TW202200390A - Production method of metal-clad laminate - Google Patents

Abstract

The production method of metal-clad laminate at least includes: introducing laminate materials into a pair of pressure rollers (r1, r2) via a pair of protective materials (C1, C2) which are in contact with the pair of pressure rollers (r1, r2), respectively; thermo-compression bonding the laminate materials, the laminate materials at least including a pair of metal foils (M1, M2) as outermost layers which are in contact with the pair of protective materials (C1, C2), respectively, and at least a pair of thermoplastic liquid crystal polymer films (F, F), and being rendered to thermo-compression bonding the laminate materials with at least the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other; and separating between the pair of thermoplastic liquid crystal polymer films (F, F) after the thermo-compression bonding.

Description

Manufacturing method of metal-clad laminate

This case claims the priority of Japanese Patent Application No. 2020-053322 filed in Japan on March 24, 2020, and is cited as a part of this case completed by reference to its entirety.

The present invention relates to a film (hereinafter sometimes referred to as a thermoplastic liquid crystal polymer film) comprising a thermoplastic polymer (hereinafter sometimes referred to as a thermoplastic liquid crystal polymer) capable of forming an optically anisotropic melt phase A method for producing a metal-clad laminate having at least one surface layer of metal foil (or a metal-clad laminate having a metal layer on at least one side of a thermoplastic liquid crystal polymer film).

Thermoplastic liquid crystal polymer films are known as materials excellent in high heat resistance, low moisture absorption, high frequency characteristics, and the like, and in recent years have been attracting attention 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 represented by copper foil is used, and as a technique for producing such a laminate comprising a thermoplastic liquid crystal polymer film and a metal foil, there are exemplified : A method of superimposing a thermoplastic liquid crystal polymer film and a metal foil that are cut to a predetermined size between the upper and lower hot plates using a hot pressing device, and then heat and press bonding in a vacuum state. However, since this method is a batch method, there is a problem of poor production efficiency.

On the other hand, the method of superimposing the thermoplastic liquid crystal polymer film and the metal foil by a roll-to-roll method to continuously perform thermocompression bonding is advantageous from the viewpoint of production efficiency. In particular, when it is produced by a roll-to-roll method, as a method for producing a metal-clad laminate with good industrial productivity, Patent Document 1 (Japanese Patent No. 5661051) discloses a method for producing a metal-clad laminate on one side, Among them, by the roll-to-roll method, a separation film (C) having a surface roughness (Rz) of 2.0 μm or less on both the front and back sides is used, and the _{ratio (r 1 ) /} ( In the order of B)/(A)/(C)/(A)/(B)/(r ₂ ), the insulating film (A), the metal foil (B), and the separation film (C) are stacked and Thermocompression bonding was performed and peeled from the separation film (C) to obtain two single-sided metal-clad laminates. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5661051

[The problem to be solved by the invention]

Patent Document 1 is characterized in that two metal-clad laminate systems are arranged symmetrically up and down to connect the separation films to each other, and thermocompression bonding is performed by a roll-to-roll method, with the separation film as the center, and the separation film is attached to the introduction of the pressure roller. At the same time, it is in direct contact with the insulating film.

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 before being introduced between the pressure rolls, and thus slightly relaxes. Defects in appearance, such as wrinkles, occur in the portion due to contact with a portion of the separation film having different thermal expansion coefficients and elastic coefficients.

In addition, as described in Patent Document 1, when a separation film is not used, appearance defects occur due to thermal fusion of the liquid crystal polymer films, and when the thermoplastic liquid crystal polymer films are brought into contact with each other, they are introduced into a pressure roller. sticking problem.

Therefore, an object of the present invention is to provide a method for efficiently producing a metal-clad laminate by a roll-to-roll method without causing appearance defects such as wrinkles. [means to solve the problem]

The inventors of the present invention have made intensive studies in order to achieve the above-mentioned object, and as a result, they have found that if the protective material is arranged in the outermost layer so as to sandwich the layered body material introduced into a pair of pressure rollers, the protective material can be divided into different layers. In addition to (i) the protective material is not in contact with the thermoplastic liquid crystal polymer film, it is possible to suppress the occurrence of poor appearance caused by such partial contact, and surprisingly (ii) even within the Layers have a point where the thermoplastic liquid crystal polymer films are connected to each other, and the adhesion of the films can also be suppressed. As a result, the occurrence of appearance defects such as wrinkles can be suppressed, and the present invention has been completed.

That is, the present invention can be constituted by the following aspects. [Aspect 1] A method for producing a metal-clad laminate, which is a method for producing a plurality of metal-clad laminates, which includes at least a thermocompression bonding step and a separation step from a thermoplastic liquid crystal polymer film; the thermocompression bonding step involves a A pair of protective materials (C ₁ , C ₂ ) are respectively connected to a pair of pressure rollers (r ₁ , r ₂ ) to introduce the layered material, and the layered material is bonded by thermocompression using the aforementioned pressure roller, wherein The above-mentioned laminate material is formed by connecting at least one pair of outermost metal foils (M ₁ , M ₂ ) and at least one pair of thermoplastic liquid crystal polymer films (F, F) to each of the pair of protective materials (C ₁ , C ₂ ), respectively. It is constituted by thermocompression bonding of the laminate material in a state where the at least one pair of thermoplastic liquid crystal polymer films (F, F) in the laminate material are connected to each other; the thermoplastic liquid crystal polymer film separation step is performed in the thermocompression bonding. After the step, the aforementioned at least one pair of thermoplastic liquid crystal polymer films (F, F) are separated. [Aspect 2] The method for producing a metal-clad laminate according to Aspect 1, which includes a metal foil separation step; in the metal foil separation step, in the above-mentioned thermocompression bonding step, at least one pair of the above-mentioned laminate materials is included. Thermocompression bonding of the laminate material is performed in a state where the metal foils (M, M) are connected to each other, and the at least a pair of the mutually connected metal foils (M, M) are separated after the thermocompression bonding step. [Aspect 3] The method for producing a metal-clad laminate according to Aspect 1 or 2, wherein the pair of pressure rollers (r ₁ , r is introduced through the pair of protective materials ( C ₁ , C ₂ ) ₂ ) The laminated body material is arranged in any order of (i) to (vi) below; (i) r ₁ /C ₁ /M ₁ /F/F/M ₂ /C ₂ /r ₂ (ii) r ₁ /C ₁ /M ₁ /F/F/M/M/F/M ₂ /C ₂ /r ₂ (iii)r ₁ /C ₁ /M ₁ /F/M/M/F/F/M /M/F/M ₂ /C ₂ /r ₂ (iv)r ₁ /C ₁ /M ₁ /F/F/M/M/F/F/M ₂ /C ₂ /r ₂ (v)r ₁ /C ₁ /M ₁ /F/F/M/M/F/F/M/M/F/M ₂ /C ₂ /r ₂ (vi)r ₁ /C ₁ /M ₁ /F/M/M /F/F/M/M/F/F/M/M/F/M ₂ /C ₂ /r ₂ (here, r ₁ , r ₂ : pressure rollers, C ₁ , C ₂ : protection material, M ₁ , M ₂ : represent the outermost metal foil, F: represent a thermoplastic liquid crystal polymer film, M: represent a metal foil). [Aspect 4] The method for producing a metal-clad laminate according to any one of Aspects 1 to 3, wherein at least one of the pair of thermoplastic liquid crystal polymer films (F, F) is a crystal orientation in a plane direction The degree fp is smaller than the degree of crystallographic orientation fv in the thickness direction of the thermoplastic liquid crystal polymer film. [Aspect 5] The method for producing a metal-clad laminate according to any one of aspects 1 to 4, wherein the thermocompression bonding temperature is the lowest among the thermoplastic liquid crystal polymer films in the laminate material. For the melting point ( _TmL ) of the thermoplastic liquid crystal polymer film, it is in the range of ( _TmL -120)℃～( _TmL )℃ (preferably ( _TmL -100)℃～( _TmL )℃ range). [Aspect 6] The method for producing a metal-clad laminate according to any one of Aspects 1 to 5, wherein the thermoplastic liquid crystal polymer film (F) and the thermoplastic liquid crystal polymer film (F) after thermocompression bonding The peel strength is 0.3 kN/m or less (preferably 0.2 kN/m or less, more preferably 0.1 kN/m or less). [Aspect 7] The method for producing a metal-clad laminate according to any one of aspects 1 to 6, wherein the difference in melting points of the thermoplastic liquid crystal polymer films connected to each other in the laminate material is 0 to 70 The range of ℃ (preferably the range of 0-60 degreeC, the range of 0-50 degreeC is more preferable). [Aspect 8] The method for producing a metal-clad laminate according to any one of Aspects 1 to 7, wherein the protective material (C ₁ ) and/or the protective material (C ₂ ) are selected from the group consisting of heat-resistant resins The protective material (preferably the protective material (C ₁ ) and the protective material (C ₂ ) of the group of the film, the heat-resistant composite film, and the heat-resistant non-woven fabric are respectively selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film, and Heat-resistant non-woven group of protective materials).

In addition, any combination of at least two constituent elements disclosed in the scope of the invention application and/or description and/or drawings is included in the present invention. In particular, any combination of two or more of the claims described in the scope of the invention application is included in the present invention. [Effect of invention]

According to the present invention, since the thermoplastic liquid crystal polymer film and the protective material are arranged so as not to be adjacent to each other, the thermoplastic liquid crystal polymer film is introduced into the pressure roller and thermocompression-bonded, so that the occurrence of defective appearance can be efficiently produced.

[Form for carrying out the invention]

In the method for producing a metal-clad laminate of the present invention, a plurality of sets of metal-clad laminates in which the metal foil is layered on at least one area of the thermoplastic liquid crystal polymer film can be continuously produced.

(thermoplastic liquid crystal polymer film) The thermoplastic liquid crystal polymer film used in the production method of the present invention is formed from a melt-moldable liquid crystal polymer. The thermoplastic liquid crystal polymer is a polymer that can form an optically anisotropic melt phase, and its chemical composition is not particularly limited as long as it is a melt moldable liquid crystal polymer, but for example, thermoplastic liquid crystal polyester , or a thermoplastic liquid crystal polyester amide into which an amide bond is introduced.

In addition, the thermoplastic liquid crystal polymer may be an isocyanate-derived compound such as an aromatic polyester or an aromatic polyester amide further introduced with an imide bond, a carbonate bond, a carbodiimide bond, and an isocyanurate bond. Bonded polymers, etc.

Specific examples of the thermoplastic liquid crystalline polymer used in the present invention include well-known thermoplastic liquid crystalline polyesters and thermoplastic liquid crystalline polyesters derived from the compounds classified into (1) to (4) and their derivatives as exemplified below. amine. However, in order to form a polymer capable of forming an optically anisotropic melt phase, it goes without saying that the combination of various raw material compounds has an appropriate range.

(1) Aromatic or aliphatic diols (refer to Table 1 for representative examples) [Table 1]

(2) Aromatic or aliphatic dicarboxylic acids (refer to Table 2 for representative examples) [Table 2]

(3) Aromatic hydroxycarboxylic acid (refer to Table 3 for a representative example) [Table 3]

(4) Aromatic diamine, aromatic hydroxylamine or aromatic aminocarboxylic acid (refer to Table 4 for representative examples) [Table 4]

Copolymers having repeating units shown in Tables 5 and 6 can be cited as representative examples of thermoplastic liquid crystal polymers obtained from these raw material compounds.

[table 5]

[Table 6]

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

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

Moreover, in the case of the copolymer of (ii), at least one aromatic hydroxycarboxylic acid (C) selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, selected from the group consisting of 4,4'- At least one aromatic diol (D) selected from the group consisting of dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, and selected from the group consisting of terephthalic acid, m-phenylene The molar ratio of each repeating unit in the thermoplastic liquid crystal polymer of at least one aromatic dicarboxylic acid (E) of the group of dicarboxylic acid and 2,6-naphthalenedicarboxylic acid may be the aforementioned aromatic hydroxycarboxylic acid (C): The above-mentioned aromatic diol (D): the above-mentioned aromatic dicarboxylic acid (E)=(30-80):(35-10):(35-10) or so, more preferably (C):(D): (E)=(35～75):(32.5～12.5):(32.5～12.5), more preferably (C):(D):(E)=(40～70):(30～15 ): (30 to 15) or so.

Moreover, 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, more preferably 85 mol % or more. is more than 95 mol%. The molar ratio of the 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, and more preferably 95 mol % ear % or more.

Also, the aromatic diol (D) may be derived from a group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether Repeating units (D1) and (D2) of two different aromatic diols, in this case, the molar ratio of the two aromatic diols can be (D1)/(D2)=23/77～77/23 , more preferably 25/75 to 75/25, further preferably 30/70 to 70/30.

Moreover, 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 better. If it deviates from this range, the degree of polymerization does not increase, and the mechanical strength tends to decrease.

In addition, the optically anisotropic molten phase mentioned in the present invention can be identified by, for example, placing a sample on a hot stage, heating it under a nitrogen atmosphere, and observing the transmitted light of the sample.

For the thermoplastic liquid crystal polymer, the melting point (hereinafter referred to as Tm ₀ ) is preferably in the range of, for example, 200 to 360° C., preferably in the range of 240 to 350° C., and more preferably Tm ₀ is 260 to 330 ℃. In addition, the melting point can be obtained by observing the thermal behavior of thermoplastic liquid crystal polymer samples using a differential scanning calorimeter. That is, after the thermoplastic liquid crystal polymer sample is heated from room temperature (for example, 25°C) at a rate of 10°C/min to be completely melted, the melt is cooled to 50°C at a rate of 10°C/min, and the sample is again heated at a rate of 10°C/min. The position of the endothermic peak which appeared after the temperature was raised at a rate of /min was determined as the melting point of the thermoplastic liquid crystal polymer sample.

The aforementioned thermoplastic liquid crystal polymer can also be added within the scope of not impairing the effect of the present invention: polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyaromatic Thermoplastic polymers such as ester, polyamide, polyphenylene sulfide, polyether ether ketone, fluororesin, various additives, fillers, etc.

The thermoplastic liquid crystal polymer film used in the production method of the present invention can be obtained, for example, by extruding a melt-kneaded product of the aforementioned thermoplastic liquid crystal polymer. Although any method can be used as an extrusion molding method, well-known T-die method, blow molding method, etc. are industrially advantageous. In particular, the blow molding method applies stress not only in the mechanical axis direction of the thermoplastic liquid crystal polymer film (hereinafter abbreviated as the MD direction), but also in the direction perpendicular to it (hereinafter abbreviated as the TD direction), and can extend uniformly in the MD and TD directions. Therefore, a thermoplastic liquid crystal polymer film in which molecular orientation, dielectric properties, and the like in the MD and TD directions are controlled can be obtained.

For example, in extrusion by the T-die method, the molten sheet extruded from the T-die can be made not only for the MD direction of the thermoplastic liquid crystal polymer film, but also for both the MD and TD directions simultaneously. A film, or a molten sheet extruded from a T die can be stretched first in the MD direction and then in the TD direction to form a film.

In addition, in extrusion molding by blow molding, the cylindrical sheet melt-extruded from the ring die is subjected to a predetermined stretching ratio (equivalent to the stretching ratio in the MD direction) and blowing ratio (equivalent to TD). The stretching ratio in the direction) is stretched to form a film, and the crystal orientation degree f, which will be described later, can be controlled.

The stretching ratio of such extrusion molding is the stretching ratio (or stretching ratio) in the MD direction, and may be, for example, about 1.0 to 10, preferably about 1.2 to 7, and more preferably about 1.3 to 7. Moreover, as a draw ratio (or blow ratio) in the TD direction, for example, it may be about 1.5 to 20, preferably about 2 to 15, and more preferably about 2.5 to 14.

Since the thermal properties of the thermoplastic liquid crystal polymer, the desired thickness of the thermoplastic liquid crystal polymer film, and other manufacturing conditions are affected, the specific relationship between the stretching ratio and the blowing ratio cannot be shown. Within the range, the blow ratio can be adjusted to be larger than the draw ratio, etc., whereby the crystal orientation degree fp in the plane direction can be controlled to be smaller than the crystal orientation degree fv in the thickness direction.

In addition, the melting point and/or the thermal expansion coefficient of the thermoplastic liquid crystal polymer film may be adjusted by performing a known or conventional heat treatment as required. The heat treatment conditions can be appropriately set according to the purpose. For example, with respect to the melting point (Tm ₀ ) of the thermoplastic liquid crystalline polymer, it can be above (Tm ₀ -10)° C. (for example, (Tm ₀ -10) to (Tm ₀ +30) About ℃, preferably (Tm ₀ ) ~ (Tm ₀ +20) ℃) heating for several hours, thereby raising 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 to 380°C, and preferably within the range of 280 to 370°C. In addition, 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 obtained by taking the position of the endothermic peak that appears when the thermoplastic liquid crystal polymer film sample is heated from room temperature (eg, 25° C.) at a rate of 10° C./min.

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

(metal foil) The metal foil used in the production method of the present invention is not particularly limited. For example, it can be gold, silver, copper, iron, nickel, aluminum, or an alloy of these metals. From the viewpoint of electrical conductivity, workability, and cost, etc. From the point of view, copper foil and stainless steel foil are preferable. Moreover, as a copper foil, what was manufactured by a rolling method and an electrolytic method can be used.

The thickness of the metal foil can be appropriately set according to needs, for example, it can be about 5 to 50 μm, and more preferably, it can be in the range of 8 to 35 μm. Moreover, surface treatment, such as a roughening process normally given, may be performed on the metal foil.

(protective material) The protective material used in the production method of the present invention 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, and examples thereof include non-thermoplastic polyimide films and polyarylenes. Heat-resistant resin films such as amide films and Teflon (registered trademark) films; heat-resistant composite films (such as composite films comprising multiple heat-resistant resin films, composite films comprising metal foils and heat-resistant resin films); aluminum foils and stainless steel foils and other metal foils; and heat-resistant non-woven fabrics composed of heat-resistant fibers (such as heat-resistant resin fibers, metal fibers). These protective materials may be used alone or in combination of two or more. Among these protective materials, a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant nonwoven fabric are preferable from the viewpoint of being excellent in heat resistance and rebound elasticity.

The thickness of the protective material can be appropriately set according to needs, for example, it can be about 10-300 μm, preferably 15-150 μm, more preferably 15-130 μm. In addition, the protective material may be subjected to mold release treatment on one side or both sides for the purpose of improving the peelability from the metal foil after thermocompression bonding. As a method of the mold release treatment, for example, a method of forming a heat-resistant mold release resin film such as polysiloxane or fluororesin on at least one surface of the protective material, etc. may be mentioned.

(Manufacturing method of metal-clad laminate) The method of manufacturing a metal-clad laminate of the present invention includes at least a thermocompression bonding step and a separation step from the thermoplastic liquid crystal polymer film; the thermocompression bonding step is to connect a pair of pressure rollers respectively via a space between them. (r ₁ , r ₂ ) a pair of protective materials (C ₁ , C ₂ ) is introduced into the laminate material, and the laminate material is thermocompression-bonded by the pressing roller, wherein the laminate material is at least separated by A pair of outermost metal foils (M ₁ , M ₂ ) and at least a pair of thermoplastic liquid crystal polymer films (F, F) are connected to one of the pair of protective materials (C ₁ , C ₂ ). In the above-mentioned at least one pair of thermoplastic liquid crystal polymer films (F, F), the laminate material is thermocompression-bonded with each other; the thermoplastic liquid crystal polymer film separation step is after the thermocompression bonding step. Separation between liquid crystal polymer films (F, F).

Thermoplastic liquid crystal polymer films and metal foils are not particularly limited as long as they can be formed into a laminate material, and the laminate material is introduced into a pressure roller through a protective material. The unwinding rolls of each material are arranged so that the laminated body material of the desired structure can be formed. In the present invention, the laminated body material refers to a material that is stacked in a predetermined arrangement in order to manufacture a desired plurality of metal-clad laminated bodies, and a pair of protective materials (C ₁ , C ₂ ) are sandwiched and introduced into the whole. To the pressure rollers (r ₁ , r ₂ ).

Here, the thermoplastic liquid crystal polymer film (F) used as a constituent material of one metal-clad laminate in the laminate material may be singular or plural. In addition, the metal foil (M) may be singular or plural. In addition, when plural numbers are included, they may be the same or different from each other.

Furthermore, each constituent material of the laminate material may be a monomer of the thermoplastic liquid crystal polymer film (F) and a monomer of the metal foil (M), or may be disposed on one surface of the thermoplastic liquid crystal polymer film (F). Single-sided metal-clad laminate (M/F) with metal foil (M). Therefore, when using a plurality of unwinding rolls for unwinding the constituent materials for forming a plurality of metal-clad laminates composed of the thermoplastic liquid crystal polymer film (F) and the metal foil (M), it may also include: ( i) unwinding roll for unwinding thermoplastic liquid crystal polymer film (F), (ii) unwinding roll for unwinding metal foil (M), and/or (iii) unwinding for single-sided metal cladding Unwinding roll for laminated body (M/F). These respective constituent materials may be the same or different. In addition, the single-sided metal-clad laminate (M/F), which is a constituent material of the laminate material, can also be used as a material for producing a double-sided metal-clad laminate (M/F/M).

As long as the arrangement of each constituent material of the laminate material does not impair the effect of the present invention, as long as it is an arrangement in which the protective material (C) and the thermoplastic liquid crystal polymer film (F) are not connected, other than forming a metal-clad laminate may be included. For example, the protective material (C) may be arranged between a pair of metal foils (M, M), or the order of M/C/M may be arranged.

When forming a laminated body material, when preparing each constituent material by the unwinding roll, each unwinding roll may be arrange|positioned so that the following conditions may be satisfied, for example. (i) A pair of outermost metal foils (M ₁ , M ₂ ) are rolled out from a metal foil take-up roll to form the outermost layers in the laminate material, respectively, and a pair of protective materials (C ₁ , C ₂ ) are connected to each other. (ii) A pair of thermoplastic liquid crystal polymer films (F, F) unwound from a thermoplastic liquid crystal polymer film take-up roll has at least a portion connected to each other in the laminate material.

The laminate material may be connected to each other at least one pair of metal foils (M, M). Since the parts where the metal foils are connected to each other can be easily separated after the thermocompression bonding step, when manufacturing a plurality of metal-clad laminates (for example, three or more metal-clad laminates), a pair of laminates should be included in the laminate material. Parts where the metal foils (M, M) are connected to each other are preferred.

The layered material may be introduced into a pair of pressure rollers (r ₁ , r ₂ ) via a pair of protective materials (C ₁ , C ₂ ) by disposing in any order of the following (i) to (vi). . (i) _r1 / _C1 /M1/F/F/ _M2 /C2/ _{r2 (} ii) _r1 / _C1 /M1/ _F / _F /M/M/F/ _M2 /C ₂ /r ₂ (iii)r ₁ /C ₁ /M ₁ /F/M/M/F/F/M/M/F/M ₂ /C ₂ /r ₂ (iv)r ₁ /C ₁ /M ₁ /F/F/M/M/F/F/M ₂ /C ₂ /r ₂ (v)r ₁ /C ₁ /M ₁ /F/F/M/M/F/F/M/M/ F/M ₂ /C ₂ /r ₂ (vi)r ₁ /C ₁ /M ₁ /F/M/M/F/F/M/M/F/F/M/M/F/M ₂ /C ₂ /r ₂

At least one of the pair of thermoplastic liquid crystal polymer films (F, F) connected to each other in the laminate material may be a thermoplastic liquid crystal polymer with a crystal orientation degree fp in the plane direction smaller than the crystal orientation degree fv in the thickness direction material film. The greater the degree of crystallographic orientation fv in the thickness direction of the thermoplastic liquid crystal polymer film, the more difficult it becomes for the film to adhere to the thermoplastic liquid crystal polymer film attached thereto, thus becoming easier to separate after the thermocompression bonding step. In addition, as the crystal orientation degree fp in the plane direction is smaller, it becomes more difficult to generate peeling anisotropy when the film is separated from the thermoplastic liquid crystal polymer film attached thereto.

Here, the crystal orientation degree f refers to an index of the degree of orientation imparted to the crystal region of the polymer, and is calculated as follows. The crystal orientation degree f can be measured as follows using a rotary counter-cathode X-ray diffraction apparatus Ru-200 manufactured by Rigaku Electric Co., Ltd., and the X-ray output can be measured using a voltage of 40 kV, a current of 100 mA, and a target CuKα (λ=1.5405 Å). Changes in crystal orientation can be obtained from wide-angle X-ray photographs. First, a thermoplastic liquid crystal polymer film is cut out in the MD direction, and mounted on a sample holder. The crystal orientation degree fp in the plane direction is made by X-rays incident from the through direction, and the crystal orientation degree fv in the thickness direction is made by X-rays from the edge direction. The ray is incident, and the diffraction image is exposed on the imaging plate. Then, with respect to the obtained diffraction image, the thickness direction and the plane direction (MD direction) can be respectively converted into an alignment distribution curve, and from the half width H of the peak of the curve of the diffraction intensity with respect to the angle β in the circumferential direction, by the following According to the formula (1), the crystal orientation degree f (the crystal orientation degree fp in the plane direction and the crystal orientation degree fv in the thickness direction) is calculated. f=(180-H)/180 (1) In the formula, H is the half-height width. In addition, the full width at half maximum H may be an intensity distribution obtained by circularly integrating the diffraction angle 2θ=15° to 30° (for example, around 20° (the (110) plane)) measured by wide-angle X-ray diffraction The half-height width of the crest.

At least one of the pair of thermoplastic liquid crystal polymer films (F, F) interconnected in the laminate material has a crystal orientation degree fp in the plane direction of the thermoplastic liquid crystal polymer film (F) of 0.4 to 0.8, preferably Can be 0.5 to 0.7. In addition, the crystal orientation degree fv in the thickness direction may be 0.7 to 0.9, preferably 0.7 to 0.8.

A pair of thermoplastic liquid crystal polymer films (F, F) connected to each other in the laminate material may be the same as or different from each other, for example, the difference in melting point between these films may be in the range of 0 to 70°C, preferably 0 to 70°C. The range of 60°C is preferably the range of 0 to 50°C.

When the melting points of a plurality of thermoplastic liquid crystal polymer films in the laminate material are different, the melting point of one pair of thermoplastic liquid crystal polymer films (F, F) connected to each other may be higher than that of the other thermoplastic liquid crystal polymer films in the laminate material. It has the lowest melting point ( _TmL ). 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 included in the laminate material.

In the method for producing a metal-clad laminate of the present invention, since the protective material and the thermoplastic liquid crystal polymer film are not adjacent to each other, even before the thermocompression bonding step, the thermoplastic liquid crystal polymer in the laminate material is further heated by heating The heating step for softening the films (F, F) can also suppress the occurrence of poor appearance of the obtained metal-clad laminate.

In addition, from the viewpoint of reducing the moisture content of the protective material and suppressing the occurrence of defects derived from moisture in the metal-clad laminate, the method for producing the metal-clad laminate of the present invention may further include a further step before the thermocompression bonding step. A protective material heating step for heating a pair of protective materials (C ₁ , C ₂ ) is provided.

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 ) can be heated by external heating means such as a heater, or The pair of protective materials (C ₁ , C ₂ ) can be heated by heating rollers provided separately from the pressure rollers (r ₁ , r ₂ ). Alternatively, a pair of protective materials (C ₁ , C ₂ ) may be heated by externally surrounding a pair of protective materials (C ₁ , C ₂ ) with a pair of pressure rollers (r ₁ , r ₂ ).

When a pair of protective materials (C ₁ , C ₂ ) are externally connected to the pressure rollers (r ₁ , r ₂ ), the time between the protective materials and the pressure rollers can be adjusted according to the type of the protective material, the state of the protective material, and the pressure Although various conditions, such as the heating temperature of a roll, are suitably set, from a viewpoint of removing moisture from a protective material, for example, 1.0 second or more is preferable, for example, 1.0-200 second, or 3.0-125 second may be sufficient.

The heating step of the protective material can also be determined based on the thermocompression bonding temperature. For example, when the thermocompression bonding temperature is set to T°C, the temperature of the protective material heating step can be, for example, T-30 to T+30°C, preferably It is T-15～T+15℃.

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

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

Hereinafter, a specific embodiment will be described with reference to the drawings. FIG. 1 is a schematic side view for explaining the method of manufacturing the metal-clad laminate of the first embodiment. As shown in FIG. 1 , in the first embodiment, on the upstream side of a pair of pressure rolls (r ₁ , r ₂ ), _a pair of protective material take _- up rolls 11 , 11. Roll out a pair of outermost metal foils (M ₁ , M ₂ ) with metal foil roll-out rolls 12, 12, and roll out a pair of thermoplastic liquid crystal polymer films (F, F) The thermoplastic liquid crystal polymer film is rolled out Rollers 13,13.

Here, in the first embodiment, a pair of protective materials (C ₁ , C ₂ ), a pair of outermost metal foils (M ₁ , M ₂ ), and a pair of thermoplastic liquid crystal polymer films (F, F) are arranged in a pair of Each unwinding roller was arranged so that the pressure rollers (r ₁ , r ₂ ) were in the order of r ₁ /C ₁ /M ₁ /F/F/M ₂ /C ₂ /r ₂ .

Specifically, on the upstream side of the pair of pressure rolls (r ₁ , r ₂ ), protective material take-up rolls 11 , which wind up the pair of protective materials (C ₁ , C ₂ ) are arranged so as to be the outermost layers, respectively. 11. A pair of metal foil take-up rolls 12, 12 for rolling out a pair of outermost metal foils (M ₁ , M ₂ ) are arranged on the inner side, and a pair of thermoplastic liquid crystal polymer films (F, F) are further arranged on the inner side. The thermoplastic liquid crystal polymer film is taken off the rolls 13, 13.

As shown in FIG. 1 , after disposing each unwinding roll with respect to a pair of pressure rolls (r ₁ , r ₂ ), 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 unwound from the respective unwinding rolls as indicated by the arrows, and the pair of pressure rolls (r ₁ , r ₂ ) are shown by the arrows. The MD direction (or stacking direction) is imported.

The laminated body material M ₁ /F/F/M ₂ is introduced into a pair of protective materials (C 1 , C 2 ) through a pair of protective materials (C ₁ , C ₂ ), that is, overlapped in the order of C ₁ /M ₁ /F/F/M ₂ /C ₂ . The pressure rolls (r ₁ , r ₂ ) apply pressure to the laminate material at a predetermined heating temperature. Since the production method of the present invention is an arrangement in which the protective material and the thermoplastic liquid crystal polymer film do not come into contact with each other, it is possible to suppress the resulting metallization caused by the partial contact between the thermoplastic liquid crystal polymer film and the protective material having different thermal expansion coefficients and elastic coefficients. Occurrence of poor appearance of the laminate. In addition, by interposing a protective material between the pressure roller and the metal foil, it is possible to disperse the pressure from the pressure roller at the time of thermocompression bonding, so that it is possible to suppress the unevenness of the pressure applied to the laminate material. caused by wrinkles. Furthermore, by arranging the protective material in the outermost layer so as to sandwich the laminate material, it is possible to suppress thermal conduction more than necessary to the inner layer of the laminate material, thereby suppressing the thermocompression bonding of the thermoplastic liquid crystal polymer films to each other. As a result of sticking, the metal-clad laminate can be efficiently produced while suppressing the occurrence of poor appearance of the obtained metal-clad laminate.

As a pressing roll, a well-known heating and pressing apparatus can be used, for example, a metal roll, a rubber roll, a resin-coated metal roll, etc. are mentioned. A pair of pressure rollers (r ₁ , r ₂ ) may be the same or different from each other. For example, from the viewpoint of improving the heating efficiency, the pressure roll (r ₁ ) may be a metal roll, and the pressure roll (r ₂ ) may be a metal roll like the pressure roll (r ₁ ), or a rubber roll may be used. Rolls or resin-coated metal rolls.

Moreover, each heating temperature of a pair of pressure rolls ( _r1 , _r2 ) may mutually be the same, and may differ. For example, when the form and constituent material of the laminate are asymmetric, considering the melting point of the thermoplastic liquid crystal polymer film, etc., the heating temperature of one pressure roller can be set higher than the heating temperature of the other pressure roller. When the heating temperature of the pressure roller (r ₂ ) is higher than that of the pressure roller (r ₁ ), for example, the temperature difference between the heating temperature of the pressure roller (r ₂ ) and the heating temperature of the pressure roller (r ₁ ) may be 5 to 80°C, preferably 10 to 70°C, more preferably 20 to 50°C.

In addition, the thermocompression bonding temperature and the pressure conditions of the pressing roller are not particularly limited, but from the viewpoints of improving the adhesion between the thermoplastic liquid crystal polymer film and the metal foil and suppressing the occurrence of wrinkles, for example, the thermoplastic Regarding the melting point (Tm) of the liquid crystal polymer film, the thermocompression bonding temperature can be in the range of (Tm-120)°C to (Tm)°C, preferably (Tm-100)°C to (Tm)°C. When the melting points of a plurality of thermoplastic liquid crystal polymer films in the laminate material are different, relative to the melting point ( _TmL ) of the thermoplastic liquid crystal polymer film having the lowest melting point among the thermoplastic liquid crystal polymer films in the laminate material , the thermocompression bonding temperature can be in the range of (Tm _L -120)°C to (Tm _L )°C, preferably (Tm _L -100)°C to (Tm _L )°C. In addition, the thermocompression bonding temperature may be the heating temperature of the pressure rollers (r ₁ , r ₂ ), and when the heating temperature of the pair of pressure rollers (r ₁ , r ₂ ) is different, the pair of pressure rollers may be used. The higher one of the heating temperatures of (r ₁ , r ₂ ) is the thermocompression bonding temperature.

The pressing pressure can be in the range of 1.0t/m(9.8kN/m)～15t/m(147kN/m), preferably 1.5t/m(14.7kN/m)～12t/m(117.6kN/m) ) range. In addition, the pressing pressure is a value obtained by dividing the force (press-bonding load) given to the pressing roller by the work width.

In addition, the speed at which the protective material and the laminate material pass through the pair of pressing rollers (r ₁ , r ₂ ) can be appropriately set according to the thermocompression bonding temperature, the pressure conditions of the pressing roller, and the size of the pressing roller. It is 0.5 to 5.0 m/min, preferably 1.0 to 4.0 m/min.

The manufacturing method of the present invention includes a step of separating the thermoplastic liquid crystal polymer films for separating at least a pair of thermoplastic liquid crystal polymer films ( _F , F) after the thermocompression bonding step. r ₂ ), immediately separate the pair of thermoplastic liquid crystal polymer films (F, F), or separate the pair of thermoplastic liquid crystal polymer films (F) by at least one separation roller provided in addition to the pressure roller. , F).

In the production method of the present invention, since the protective material is disposed on the outermost layer so as to sandwich the laminate material, the thermoplastic liquid crystal polymer films can be prevented from sticking to each other by thermocompression bonding, and the thermoplastic liquid crystal polymer films can be easily separated. . For example, the peel strength of the thermoplastic liquid crystal polymer film (F) and the thermoplastic liquid crystal polymer film (F) in the laminate after thermocompression bonding may be 0.3 kN/m or less, preferably 0.2 kN/m or less, more preferably 0.1kN/m or less. In addition, in the present invention, the peel strength is the peel strength (tear strength) measured in accordance with JIS C 6471:1995 (90° direction peeling).

Moreover, the manufacturing method of this invention may be equipped with the protective material isolation|separation process which isolate|separates the protective material and the outermost metal foil which are mutually connected at least on one side. At this time, the protective material separation step and the thermoplastic liquid crystal polymer film separation step can be performed in stages by performing any one of the separation steps first, followed by the other separation step, or the protective material separation step and the thermoplastic liquid crystal polymer film can be simultaneously performed. Membrane separation step. When these separation steps are performed in stages, it is preferable to perform the protective material separation step before the thermoplastic liquid crystal polymer film separation step. That is, the separation of the protective material and the outermost metal foil can be performed in stages, and then the separation between a pair of thermoplastic liquid crystal polymer films can be performed.

In the present invention, since the protective material is arranged in the outermost layer, the protective material can be separated extremely easily. As a result, it is possible to suppress the occurrence of wrinkles that are easily generated when separation is difficult, and to manufacture a high-quality metal-clad laminate with good productivity.

These separation steps can be performed by well-known or conventional methods. For example, the separation step can be performed by using a pair of pressure rollers (r ₁ , r ₂ ) as separation rollers, or at least one other than the pressure rollers can be used. One separation roll is used for separation. At least one separation roll may be a pair of separation rolls, a plurality of separation rolls arranged independently, or a combination thereof. In addition, the order of the separation rolls may be appropriately set, and any one of them may be on the upstream side.

Moreover, in the production method of the present invention, the protective material separation step may not be performed, and the metal-clad laminate obtained after the thermocompression bonding step may be wound together with the protective material in a state where the metal-clad laminate and the protective material are overlapped.

The production 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 on the downstream side of the pressure roll as necessary. The cooling roll is preferably provided between the pressure roll and the first separation roll. The cooling roll may be constituted by a pair of rolls, or may be constituted by a single roll.

For example, in the first embodiment shown in FIG. 1, the laminate C ₁ /M ₁ /F/F/M ₂ /C ₂ obtained by the thermocompression bonding step is passed through a pair of pressing rollers (r ₁ , r ₂ ), immediately after separation between C ₁ /M ₁ , M ₂ /C ₂ and F/F simultaneously. One pair of protective materials (C ₁ , C ₂ ) separated between C ₁ /M ₁ and M ₂ /C ₂ are wound by protective material winding rolls 31 and 31 , respectively. One of the separated protective materials (C ₁ , C ₂ ) can be reused as needed. Moreover, two single-sided metal-clad laminates (M ₁ F, M ₂ F) were produced by separating F/F at the same time. In addition, the obtained single-sided metal-clad laminate system was wound by the metal-clad laminate winding rollers 32 and 32 after passing through guide rolls 21 and 21, respectively. In addition, one or a plurality of guide rollers or the like may be arranged between the pressure roller and the winding by each winding roller, and it may be used for inducing and adjusting tension, widening, and the like.

Moreover, FIG. 2 is a schematic side view for demonstrating the manufacturing method of the metal-clad laminated body of 2nd Embodiment. Components having the same functions as those in FIG. 1 are assigned the same symbols, and their descriptions are omitted. As shown in FIG. 2 , in the second 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 , M 2 ) are used. C ₂ ) between the pair of pressure rollers (r ₁ , r ₂ ) in the order of r ₁ /C ₁ /M ₁ /F/F/M/M/F/M ₂ /C ₂ /r ₂ , Each unwinding roller is arranged on the upstream side of the pair of pressure rollers (r ₁ , r ₂ ).

The laminated body material M ₁ /F/F/M/M/F/M ₂ is separated by a pair of protective materials (C ₁ , C ₂ ), that is, C ₁ /M ₁ /F/F/M/M/F The sequence of /M ₂ /C ₂ overlaps and is introduced into a pair of pressure rollers (r ₁ , r ₂ ). The laminate material may also be connected to each other by at least one pair of metal foils (M, M). When thermocompression bonding of the laminate material is performed with at least one pair of metal foils (M, M) connected to each other in the laminate material, this The manufacturing method of the invention may further include a metal foil separation step of separating at least a pair of metal foils (M, M) connected to each other after the thermocompression bonding step. The parts where the metal foils are connected to each other can be easily separated after the thermocompression bonding step. For example, the peel strength of the metal foil (M) and the metal foil (M) in the laminated body after thermocompression bonding can be 0.3 kN/m or less, which is relatively high. It is preferably 0.2 kN/m or less, more preferably 0.1 kN/m or less.

The separation steps of the thermoplastic liquid crystal polymer film separation step, the metal foil separation step, and the protective material separation step can be carried out by well-known or conventional methods. For example, the separation step can be carried out by at least one separation roller. (i) A pair of protection separation between the material (C ₁ , C ₂ ) and a pair of outermost metal foils (M ₁ , M ₂ ), (ii) separation between a pair of thermoplastic liquid crystal polymer films (F, F), (iii) a pair of metal foils At least any one of the separations between the foils (M, M). The order of the above-mentioned (i), (ii) and (iii) is not particularly limited, and a plurality of them may be performed simultaneously, or may be performed in stages. In addition, a pair of pressure rolls (r ₁ , r ₂ ) may also be used as separation rolls.

For example, the above-mentioned (i), (ii) and (iii) can be performed at one time by passing between a pair of separation rolls. Alternatively, any two of (i), (ii) and (iii) may be carried out at a time between a pair of separation rolls, and the remaining separations may be carried out in stages with a single separation roll; The separation is performed stepwise by a single separation roll, and the remaining separation is carried out by passing between a pair of separation rolls.

For example, when the separation is carried out in stages, the separation between the protective material and the outermost metal foil, that is, the separation between C ₁ /M ₁ and M ₂ /C ₂ may be carried out as the first separation step, and thereafter, it may be carried out continuously or simultaneously. At least one separation step selected from M/M between metal foils and F/F between thermoplastic liquid crystal polymer films.

In addition, when the separation is performed in stages, at least one separation step selected from M/M between metal foils and F/F between thermoplastic liquid crystal polymer films may be continued or simultaneously performed, and thereafter, protective materials may be performed as necessary. separation step.

For example, in the second embodiment shown in FIG. 2 , the laminate C ₁ /M ₁ /F/F/M/M/F/M ₂ /C ₂ obtained by the thermocompression bonding step is formed by passing through the first The separation rollers 41 and 41 separate a pair of protective materials (C ₁ and C ₂ ) between C ₁ /M ₁ and between M ₂ /C ₂ . One pair of protective materials (C ₁ , C ₂ ) separated is wound up by protective material winding rolls 31 , 31 , respectively. One of the separated protective materials (C ₁ , C ₂ ) can be reused as needed. After that, the layered body M ₁ /F/F/M/M/F/M ₂ from which the pair of protective materials (C ₁ , C ₂ ) was separated is separated between M/M by passing through the second separation rollers 42 and 42 After separation, it was separated between F/F by the third separation roll 43, and two single-sided metal-clad laminates (M ₁ F, MF) and one double-sided metal-clad laminate (M ₂ FM) were produced. In addition, the obtained metal-clad laminate system was wound by the metal-clad laminate winding rolls 32 , 32 , and 32 , respectively. The two single-sided metal-clad laminates (M ₁ F, MF) may be the same or different from each other.

Moreover, FIG. 3 is a schematic side view for demonstrating the manufacturing method of the metal-clad laminated body of 3rd Embodiment. 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 , M 2 ) are used. C ₂ ) between the pair of pressure rollers (r ₁ , r ₂ ) in the order of r ₁ /C ₁ /M ₁ /F/F/M/M/F/F/M ₂ /C ₂ /r ₂ In this way, each unwinding roller is arranged on the upstream side of the pair of pressure rollers (r ₁ , r ₂ ). Here, members having the same functions as those in FIGS. 1 and 2 are given the same reference numerals, and their descriptions are omitted.

The laminated body material M ₁ /F/F/M/M/F/F/M ₂ is separated by a pair of protective materials (C ₁ , C ₂ ), that is, C ₁ /M ₁ /F/F/M/M The sequence of /F/F/M ₂ /C ₂ is overlapped and introduced into a pair of pressure rollers (r ₁ , r ₂ ).

Here, a pair of protective materials (C ₁ , C ₂ ) unwound from the protective material unwinding rolls 11 , 11 are introduced into a pair of pressure rolls in contact with the layered body material, and each pair is heated for a pair of protective materials (C 1 , C 2 ). The pressing rollers (r ₁ , r ₂ ) perform the step of heating the protective material outside for a predetermined time.

In the protective material heating step, the pair of protective materials (C ₁ , C ₂ ) are in contact with the outer peripheries of the pair of pressing rollers (r ₁ , r ₂ ), so that the protective material (C 1 , C 2 ) can be removed from the pair of protective materials (C ₁ , C 2 ). ₂ ) Remove moisture. Furthermore, by reducing the moisture content of the pair of protective materials (C ₁ , C ₂ ) before contacting the pair of outermost metal foils (M ₁ , M ₂ ), it is possible to suppress the generation of air bubbles and lamination defects on the surface of the laminate. and other adverse conditions. In the step of heating the protective material, the starting point of contact with the outer periphery of the pressing roller can be appropriately set according to the size of the pressing roller and the rotational speed of the pressing roller, or a pair of protective materials (C ₁ , C ₂ ) The protective material heating step is carried out along the way of the pressing roller. In addition, the circumscribed system in this invention means that a protective material is conveyed so that it may contact along the outer periphery of a pressure roller from a predetermined origin.

The position of the protective material unwinding roller is not particularly limited as long as the pair of protective materials (C ₁ , C ₂ ) can be in contact with the pair of pressure rollers (r ₁ , r ₂ ). The material can be directly externally connected to the pressure roller, and the protective material unrolled from the protective material roll-out roller can also be externally connected to the pressure roller after passing through one or more guide rollers. For example, it is preferable to provide a pair of guide rollers for circumscribing a pair of protective materials (C ₁ , C ₂ ) to a pair of pressure rollers (r ₁ , r ₂ ).

For example, as shown in FIG. 3 , after the pair of protective materials (C ₁ , C ₂ ) are unwound from the protective material unwinding rollers 11 and 11, they may not be directly introduced into the pair of pressure rollers (r ₁ , r ₂ ), but It passes through the guide rollers 21 and 21 arranged in the vicinity of the pair of pressure rollers (r ₁ , r ₂ ), and then externally extends from the guide rollers 21 and 21 to the pair of pressure rollers (r ₁ , r ₂ ). The pair of protective materials (C ₁ , C ₂ ) can be externally attached to the desired position of the pair of pressure rollers (r ₁ , r ₂ ) by the guide rollers 21 and 21 .

The installation position of the guide rollers is not particularly limited as long as the pair of protective materials (C ₁ , C ₂ ) can be circumscribed to the pair of pressure rollers (r ₁ , r ₂ ). Near the pressure roller, but can also be connected to the pressure roller.

For example, in FIG. 3 , before thermocompression bonding, the protective material (C ₁ ) is externally attached to the pressing roller (r ₁ ), and the protective material (C ₂ ) is externally attached to the pressing roller (r ₂ ). In this way, the protective material can be preheated to near the thermocompression bonding temperature while removing the moisture contained in the protective material by externally surrounding (or entraining) the protective material. The distance that the protective material is outside the pressure roller can be appropriately set, but may be, for example, 1/8 or more of the pressure roller, 1/4 or more, or 1/2 or more.

For example, in the third embodiment shown in FIG. 3 , a pair of protective materials (C ₁ , C ₂ ) sandwich the laminate material M ₁ /F/F/M/M/F after the protective material heating step. /F/M ₂ is introduced into a pair of pressure rollers (r ₁ , r ₂ ) as the outermost layer as a whole.

Furthermore, the laminated body C ₁ /M ₁ /F/F/M/M/F/F/M ₂ /C ₂ obtained by the thermocompression bonding step is passed through the first separation rollers 41 and 41 to be separated at C ₁ . The protective materials (C ₁ , C ₂ ) are separated between /M ₁ and M ₂ /C ₂ . The separated one pair of protective materials (C ₁ , C ₂ ) are wound by protective material winding rolls 31 , 31 , respectively. One of the separated protective materials (C ₁ , C ₂ ) can be reused as needed. After that, the layered body M ₁ /F/F/M/M/F/F/M 2 from which the pair of protective materials (C ₁ , C ₂ ) was separated is separated at M/F/F/M/M ₂ by passing through the second separation rollers 42 and 42 . The M space and the F/F space were separated, and four single-sided metal-clad laminates (M ₁ F, MF, MF, and M ₂ F) were produced. In addition, the obtained single-sided metal-clad laminate system was wound up by the metal-clad laminate winding rolls 32 , 32 , 32 , and 32 , respectively. The four single-sided metal-clad laminates (M ₁ F, MF, MF, M ₂ F) may be the same or different from each other. [Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples at all. 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 is taken from a thermoplastic liquid crystal polymer film, put into a sample container, and the endothermic peak appears when the temperature is raised from room temperature to 400°C at a rate of 10°C/min. The position is set as the melting point Tm of the thermoplastic liquid crystal polymer film.

[film thickness] The film thickness was measured using a digital thickness meter (manufactured by Mitutoyo Co., Ltd.) at 1 cm intervals in the TD direction of the obtained thin film, and the average value of 10 points arbitrarily selected from the center part and the edge part was set as the film thickness.

[Crystal orientation degree] Using a rotary counter-cathode X-ray diffraction apparatus Ru-200 manufactured by Rigaku Electric Co., Ltd., the X-ray output was measured as follows using a voltage of 40 kV, a current of 100 mA, and a target CuKα (λ=1.5405 Å). First, a thermoplastic liquid crystal polymer film is cut out in the MD direction, and mounted on a sample holder. The crystal orientation degree fp in the plane direction is made by X-rays incident from the through direction, and the crystal orientation degree fv in the thickness direction is made by X-rays from the edge direction. The ray is incident, and the diffraction image is exposed on the imaging plate. Then, with respect to the obtained diffraction image, the thickness direction and the plane direction (MD direction) are respectively converted into alignment distribution curves, and from the curve of the diffraction intensity with respect to the angle β in the circumferential direction, about 20° ((110) The half-height width H of the peak of the intensity distribution obtained by circular integration of the plane) is calculated by the following formula (1) to calculate the crystal orientation degree f (crystal orientation degree fp in the plane direction and crystal orientation degree fv in the thickness direction) . f=(180-H)/180 (1)

[Appearance evaluation] The obtained metal-clad laminate was observed by visual observation, and those in which no wrinkles, streaks, deformation, swelling, and non-adhering parts were not observed in a length of 20 m or more were rated as A, and those who were observed were rated as B.

(Example 1) A thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., "Vecstar" (registered trademark), melting point 310° C., thickness 25 μm), and electrolytic copper foil (Fukuda Metal Foil Industry Co., Ltd.) as metal foil were prepared. Company made, "CF-H9A-DS-HD2", thickness 12μm), and a polyimide film (Kaneka Co., Ltd. make, "Apical NPI", thickness 75μm) as a protective material were used as unwinding rolls. In addition, the crystal orientation degree fp in the plane direction of the thermoplastic liquid crystal polymer film was 0.65, and the crystal orientation degree fv in the thickness direction was 0.80. As shown in FIG. 1 , these unwinding rolls were assembled with 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 the pair of pressure rollers (r ₁ , r ₂ ), the unwinding rollers were arranged so that the order of r ₁ /C ₁ /M ₁ /F/F/M ₂ /C ₂ /r ₂ was achieved.

The laminated body material M ₁ /F/F/M ₂ was introduced into a pair of pressure rollers (r ₁ , r ₂ ) via a pair of polyimide films (C ₁ , C ₂ ). Metal rolls with diameters of 300 mm were used as a pair of pressure rolls (r ₁ , r ₂ ). The laminate material M ₁ /F/F/M ₂ sandwiched by the amine films (C ₁ , C ₂ ) was thermocompression-bonded by passing through a pair of pressure rollers (r ₁ , r ₂ ) at a speed of 3.0 m/min.

After thermocompression bonding, as shown in FIG. 1 , after passing through a pair of pressure rolls (r ₁ , r ₂ ), using the pair of pressure rolls (r ₁ , r ₂ ), a pair of polyimide films were (C ₁ , C ₂ ) were separated simultaneously, and the pair of thermoplastic liquid crystal polymer films (F, F) were separated to obtain two single-sided copper-clad laminates (M ₁ F, M ₂ F), which were taken up by winding rolls. Roll up separately. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.

(Example 2) A thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., "Vecstar" (registered trademark), melting point 310° C., thickness 100 μm) and electrolytic copper foil (Futian Metal Foil Powder Co., Ltd.) as metal foil were prepared. Company made, "CF-H9A-DS-HD2", thickness 12μm), and a polyimide film (Kaneka Co., Ltd. make, "Apical NPI", thickness 75μm) as a protective material were used as unwinding rolls. In addition, the crystal orientation degree fp in the plane direction of the thermoplastic liquid crystal polymer film was 0.60, and the crystal orientation degree fv in the thickness direction was 0.70. As shown in FIG. 1 , these unwinding rolls were assembled with 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 the pair of pressure rollers (r ₁ , r ₂ ), the unwinding rollers were arranged so that the order of r ₁ /C ₁ /M ₁ /F/F/M ₂ /C ₂ /r ₂ was achieved.

The laminated body material M ₁ /F/F/M ₂ was introduced into a pair of pressure rollers (r ₁ , r ₂ ) via a pair of polyimide films (C ₁ , C ₂ ). Metal rolls with diameters of 300 mm were used as a pair of pressure rolls (r ₁ , r ₂ ). The laminate material M ₁ /F/F/M ₂ sandwiched by the amine films (C ₁ , C ₂ ) was thermocompression-bonded by passing through a pair of pressure rollers (r ₁ , r ₂ ) at a speed of 3.0 m/min.

After thermocompression bonding, as shown in FIG. 1 , after passing through a pair of pressure rolls (r ₁ , r ₂ ), using the pair of pressure rolls (r ₁ , r ₂ ), a pair of polyimide films were (C ₁ , C ₂ ) were separated simultaneously, and the pair of thermoplastic liquid crystal polymer films (F, F) were separated to obtain two single-sided copper-clad laminates (M ₁ F, M ₂ F), which were taken up by winding rolls. Roll up separately. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.

(Comparative Example ₁ ) A thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., " _Vecstar " (registered trademark), melting point 310 ℃, thickness 100 μm), electrolytic copper foil, and each unwinding roll of the polyimide film, except that they passed through the pressure roll, thermocompression bonding was carried out in the same manner as in Example 2, and after thermocompression bonding, the separation roll was used to The polyimide film (C) was separated from the laminate to produce two single-sided copper-clad laminates F/M. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.

(Comparative Example 2) Except that the thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., "Vecstar" (registered trademark) was arranged in the order of r ₁ /C ₁ /F/M/M/F/C ₂ /r ₂ ), melting point 310° C., thickness 100 μm), electrolytic copper foil, and each unwinding roll of the polyimide film, except that they passed through the pressure roll, thermocompression bonding was performed in the same manner as in Example 2, and a pair of pressure After the rolls (r ₁ , r ₂ ), using the pair of pressure rolls (r ₁ , r ₂ ), while separating the pair of polyimide films (C ₁ , C ₂ ), the pair of electrolytic copper The foils (M, M) were separated to obtain two single-sided copper-clad laminates (MF, MF), which were respectively wound up with winding rolls. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.

[Table 7] configuration mode Thermoplastic liquid crystal polymer film thickness [μm] Appearance evaluation Example 1 r ₁ /C ₁ /M ₁ /F/F/M ₂ /C ₂ /r ₂ 25 A Example 2 r ₁ /C ₁ /M ₁ /F/F/M ₂ /C ₂ /r ₂ 100 A Comparative Example 1 _r1 /M/F/C/F/M/ _r2 100 B Comparative Example 2 r ₁ /C ₁ /F/M/M/F/C ₂ /r ₂ 100 B

As shown in Table 7, in Examples 1 and 2, since a polyimide film was disposed as a protective material in the outermost layer so as to sandwich the laminate material, these protective materials were connected to the copper foil. Since a pair of pressure rolls were introduced in the arrangement|positioning manner, the appearance defect, such as a wrinkle, was not seen in the obtained copper clad laminated body.

On the other hand, in Comparative Examples 1 and 2, since the protective material was introduced into the pressure roll so as to be adjacent to the thermoplastic liquid crystal polymer film, wrinkles were generated in the obtained copper-clad laminate. [Possibility of Industrial Use]

According to the manufacturing method of the present invention, a metal-clad laminate can be efficiently manufactured, and the obtained metal-clad laminate can be effectively used as a part used in the electrical and electronic fields, office equipment and precision equipment fields, power semiconductor fields, and the like. For example, a circuit board (especially a board for millimeter wave radar).

As above, ideal embodiments of the present invention have been described with reference to the drawings, but those with ordinary knowledge in the technical field to which the present invention pertains can easily conceive various changes and modifications within the scope of self-evidentness in view of the present specification. Therefore, such changes and corrections are to be construed as being within the scope of the invention defined in the scope of the invention.

11: Protective material take-up roll 12: Metal foil take-up roll 13: Thermoplastic liquid crystal polymer film take-up roll 21: Guide roll 31: Protective material take-up roll 32: Metal-clad laminate take-up roll 41, 42, 43: Separation rolls r ₁ , r ₂ : pressure rolls C ₁ , C ₂ : protective material M ₁ , M ₂ : outermost metal foil F: thermoplastic liquid crystal polymer film M: metal foil M ₁ F, M ₂ F, MF, M ₂ FM: Metal-clad laminate

The present invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiment and the drawings are merely for illustration and description, and should not be used to define the scope of the present invention. The scope of the present invention is defined by the scope of the patent application in the appendix. In the attached drawings, the same reference signs in the several drawings refer to the same parts. The drawings are not necessarily shown to a certain scale, and are exaggerated in order to represent the principles of the present invention. 1 is a schematic side view for explaining a method for producing a metal-clad laminate according to a first embodiment of the present invention. [ Fig. 2] Fig. 2 is a schematic side view for explaining a method for producing a metal-clad laminate according to a second embodiment of the present invention. [ Fig. 3] Fig. 3 is a schematic side view for explaining a method for producing a metal-clad laminate according to a third embodiment of the present invention.

11: Protective material roll-out roller

12: Metal foil roll-out roll

13: Thermoplastic liquid crystal polymer film take-up roll

21: Guide roller

31: Protective material take-up roller

32: Metal-clad laminate winding roll

r ₁ , r ₂ : pressure rollers

C ₁ , C ₂ : Protective material

M ₁ , M ₂ : outermost metal foil

F: Thermoplastic liquid crystal polymer film

M ₁ F, M ₂ F: Metal-clad laminate

Claims (8)

A method for manufacturing a metal-clad laminate, which is a method for manufacturing a plurality of metal-clad laminates, which at least includes a thermocompression bonding step and a separation step from a thermoplastic liquid crystal polymer film; the thermocompression bonding step is to connect a pair of One of the pressing rollers (r ₁ , r ₂ ) introduces the laminate material to the protective material (C ₁ , C ₂ ), and uses the pressing roller to bond the laminate material by thermocompression, wherein the laminate material is At least one pair of outermost metal foils (M ₁ , M ₂ ) and at least one pair of thermoplastic liquid crystal polymer films (F, F) are respectively connected to the pair of protective materials (C ₁ , C ₂ ). The laminate material is thermocompression-bonded in a state where the at least one pair of thermoplastic liquid crystal polymer films (F, F) in the laminate material is connected to each other; the thermoplastic liquid crystal polymer film separation step is performed after the thermocompression bonding step. A pair of thermoplastic liquid crystal polymer films (F, F) are separated. The method for producing a metal-clad laminate according to claim 1, comprising a metal foil separation step; The metal foil separation step is performed in the thermocompression bonding step to perform thermocompression bonding of the laminate material in a state in which at least a pair of metal foils (M, M) in the laminate material are connected to each other, The at least one pair of metal foils (M, M) connected to each other are separated after the thermocompression bonding step. The method for producing a metal-clad laminate according to claim 1 or 2, wherein the laminate material is introduced into the pair of pressing rollers (r ₁ , r ₂ ) through the pair of protective materials (C ₁ , C ₂ ) Arrangement in any order of (i) to (vi) below; (i) r ₁ /C ₁ /M ₁ /F/F/M ₂ /C ₂ /r ₂ (ii) r ₁ /C ₁ /M ₁ /F/F/M/M/F/M ₂ /C ₂ /r ₂ (iii)r ₁ /C ₁ /M ₁ /F/M/M/F/F/M/M/F/M ₂ /C ₂ /r ₂ (iv)r ₁ /C ₁ /M ₁ /F/F/M/M/F/F/M ₂ /C ₂ /r ₂ (v)r ₁ /C ₁ /M ₁ / F/F/M/M/F/F/M/M/F/M ₂ /C ₂ /r ₂ (vi)r ₁ /C ₁ /M ₁ /F/M/M/F/F/M/ M/F/F/M/M/F/M ₂ /C ₂ /r ₂ (here, r ₁ , r ₂ : pressure rollers, C ₁ , C ₂ : protective materials, M ₁ , M ₂ : represents the outermost metal foil, F: represents the thermoplastic liquid crystal polymer film, M: represents the metal foil). The method for producing a metal-clad laminate according to any one of claims 1 to 3, wherein at least one of the pair of thermoplastic liquid crystal polymer films (F, F) is a crystal orientation degree fp in the plane direction that is greater than the crystal orientation in the thickness direction Thermoplastic liquid crystal polymer films with a smaller degree fv. The method for producing a metal-clad laminate according to any one of claims 1 to 4, wherein the thermocompression bonding temperature is relative to the thermoplastic liquid crystal polymer film having the lowest melting point among the thermoplastic liquid crystal polymer films in the laminate material The melting point ( _TmL ) is in the range of ( _TmL -120)°C to ( _TmL )°C. The method for producing a metal-clad laminate according to any one of claims 1 to 5, wherein the peel strength of the thermoplastic liquid crystal polymer film (F) and the thermoplastic liquid crystal polymer film (F) after thermocompression bonding is 0.3 kN/m the following. The method for producing a metal-clad laminate according to any one of claims 1 to 6, wherein the difference in melting points of the thermoplastic liquid crystal polymer films connected to each other in the laminate material is in the range of 0 to 70°C. The method for producing a metal-clad laminate according to any one of claims 1 to 7, wherein the protective material (C ₁ ) and/or the protective material (C ₂ ) are selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film, and A protective material for the group of heat-resistant non-woven fabrics.

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