 (1)
In the formula, H is the half width.
In addition, the half width H is the peak of the intensity distribution obtained by annular integration of the diffraction angle 2θ = 15° to 30° (for example, around 20° ((110) plane)) by wide-angle X-ray diffraction measurement. It may be half width.

In the thermoplastic liquid crystal polymer film used in the production method of the present invention, at least one thermoplastic liquid crystal polymer film (F) of the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other in the laminate material is The crystal orientation degree fp in the planar direction may be 0.4 to 0.7, preferably 0.5 to 0.6. By setting it to such a range, when separating the pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other after thermocompression bonding, anisotropic delamination is less likely to occur in the MD direction and the TD direction. , and the appearance defects such as wrinkles can be suppressed. For example, if the degree of crystal orientation fp in the planar direction is too large, delamination tends to occur only in the MD direction, which may cause the surface shape of the delaminated surface to become rough, resulting in poor appearance.

Further, the crystal orientation degree fv in the thickness direction may be 0.7 to 0.9, preferably 0.7 to 0.8. By setting it to such a range, when separating the pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other after thermocompression, delamination tends to occur easily, and appearance defects such as wrinkles tend to occur. The occurrence can be suppressed. For example, if the crystal orientation degree fv in the thickness direction is too small, the pair of thermoplastic liquid crystal polymer films (F, F) tends to be easily adhered after thermocompression bonding, and wrinkles and the like are caused by being difficult to separate. Defective appearance may occur.

For example, in the thermoplastic liquid crystal polymer film, the difference (fv-fp) between the crystal orientation degree fp in the plane direction and the crystal orientation degree fv in the thickness direction may be 0.05 or more, preferably 0.1. It may be 0.2 or more, more preferably 0.2 or more. The upper limit of the difference (fv-fp) between the degree of crystal orientation fp in the plane direction and the degree of crystal orientation fv in the thickness direction is not particularly limited, but may be, for example, 0.5 or less.

A pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other in the laminate material may be the same or different. It may be in the range of 0 to 60°C, more preferably in the range of 0 to 50°C.

When the plurality of thermoplastic liquid crystal polymer films in the laminate material have different melting points, the melting point of the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other is the same as that of the other thermoplastic liquid crystal polymer in the laminate material. It may exceed the lowest melting point (Tm _L ) that the film has. In the present invention, the lowest melting point (Tm _L ) means the lowest melting point among the melting points (Tm) of all the thermoplastic liquid crystal polymer films contained in the laminate material.

Also, in the laminate material, at least a pair of inner layer metal foils (M, M) may be in contact with each other. Since the portions where the metal foils are in contact with each other can be easily separated after the thermocompression bonding process, when manufacturing a plurality of metal-clad laminates (for example, three or more metal-clad laminates), the laminate material It is preferable that the pair of inner layer metal foils (M, M) have portions in contact with each other. One of the pair of inner layer metal foils (M, M) is a pair of metal foils (M, M) disposed in contact with the outer surfaces of the pair of thermoplastic liquid crystal polymer films (F, F). ).

As long as the effects of the present invention are not impaired, the arrangement of each constituent material of the laminate material may include materials other than those forming the metal-clad laminate. For example, a pair of inner layer metal foils (M, M) A protective material (C) may be arranged between and may be arranged in the order of M/C/M.

The laminate material may have outermost metal foils (M ₁ , M ₂ ). Since the outermost layer metal foil (M ₁ ) and the outermost layer metal foil (M ₂ ) form the outermost layers of the laminated body material, the outermost layer metal foil (M 1 ) and the outermost layer metal foil (M 2 ) do not adhere to pressure rolls or the like in the thermocompression bonding process and cause poor appearance. Moreover, even when the laminate material is thermocompression bonded via a pair of protective materials (C ₁ , C ₂ ) described later, the protective materials can be prevented from coming into contact with the thermoplastic liquid crystal polymer film. It is possible to suppress the occurrence of poor appearance such as

The laminate material may be arranged in any order of (i) to (vi) below.
(i) _M1 /F/F/ _M2
(ii) _M1 /F/F/M/M/F/ _M2
(iii) _M1 /F/M/M/F/F/M/M/F/ _M2
(iv) _M1 /F/F/M/M/F/F/ _M2
(v) _M1 /F/F/M/M/F/F/M/M/F/ _M2
(vi) _M1 /F/M/M/F/F/M/M/F/F/M/M/F/ _M2

In the method for producing the metal-clad laminate of the present invention, the protective material (C) may be superimposed and thermocompression bonded at the time of thermocompression bonding, if necessary. The protective material (C) is not limited to a mode of use as long as it does not impair the effects of the present invention, and may be arranged outside the laminate material, or may be arranged as a constituent material of the laminate material. good. For example, during thermocompression bonding, the laminate material may be thermocompression bonded via a pair of protective materials (C ₁ , C ₂ ). In the thermocompression bonding process, by arranging the protective material in the outermost layer so as to sandwich the laminate material, it is possible to suppress excessive heat conduction to the inner layer of the laminate material. Even if the films (F, F) are in contact with each other, mutual adhesiveness can be reduced. As described above, the protective material (C) may be a protective material selected from the group consisting of heat-resistant resin films, heat-resistant composite films, and heat-resistant nonwoven fabrics. Moreover, from the viewpoint of suppressing appearance defects such as wrinkles, the laminate material may be arranged such that the thermoplastic liquid crystal polymer film (F) and the protective material (C) are not adjacent to each other.

In addition, in the method for manufacturing a metal-clad laminate of the present invention, when the laminate material is thermocompressed via a pair of protective materials (C ₁ , C ₂ ), the moisture content of the protective materials is reduced to produce a metal-clad laminate. From the viewpoint of suppressing the occurrence of problems caused by moisture in the step, a protective material heating process for heating the pair of protective materials (C ₁ , C ₂ ) may be further provided prior to the thermocompression bonding process.

The protective material heating step is not particularly limited as long as the pair of protective materials (C ₁ , C ₂ ) can be heated, and the pair of protective materials (C ₁ , C ₂ ) may be heated by external heating means such as a heater. Then, the pair of protective materials (C ₁ , C ₂ ) may be heated by heating rolls. Further, for example, when the thermocompression bonding process is performed by a continuous isostatic press, the pair of protective members (C ₁ , C ₂ ) are brought into contact with the preheating drum by circumscribing the pair of protective members (C ₁ , C ₂ ). may be heated, or when the thermocompression bonding process is performed by a hot roll press using a pair of pressure rolls (r ₁ , r ₂ ), a pair of protective materials (C ₁ , C ₂ ) are placed on the pressure rolls ( A pair of protective members (C ₁ , C ₂ ) may be heated by circumscribing them (r ₁ , r ₂ ).

When the pair of protective materials (C ₁ , C ₂ ) are brought into contact with the pressure rolls (r ₁ , r ₂ ), the time during which the protective materials and the pressure rolls are in contact depends on the type of protective material and the state of the protective material. , It can be appropriately set according to various conditions such as the heating temperature of the pressure roll, but from the viewpoint of removing moisture from the protective material, for example, it is preferably 1.0 seconds or more, for example, 1.0 to 200 seconds, or 3.0 to 125 seconds.

The protective material heating process may be determined based on the thermocompression bonding temperature. For example, when the thermocompression bonding temperature is T ° C., the temperature of the protective material heating process may be, for example, T-30 to T + 30 ° C. It may be from T-15°C to T+15°C.

In the protective material heating step, the heating time can be appropriately set depending on the heating means. It is preferable to heat in the range of

In the method for manufacturing a metal-clad laminate of the present invention, the thermocompression bonding step may be performed by continuous isostatic pressing or hot roll pressing using a pair of pressure rolls (r ₁ , r ₂ ). In the case of continuous isostatic pressing, for example, a double belt press may be used from above and below via a pair of endless belts. In the continuous isostatic pressing, the heating or cooling may be divided into a single region or a plurality of regions during continuous pressing.

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

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, _the thermocompression bonding step is performed by hot roll pressing using a pair of pressure rolls (r ₁ , r ₂ ). ₂ ), on the upstream side of ), metal foil unwinding rolls 11, 11 for unwinding a pair of outermost layer metal foils (M ₁ , M ₂ ), and a thermoplastic liquid crystal polymer film for unwinding a pair of thermoplastic liquid crystal polymer films (F, F). Liquid crystal polymer film unwinding rolls 12, 12 are prepared.

Here, in the first embodiment, a pair of outermost metal foils (M ₁ , M ₂ ) and a pair of thermoplastic liquid crystal polymer films (F, F) are combined into a pair of pressure rolls (r ₁ , r ₂ ). The unwind rolls are arranged in the order of r ₁ /M ₁ /F/F/M ₂ /r ₂ between them.

Specifically, on the upstream side of the pair of pressure rolls (r ₁ , r ₂ ), the metal foil unwinding rolls 11, 11 for unwinding the pair of outermost layer metal foils (M ₁ , M ₂ ) are respectively the outermost layers. , and thermoplastic liquid crystal polymer film unwinding rolls 12, 12 for unwinding a pair of thermoplastic liquid crystal polymer films (F, F) are disposed inside thereof.

As shown in FIG. 1, after each unwinding roll is arranged with respect to a pair of pressure rolls (r ₁ , r ₂ ), a pair of thermoplastic liquid crystals is discharged from each unwinding roll in the direction of the arrow. A polymer film (F, F) and a pair of outermost layer metal foils (M ₁ , M ₂ ) are unwound and applied to a pair of pressure rolls (r ₁ , r ₂ ) in the MD direction ( or lamination direction).

Laminate materials M ₁ /F/F/M ₂ are introduced in this order to a pair of pressure rolls (r ₁ , r ₂ ), and pressure is applied to the laminate materials at a predetermined heating temperature. Add In the production method of the present invention, the degree of crystal orientation fp in the planar direction of at least one of the pair of thermoplastic liquid crystal polymer films (F, F) is greater than the degree of crystal orientation fv in the thickness direction of the thermoplastic liquid crystal polymer film (F). is small, it becomes easy to separate the pair of thermoplastic liquid crystal polymer films (F, F) after the thermocompression bonding even if they are in contact with each other. Therefore, it is possible to suppress the occurrence of appearance defects and eliminate the need to use a protective material or a spacing material, so that the production cost can be reduced and the metal-clad laminate can be efficiently manufactured.

A known heating and pressurizing device can be used as the pressure roll, and examples thereof include metal rolls, rubber rolls, resin-coated metal rolls, and the like. 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 enhancing heating efficiency, and the pressure roll (r ₂ ) may be a metal roll like the pressure roll (r ₁ ). It may be a rubber roll or a resin-coated metal roll.

Also, the heating temperatures of the pair of pressure rolls (r ₁ , r ₂ ) may be the same or different. For example, when the aspect of the laminate material and the constituent materials are asymmetric, the heating temperature of one pressure roll is set higher than the heating temperature of the other pressure roll in consideration of the melting point of the thermoplastic liquid crystal polymer film. may have been When the pressure roll (r ₂ ) has a higher heating temperature than 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 5 to 80°C, preferably 10 to 70°C, more preferably 20 to 50°C.

In addition, although there are no particular restrictions on the thermocompression bonding temperature and the pressure conditions of the pressure roll, from the viewpoint of improving the adhesion between the thermoplastic liquid crystal polymer film and the metal foil and suppressing the occurrence of wrinkles, for example, heat With respect to the melting point (Tm) of the plastic liquid crystal polymer film, the thermocompression bonding temperature may range from (Tm-120)°C to (Tm)°C, preferably from (Tm-100)°C to (Tm)°C. may be When the thermoplastic liquid crystal polymer films in the laminate material have different melting points, the thermocompression bonding temperature is the melting point of the thermoplastic liquid crystal polymer film having the lowest melting point (Tm _L ), it may be in the range of (Tm _L -120)°C to (Tm _L )°C, preferably (Tm _L -100)°C to (Tm _L )°C. The thermocompression bonding temperature may be _{the heating temperature of the pressure rolls (r 1 , r 2 )} . The higher heating temperature of the heating temperatures of the pressure rolls (r ₁ , r ₂ ) may be the thermocompression bonding temperature.

The applied pressure may range from 1.0 t/m (9.8 kN/m) to 15 t/m (147 kN/m), preferably from 1.5 t/m (14.7 kN/m) to 12 t/m. It may be in the range of m (117.6 kN/m). The pressing pressure is a value obtained by dividing the force (pressing load) applied to the pressing roll by the work width.

In addition, the speed at which the laminate material is passed through the pair of pressure rolls (r ₁ , r ₂ ) can be appropriately set according to the thermocompression bonding temperature, the pressure conditions of the pressure rolls, and the size of the pressure rolls. may be, for example, 0.5 to 5.0 m/min, preferably 1.0 to 4.0 m/min.

The production method of the present invention includes a thermoplastic liquid crystal polymer film separation step for separating at least a pair of thermoplastic liquid crystal polymer films (F, F) after the thermocompression bonding step. ₁ , r ₂ ), the thermoplastic liquid crystal polymer films (F, F) may be separated immediately, and at least one separation roll arranged separately from the pressure roll may be used to separate the pair of heat A separation may be provided between the plastic liquid crystal polymer films (F, F).

In the production method of the present invention, at least one thermoplastic liquid crystal polymer film (F) of the pair of thermoplastic liquid crystal polymer films (F, F) has a crystal orientation degree fp in the plane direction higher than a crystal orientation degree fv in the thickness direction. is small, it is possible to prevent the thermoplastic liquid crystal polymer films from adhering to each other by thermocompression bonding, and the thermoplastic liquid crystal polymer films can be easily separated from each other. For example, the peel strength between the thermoplastic liquid crystal polymer film (F) and the thermoplastic liquid crystal polymer film (F) in the laminate after thermocompression may be 0.3 kN/m or less, preferably 0.2 kN/m. It may be 0.1 kN/m or less, more preferably 0.1 kN/m or less. In the present invention, the peel strength is the peel strength (peeling strength) measured according to JIS C 6471:1995 (90° direction peeling).

The manufacturing method of the present invention may include a cooling step of cooling the laminate after the thermocompression bonding step. For example, a cooling roll may be provided downstream of the pressure roll, if desired. When a separation roll is provided, the cooling roll is preferably provided between the pressure roll and the separation roll. The cooling roll may be composed of a pair of rolls, or may be composed of a single roll.

For example, in the first embodiment shown in FIG. 1, the laminate M ₁ /F/F/M ₂ obtained by the thermocompression bonding process is immediately subjected to F after passing through a pair of pressure rolls (r ₁ , r ₂ ). /F to produce two single-sided metal clad laminates (M ₁ F, M ₂ F). The obtained single-sided metal-clad laminates are taken up by metal-clad laminate take-up rolls 31, 31, respectively. In addition, one or a plurality of guide rolls or the like may be disposed between the pressure roll and the winding rolls to be used for guidance, adjustment of tension, widening, and the like.

FIG. 2 is a schematic side view for explaining the method for manufacturing a metal-clad laminate according to the second embodiment. Members having the same roles as those in FIG. As shown in FIG. 2, in the second embodiment, a pair of outermost metal foils (M ₁ , M ₂ ) are wound on the upstream side of a pair of pressure rolls (r ₁ , r ₂ ). Unwinding rolls 11, 11, thermoplastic liquid crystal polymer film unwinding rolls 12, 12 for unwinding a pair of thermoplastic liquid crystal polymer films (F, F), and protective material for unwinding a pair of protective materials (C ₁ , C ₂ ) Unwind rolls 13, 13 are prepared.

Here, in the second embodiment, a pair of thermoplastic liquid crystal polymer films (F, F), a pair of outermost metal foils (M ₁ , M ₂ ), and a pair of protective materials (C ₁ , C ₂ ) are _, between a pair of pressure _{rolls ( r 1} , r ₂ ), a pair _of pressure rolls ₍ Each unwind roll is arranged upstream of r ₁ , r ₂ ).

Specifically, on the upstream side of the pair of pressure rolls (r ₁ , r ₂ ), the protective material unwinding rolls 13, 13 for unwinding the pair of protective materials (C ₁ , C ₂ ) are the outermost layers, respectively. , inside which are arranged metal foil unwinding rolls 11, 11 for unwinding a pair of outermost layer metal foils (M ₁ , M ₂ ), and further inside thereof, a pair of thermoplastic liquid crystal polymer films (F , F) are arranged.

Laminate material M ₁ /F/F/M ₂ is applied to a pair of pressure rolls (r ₁ , r ₂ ) via a pair of protective materials (C ₁ , C ₂ ), that is, C ₁ /M ₁ /F/F/M ₂ /C ₂ are superimposed in this order. At least one thermoplastic liquid crystal polymer film of the pair of thermoplastic liquid crystal polymer films (F, F) has a specific degree of crystal orientation, and protective materials are provided so as to sandwich the laminate material. Adhesion between the thermoplastic liquid crystal polymer films can be suppressed by arranging it in the outermost layer.

In addition to the thermoplastic liquid crystal polymer film separation step described above, the production method of the present invention may include a protective material separation step for separating at least one protective material and the outermost layer metal foil which are in contact with each other. In this case, the protective material separation step and the thermoplastic liquid crystal polymer film separation step may be performed stepwise such that one of the separation steps is performed first, and then the other separation step is performed. The step of separating the thermoplastic liquid crystal polymer film may be performed at the same time. When these separation steps are carried out in stages, it is preferable to carry out the protective material separation step prior to the thermoplastic liquid crystal polymer film separation step. That is, the separation between the protective material and the outermost layer metal foil, and then the separation between the pair of thermoplastic liquid crystal polymer films may be performed stepwise.

In the manufacturing method of the present invention, when the protective material is arranged in the outermost layer, the protective material can be separated very easily. As a result, wrinkles that tend to occur when separation is difficult can be suppressed, and a high-quality metal-clad laminate can be produced with good productivity.

These separation steps can be carried _out by _known or customary methods. It can be done by at least one separating roll arranged separately from the rolls. The at least one separation roll may be a pair of separation rolls, a plurality of separation rolls arranged singly, or a combination thereof. Also, the order of the separation rolls may be set as appropriate, and any of them may be on the upstream side.

Further, in the manufacturing method of the present invention, the metal-clad laminate obtained after the thermocompression bonding step may be wound together with the protective material in a state in which the metal-clad laminate and the protective material are overlapped without performing the protective material separation step. .

For example, in the second embodiment shown in FIG. 2, the laminate C ₁ /M ₁ /F/F/M ₂ /C ₂ obtained by the thermocompression bonding process is applied to a pair of pressure rolls (r ₁ , r ₂ ), separation takes place simultaneously between C ₁ /M ₁ , M ₂ /C ₂ and F/F. A pair of protective materials (C ₁ , C ₂ ) separated between C ₁ /M ₁ and M ₂ /C ₂ are wound up by protective material winding rolls 32, 32, respectively. The separated pair of protective materials (C ₁ , C ₂ ) can be reused as needed. In addition, two single-sided metal-clad laminates (M ₁ F, M ₂ F) are manufactured by being separated between the F/Fs at the same time, and the obtained single-sided metal-clad laminates are provided with guide rolls 21, 21, it is taken up by metal-clad laminate take-up rolls 31,31.

3A and 3B are schematic side views for explaining the method for manufacturing a metal-clad laminate according to the third embodiment. Members having the same roles as those in FIGS. 1 and 2 are given the same reference numerals, and descriptions thereof are omitted. As shown in FIG. 3, in the third embodiment, a thermoplastic liquid crystal polymer film (F), a pair of outermost metal foils (M ₁ , M ₂ ), a metal foil (M), and a pair of protective materials (C ₁ , C ₂ ) are r ₁ /C ₁ /M ₁ /F/F/M/M/F/M ₂ /C ₂ /r ₂ between a pair of pressure rolls (r ₁ , r ₂ ) Each unwinding roll is arranged upstream of a pair of pressure rolls (r ₁ , r ₂ ) in order.

Laminate material M ₁ /F/F/M/M/F/M ₂ is applied to a pair of pressure rolls (r ₁ , r ₂ ) via a pair of protective materials (C ₁ , C ₂ ), i.e. , _C1 / _M1 /F/F/M/M/M/F/ _M2 / _C2 .

Here, before the pair of protective materials (C ₁ , C ₂ ) unwound from the protective material unwinding rolls 13, 13 are brought into contact with the laminate material at the pair of pressure rolls, A pair of heated pressure rolls (r ₁ , r ₂ ) is subjected to a protective material heating process for a predetermined period of time.

In the protective material heating step, the pair of protective materials (C ₁ , C ₂ ) are brought into contact with the outer periphery of the pressure rolls (r ₁ , r ₂ ), thereby removing moisture from the pair of protective materials (C ₁ , C ₂ ). can be removed. By reducing the water content of the pair of protective materials (C ₁ , C ₂ ) before contacting the pair of outermost layer metal foils (M ₁ , M ₂ ), air bubbles, lamination defects, etc. on the surface of the laminate are prevented. It is possible to suppress the occurrence of the problem of In the protective material heating step, the starting point of contact with the outer circumference of the pressure roll can be appropriately set according to the size of the pressure roll and the rotation speed of the pressure roll. The protective material heating step may be performed so that C ₁ , C ₂ ) are along the pressure roll. In the present invention, circumscribing means that the protective material is transported in contact with the pressure roll from a predetermined starting point along the outer circumference of the pressure roll.

The position of the protective material unwinding roll is not particularly limited as long as the pair of protective materials (C ₁ , C ₂ ) can contact the pair of pressure rolls (r ₁ , r ₂ ). The protective material unwound from the roll may be directly circumscribed by the pressure roll, or the protective material unwound from the protective material unwinding roll is passed through one or more guide rolls and then passed through the pressure roll. may be circumscribed by For example, it is preferable to have a pair of guide rolls for circumscribing the pair of protective members (C ₁ , C ₂ ) with respect to the pair of pressure rolls (r ₁ , r ₂ ).

For example, as shown in FIG. 3, a pair of protective materials (C ₁ , C ₂ ) are unwound from protective material unwinding rolls 13, 13 and then directly applied to a pair of pressure rolls (r ₁ , r ₂ ). rather than being introduced into the pair of pressure rolls (r ₁ , r ₂ ) through guide rolls 21, 21 located in the vicinity of the pair of pressure rolls (r 1 , r 2 ), and then from the guide rolls 21, 21 to the pair of pressure rolls (r ₁ , r ₂ ). The pair of protective members (C ₁ , C ₂ ) can be circumscribed by the guide rolls 21, 21 at desired locations of the pair of pressure rolls (r ₁ , r ₂ ).

The installation location of the guide rolls is not particularly limited as long as the pair of protective materials (C ₁ , C ₂ ) can be circumscribed with respect to the pair of pressure rolls (r ₁ , r ₂ ). The roll is arranged near the pressure roll, but the guide roll may be in contact with the pressure roll.

For example, in FIG. 3, the protective material (C ₁ ) is circumscribed by the pressure roll (r ₁ ) and the protective material (C ₂ ) is circumscribed by the pressure roll (r ₂ ) before thermocompression bonding. In this way, by circumscribing (or embracing) the protective material on the pressure roll, it is possible to remove moisture contained in the protective material and preheat the protective material to near the thermocompression bonding temperature in advance. . The distance at which the protective material circumscribes the pressure roll can be set as appropriate. It may be longer than one week.

In the manufacturing method of the present invention, the laminate material may have at least a pair of metal foils (M, M) in contact with each other, and the state in which at least the pair of metal foils (M, M) are in contact with each other in the laminate material In the case of thermocompression bonding of the laminate material, a metal foil separation step may be provided for separating at least a pair of metal foils (M, M) in contact with each other after the thermocompression bonding step. The portion where the metal foils are in contact with each other can be easily separated after the thermocompression bonding process. For example, the peel strength between the metal foil (M) and the metal foil (M) in the laminate after thermocompression bonding is 0.3 kN. /m or less, preferably 0.2 kN/m or less, more preferably 0.1 kN/m or less.

Each separation step of the thermoplastic liquid crystal polymer film separation step, the metal foil separation step and the protective material separation step can be performed by a known or commonly used method. Separation between a pair of protective materials (C ₁ , C ₂ ) and a pair of outermost metal foils (M ₁ , M ₂ ), (ii) separation between at least a pair of thermoplastic liquid crystal polymer films (F, F), ( iii) At least any one separation between at least one pair of metal foils (M, M) may be performed. The order of the above (i), (ii) and (iii) is not particularly limited, and a plurality of them may be performed simultaneously or stepwise. A pair of pressure rolls (r ₁ , r ₂ ) may be used as separation rolls.

For example, the above (i), (ii) and (iii) may be performed at once by passing between a pair of separation rolls.
Alternatively, any two of (i), (ii) and (iii) may be performed at once by passing between a pair of separating rolls, and the remaining separation may be performed stepwise by a single separating roll. or stepwise separation by a single separation roll followed by passage between a pair of separation rolls for the remainder of the separation.

For example, when separation is performed in stages, the separation between the protective material and the outermost layer metal foil, that is, between C ₁ /M ₁ and between M ₂ /C ₂ is performed as the first separation step, followed by Alternatively, at the same time, at least one separation step selected from M/M between metal foils and F/F between thermoplastic liquid crystal polymer films may be performed.

In addition, when the separation is performed in stages, subsequently or simultaneously, at least one separation step selected from M / M between metal foils and F / F between thermoplastic liquid crystal polymer films is performed, and then, if necessary A protective material separation step may be performed.

For example, in the third embodiment shown in FIG. 3, the laminate C ₁ /M ₁ /F/F/M/M/F/M ₂ /C ₂ obtained by the thermocompression process is separated from the first separation roll Passing through 41, 41 separates the pair of guards (C ₁ , C ₂ ) between C ₁ /M ₁ and M ₂ /C ₂ . A pair of separated protective materials (C ₁ , C ₂ ) are wound up by protective material winding rolls 32, 32, respectively. The separated pair of protective materials (C ₁ , C ₂ ) can be reused as needed. Thereafter, the laminate _M1 /F/F/M/M/F/ _M2 from which the pair of protective materials ( _C1 , _C2 ) have been separated passes through second separation rolls 42, 42, separated between M/M and then separated between F/F by passing through a third separating roll 43 to produce two single-sided metal-clad laminates (M ₁ F, MF) and one double-sided metal-clad laminate. A laminate (M ₂ FM) is produced. The obtained metal-clad laminates are wound up by metal-clad laminate take-up rolls 31, 31, 31, respectively. The two single-sided metal-clad laminates (M ₁ F, MF) may be the same or different.

4A and 4B are schematic side views for explaining a method for manufacturing a metal-clad laminate according to the fourth embodiment. Members having the same roles as those in FIG. As shown in FIG. 4, in the fourth embodiment, the thermocompression bonding step is performed by continuous isostatic pressing, and a pair of outermost metal foils (M ₁ , M ₂ ) and a pair of thermoplastic liquid crystal polymer films Double belt press so that (F, F) is in the order b ₁ /M ₁ /F/F/M ₂ /b ₂ between a pair of endless belts (b ₁ , b ₂ ) of the double belt press Each unwinding roll is arranged upstream of 51 .

When the thermocompression bonding step is performed by a continuous isostatic press, it is sufficient that a substantially uniform pressure can be applied over the entire pressure band, and a known device can be used. For example, a double belt press is preferably used. can. The double belt press 51 includes a pair of endless belts (b ₁ , b ₂ ), heating drums 61 , 61 and cooling drums 62 , 62 over which the pair of endless belts (b ₁ , b ₂ ) are stretched, and laminate material. Heating devices 71, 71 for heating the pair of endless belts (b ₁ , b ₂ ) for heating and pressurizing, and cooling for cooling the pair of endless belts (b ₁ , b ₂ ) for cooling and pressurizing the laminate material. device 72,72. As the endless belt, known materials and shapes (e.g., thickness, etc.) can be used. Examples thereof include metal belts and rubber belts, but it is preferable to use a stainless steel endless belt. A pair of endless belts (b ₁ , b ₂ ) are stretched between the heating drums 61, 61 and the cooling drums 62, 62, respectively. to move around.

Laminate materials M ₁ /F/F/M ₂ are introduced in this order to the pair of endless belts (b ₁ , b 2 ₎ while being pressed by the pair of endless belts (b ₁ , b ₂ ). It can be passed between heating drums 61, 61 and cooling drums 62, 62 and pressurized substantially evenly therebetween. The double belt press 51 heats the pair of endless belts (b ₁ , b ₂ ) by heating drums 61, 61 and heating devices 71, 71, and heats and presses the laminate material while passing through the region. can. Therefore, the thermocompression bonding process can be performed by passing the laminate material through the pair of endless belts (b ₁ , b ₂ ) and applying heat and pressure. A thermocompression bonding temperature similar to that for the pressure roll may be set. Further, when thermocompression bonding is performed by a double belt press, since the laminated body material can be pressed by surface contact with the pair of endless belts (b ₁ , b ₂ ) for a predetermined time, the temperature condition of the thermocompression bonding temperature can be A constant temperature may be set in the region, or the temperature may be changed stepwise. Also, the pressurizing pressure for thermocompression bonding may be in the range of 0.5 to 10 MPa, preferably in the range of 1.0 to 5.0 MPa. The thermocompression bonding time can be set by changing the size of the apparatus and the transport speed of the laminate material depending on the thermocompression bonding temperature and the thermoplastic liquid crystal polymer film to be used. may be 30 to 240 seconds.

In addition, the double belt press 51 cools the pair of endless belts (b ₁ , b ₂ ) by cooling devices 72, 72 and cooling drums 62, 62, and cools and presses the laminate material while passing through the area. be able to. Therefore, the cooling process can be performed by passing the laminate material through a pair of endless belts (b ₁ , b ₂ ) and applying cooling pressure. In the double belt press 51 of the fourth embodiment, a cooling area is provided in addition to the heating area. , the cooling step may be performed by providing a cooling roll downstream of the double belt press device.

For example, in the fourth embodiment shown in FIG. 4, the laminate M ₁ /F/F/M ₂ obtained through the thermocompression bonding process and the cooling process in the double belt press 51 is separated by the first separation rolls 41, 41 are separated between the F/Fs to produce two single-sided metal-clad laminates (M ₁ F, M ₂ F). The obtained single-sided metal-clad laminates are taken up by metal-clad laminate take-up rolls 31, 31, respectively.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, in the following examples and comparative examples, various physical properties were measured by the following methods.

[Melting point]
Using a differential scanning calorimeter (manufactured by Shimadzu Corporation), a sample of a predetermined size was sampled from the thermoplastic liquid crystal polymer film, placed in a sample container, and heated from room temperature to 400 ° C. at a rate of 10 ° C./min. was taken as the melting point Tm of the thermoplastic liquid crystal polymer film.

[Thickness]
The film thickness was measured at intervals of 1 cm in the TD direction using a digital thickness gauge (manufactured by Mitutoyo Co., Ltd.), and the average value of 10 points arbitrarily selected from the center and edges was taken as the film thickness. .

[Degree of crystal orientation]
Using a rotating anticathode X-ray diffractometer Ru-200 manufactured by Rigaku Denki Co., Ltd., the X-ray output was measured using a voltage of 40 kV, a current of 100 mA, and a target of CuKα (λ=1.5405 A) as follows. First, a thermoplastic liquid crystal polymer film is cut out in the MD direction and attached to a sample holder. A line was incident and the imaging plate was exposed to a diffraction pattern. Then, the thickness direction and plane direction (MD direction) of the obtained diffraction image are converted into an orientation distribution curve, and the curve of the diffraction intensity with respect to the β angle in the circumferential direction is around 20° ((110) plane ) is calculated from the half-value width H of the peak of the intensity distribution obtained by circularly integrating did.
f=(180−H)/180 (1)

[Appearance evaluation]
The obtained metal-clad laminate was visually observed, and evaluated as A when no wrinkles, streaks, deformations, or blisters were observed at a length of 20 m or more, and as B when observed.

(Reference example)
A copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (molar ratio: 73/27), a thermoplastic liquid crystal polymer having a melting point of 280°C, is melt-extruded, and a thermoplastic liquid crystal is produced by inflation molding. A polymer film was produced. A film having a thickness of 50 μm, fp of 0.5 and fv of 0.7 is type A, and a film of fp of 0.8 and fv is type B.
In addition, a thermoplastic liquid crystal polymer having a melting point of 325° C., which is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (molar ratio: 80/20), was melt-extruded and heat-treated by inflation molding. A plastic liquid crystal polymer film was produced. A film having a film thickness of 100 μm, fp of 0.6 and fv of 0.8 was type C, and a film of fp of 0.5 and fv of 0.7 was type D, fp of 0.5 and fv of 0.8. 5 film is type E.

(Example 1)
Thermoplastic liquid crystal polymer film of type A obtained in Reference Example, electrolytic copper foil as metal foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd., "CF-H9A-DS-HD2", thickness 12 μm), and polyimide as protective material A film (manufactured by Kaneka Corporation, “Apical NPI”, thickness 75 μm) was prepared as an unwinding roll. As shown in FIG. 2, these unwinding rolls consisted of a pair of thermoplastic liquid crystal polymer films (F, F), a pair of electrolytic copper foils (M ₁ , M ₂ ), and a pair of polyimide films (C ₁ , C _{2 )} . ) between a pair of pressure rolls (r ₁ , r ₂ ), each unwinding roll so that the order is r ₁ /C ₁ /M ₁ /F/F/M ₂ /C ₂ /r ₂ placed.

Laminate material M ₁ /F/F/M ₂ was introduced into a pair of pressure rolls (r ₁ , r ₂ ) via a pair of polyimide films (C ₁ , C ₂ ). Metal rolls with a diameter of 300 mm were used as the pair of pressure rolls (r ₁ , r ₂ ), the surface temperature of the metal rolls was set to 230° C., the pressure was set to 8 t/m, and a pair of polyimide films (C ₁ , C ₂ ) sandwiched between the laminate materials C ₁ /M ₁ /F/F/M ₂ /C ₂ are passed through pressure rolls (r ₁ , r ₂ ) at a speed of 3.0 m/min for thermocompression bonding. rice field.

After thermocompression bonding, as shown in FIG. 2, after passing through a pair of pressure rolls (r ₁ , r ₂ ), using the pair of pressure rolls (r ₁ , r ₂ ), the thermoplastic liquid crystal polymer film could be separated well, after which two single-sided copper-clad laminates were obtained and each wound on a winding roll. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.

(Example 2)
Same as Example 1 except that the thermoplastic liquid crystal polymer film was changed to the type C thermoplastic liquid crystal polymer film obtained in Reference Example, the surface temperature of the metal roll was 255 ° C., and the pressure was 12 t / m. A copper-clad laminate was produced. Separation between the thermoplastic liquid crystal polymer films after thermocompression bonding could be facilitated. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.

(Example 3)
A type D thermoplastic liquid crystal polymer film obtained in Reference Example and an electrolytic copper foil (“CF-T8” manufactured by Fukuda Metal Foil & Powder Co., Ltd., thickness 35 μm) as a metal foil were prepared as unwind rolls. As shown in FIG. 4, a pair of thermoplastic liquid crystal polymer films (F, F) and a pair of electrolytic copper foils (M ₁ , M ₂ ) are placed between a pair of endless belts (b ₁ , b ₂ ), b The unwinding rolls were arranged in the order of ₁ / _M1 /F/F/ _M2 / _b2 .

Laminate material M ₁ /F/F/M ₂ was introduced into a pair of endless belts (b ₁ , b ₂ ). A metal drum with a diameter of 0.8 m was used as a heating drum, the surface temperature of the pair of endless belts (b ₁ , b ₂ ) was set to 230° C., the pressure was set to 3 MPa, and the laminate material M ₁ /F/F /M ₂ was passed through endless belts (b ₁ , b ₂ ) at a speed of 1 m/min to be thermally compressed.

After thermocompression, as shown in FIG. 4, a first separation roll can provide good separation between the thermoplastic liquid crystal polymer films, after which two single-sided copper-clad laminates are obtained, which are respectively separated by a take-up roll. rolled up. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.

(Comparative example 1)
A copper-clad laminate was produced in the same manner as in Example 1, except that the thermoplastic liquid crystal polymer film was changed to the type B thermoplastic liquid crystal polymer film obtained in Reference Example. Since the films were adhered to each other, it was difficult to separate the thermoplastic liquid crystal polymer films, and the obtained copper-clad laminate had wrinkles.

(Comparative example 2)
A copper clad laminate was produced in the same manner as in Example 2, except that the thermoplastic liquid crystal polymer film was changed to the type E thermoplastic liquid crystal polymer film obtained in Reference Example. Since the films were adhered to each other, it was difficult to separate the thermoplastic liquid crystal polymer films, and the obtained copper-clad laminate had wrinkles.

As shown in Table 7, in Examples 1 to 3, a thermoplastic liquid crystal polymer film having a crystal orientation degree fp in the plane direction smaller than a crystal orientation degree fv in the thickness direction was used. The peelability between the films was good, and the obtained copper-clad laminate was free from appearance defects such as wrinkles.

On the other hand, in Comparative Examples 1 and 2, since the degree of crystal orientation fp in the planar direction of the thermoplastic liquid crystal polymer films used was not smaller than the degree of crystal orientation fv in the thickness direction, the thermoplastic liquid crystal polymer films adhered to each other after thermocompression bonding. The separation is difficult, and the obtained copper-clad laminate has wrinkles.

According to the manufacturing method of the present invention, a metal-clad laminate can be efficiently manufactured, and the obtained metal-clad laminate is used in the fields of electric/electronics, office equipment/precision equipment, power semiconductors, and the like. It can be effectively used as a component, for example, a circuit board (especially a board for millimeter wave radar).

As described above, preferred embodiments of the present invention have been described with reference to the drawings. be. Accordingly, such changes and modifications are intended to be within the scope of the invention as defined by the appended claims.

11 Metal foil unwinding roll 12 Thermoplastic liquid crystal polymer film unwinding roll 13 Protective material unwinding roll 21 Guide roll 31 Metal-clad laminate winding roll 32 Protective material take-up rolls 41, 42, 43 Separation roll 51 Double belt press 61 Heating drum 62 Cooling drum 71 Heating device 72 Cooling device r ₁ , _r2 ... Pressure rolls _b1 , _b2 ... Endless belts _M1 , _M2 ... Outermost layer metal foil F... Thermoplastic liquid crystal polymer films _C1 , _C2 ... Protective material M ... Metal foil _M1F , _M2F , MF, _M2FM ... Metal-clad laminate

Claims (12)

A method for manufacturing a plurality of metal-clad laminates,
A step of continuously thermocompressing a laminate material, wherein the laminate material comprises at least a pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other, and the pair of thermoplastic liquid crystal polymer films (F, F ) and at least a pair of metal foils (M, M) respectively arranged in contact with the outer surface of the
a thermocompression bonding step of thermocompression bonding the laminate material with the at least one pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other in the laminate material;
a thermoplastic liquid crystal polymer film separation step of separating the at least one pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other after the thermocompression bonding step;
with at least
At least one of the pair of separated thermoplastic liquid crystal polymer films (F, F) is a thermoplastic liquid crystal polymer film in which the crystal orientation degree fp in the planar direction is smaller than the crystal orientation degree fv in the thickness direction. A method for producing a tension laminate. 2. The method for producing a metal-clad laminate according to claim 1, wherein the thermoplastic liquid crystal polymer film has a crystal orientation degree fp in the planar direction within the range of 0.4 to 0.7. Production method. 3. The method for producing a metal-clad laminate according to claim 1, wherein the thickness direction crystal orientation fv of the thermoplastic liquid crystal polymer film is in the range of 0.7 to 0.9. A method for manufacturing a laminate. 4. The method for manufacturing a metal-clad laminate according to any one of claims 1 to 3, wherein the thermocompression bonding step comprises continuous isostatic pressing or hot rolls using a pair of pressure rolls (r ₁ , r ₂ ). A method for manufacturing a metal-clad laminate using a press. A method for producing a metal-clad laminate according to any one of claims 1 to 4,
In the thermocompression bonding step, the laminate material is thermocompressed with at least a pair of inner layer metal foils (M, M) in contact with each other in the laminate material,
A metal foil separation step of separating the at least one pair of inner layer metal foils (M, M) that are in contact with each other after the thermocompression bonding step,
A method for producing a metal-clad laminate. 6. The method for producing a metal-clad laminate according to any one of claims 1 to 5, wherein the laminate material has an outermost metal foil (M ₁ , M ₂ ). . A method for manufacturing a metal-clad laminate according to claim 6,
A method for producing a metal-clad laminate, wherein the laminate material is arranged in any one of the following order of (i) to (vi).
(i) _M1 /F/F/ _M2
(ii) _M1 /F/F/M/M/F/ _M2
(iii) _M1 /F/M/M/F/F/M/M/F/ _M2
(iv) _M1 /F/F/M/M/F/F/ _M2
(v) _M1 /F/F/M/M/F/F/M/M/F/ _M2
(vi) _M1 /F/M/M/F/F/M/M/F/F/M/M/F/ _M2
(Here, M ₁ , M ₂ : outermost layer metal foil, F: thermoplastic liquid crystal polymer film, M: metal foil) The manufacturing method according to any one of claims 1 to 7, wherein the laminate material is thermocompression bonded via a pair of protective materials (C ₁ , C ₂ ) during thermocompression bonding. A method for producing a tension laminate. The manufacturing method according to claim 8, wherein the protective material (C ₁ ) and/or the protective material (C ₂ ) is selected from the group consisting of heat-resistant resin films, heat-resistant composite films, and heat-resistant nonwoven fabrics. A method for manufacturing a metal-clad laminate, which is a protective material. The manufacturing method according to any one of claims 1 to 9, wherein the thermocompression bonding temperature is the melting point (Tm _L ) is in the range of (Tm _L -120)°C to (Tm _L )°C. The production method according to any one of claims 1 to 10, wherein the peel strength between the thermoplastic liquid crystal polymer film (F) and the thermoplastic liquid crystal polymer film (F) after thermocompression bonding is 0.3 kN/m A method for manufacturing a metal-clad laminate, which is as follows. The manufacturing method according to any one of claims 1 to 11, wherein the difference in melting points of the thermoplastic liquid crystal polymer films that are in contact with each other in the laminate material is in the range of 0 to 70°C. manufacturing method.

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