JP6316178B2 - Single-sided metal-clad laminate and manufacturing method thereof - Google Patents

Description

  The present invention relates to a film comprising a thermoplastic polymer that can form an optically anisotropic melt phase (hereinafter sometimes abbreviated as a thermoplastic liquid crystal polymer) (hereinafter abbreviated as a thermoplastic liquid crystal polymer film). And a method of manufacturing the same.

  Conventionally, when a metal-clad laminate used for a printed wiring board or the like is manufactured using a thermoplastic liquid crystal polymer film, a method for continuously producing the metal-clad laminate has been proposed. For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 5-42603), a film made of a liquid crystal polymer that forms an optically anisotropic molten layer and a metal foil are overlapped to form a pressure roll as a thermocompression bonding means. The laminate and the metal foil are pressure-bonded at a temperature within a range from 80 ° C. to 5 ° C. lower than the melting point of the liquid crystal polymer. Is disclosed.

JP-A-5-42603

  A conventional method for producing a single-sided metal-clad laminate, in which a thermoplastic liquid crystal polymer film and a metal sheet are passed between heated rolls to form a laminate by thermocompression bonding, and the metal sheet is bonded to one side of the film Therefore, in order to prevent fusion between the thermoplastic liquid crystal polymer film and the roll as the thermocompression bonding means during the thermocompression bonding, a release material such as a polyimide film needs to be interposed between the roll and the thermoplastic liquid crystal polymer film. there were.

  Thermoplastic liquid crystal polymer film may be subjected to surface treatment such as roughening treatment on its surface in order to increase the adhesive strength (peel strength) with other materials. When thermocompression bonding is performed, if a release material is interposed between the thermocompression bonding means such as a roll and the thermoplastic liquid crystal polymer film, the surface roughness of the surface of the thermoplastic liquid crystal polymer film on the side in contact with the release material during thermocompression bonding is reduced. It will decline. In such a case, since the surface roughness of the surface of the thermoplastic liquid crystal polymer film in the single-sided copper-clad laminate formed as a result of thermocompression bonding that is not joined to the metal sheet is low, the single-sided copper-clad laminate However, there is a problem that the peel strength is lowered when the film is laminated with another material in a later step.

  In addition, the polyimide film once used as a mold release material is difficult to reuse due to scratches and foreign matter adhering, and there are problems in terms of productivity and cost.

  In addition, when a release material such as a polyimide film is not used, a part of the thermoplastic liquid crystal polymer film is fused to the roll during the thermocompression bonding, and the appearance of the thermoplastic liquid crystal polymer film surface after the pressure bonding or mixing of foreign matters, There was a problem that caused tearing of the single-sided metal-clad laminate.

  As described above, in the conventional technique, when the thermoplastic liquid crystal polymer film and the metal sheet are thermocompression bonded using a thermocompression bonding means such as a roll, a release material is provided between the thermoplastic liquid crystal polymer film and the thermocompression bonding means. In this case, there is a problem that the surface roughness of the surface of the thermoplastic liquid crystal polymer film on the side in contact with the mold release material is lowered. On the other hand, the thermoplastic liquid crystal polymer film and the metal sheet are not interposed with the mold release material. When thermocompression bonding, there is a problem that fusion between the thermoplastic liquid crystal polymer film and the thermocompression bonding means occurs.

  The inventors of the present invention produce a single-sided metal-clad laminate in which a thermoplastic liquid crystal polymer film and a metal sheet are thermocompression-bonded to form a laminate, and the metal sheet is bonded to one side of the thermoplastic liquid crystal polymer film. In this case, the temperature of the thermoplastic liquid crystal polymer film is adjusted to a temperature at which the compression modulus (G ′) is within a specific value range, thereby separating the thermoplastic liquid crystal polymer film from the thermocompression bonding means. Even without using a mold material, it is possible to prevent fusion between the thermoplastic liquid crystal polymer film and the thermocompression bonding means. Further, by not using a mold release material, the surface roughness of the thermoplastic liquid crystal polymer film during the thermocompression bonding can be reduced. The surface roughness of the thermoplastic liquid crystal polymer film in the formed single-sided metal-clad laminate can be kept high, and good peel strength, film appearance and soldering can be achieved. It found to be able to produce a single-sided metal-clad laminate having heat resistance, and have completed the present invention.

That is, the present invention is a single-sided metal-clad laminate in which a metal sheet is bonded to one side of a thermoplastic liquid crystal polymer film, and the single-sided metal-clad laminate is bonded to a metal sheet of a thermoplastic liquid crystal polymer film. The arithmetic mean roughness (Ra) measured by a method according to ISO 4287-1997 on the non-side surface is 0.1 to 0.5 μm, and the ten-point average roughness (Rz _JIS ) is 0.5 to 2.0 μm. It is a single-sided metal-clad laminate.

The present invention also relates to a method for producing a single-sided metal-clad laminate in which a thermoplastic liquid crystal polymer film and a metal sheet are thermocompression bonded to form a laminate, and the metal sheet is bonded to one side of the thermoplastic liquid crystal polymer film. In the thermocompression bonding, a release material is not interposed between the thermocompression bonding means and the thermoplastic liquid crystal polymer film, and the side of the single-sided metal-clad laminate that is not joined to the metal sheet of the thermoplastic liquid crystal polymer film The arithmetic average roughness (Ra) measured by a method based on ISO 4287-1997 is 0.1 to 0.5 μm, and the ten-point average roughness (Rz _JIS ) is 0.5 to 2.0 μm. A method for producing a single-sided metal-clad laminate.

In the production method, the temperature of the thermoplastic liquid crystal polymer film is adjusted to a temperature at which the compression modulus (G ′) of the thermoplastic liquid crystal polymer film is 1 × 10 ⁷ Pa or more during thermocompression bonding. The manufacturing method of the single-sided metal-clad laminated board characterized by these may be sufficient.

Further, the manufacturing method is such that a thermoplastic liquid crystal polymer film and a metal sheet are run, passed between heated rolls while being combined, and subjected to thermocompression bonding, and a metal sheet is provided on one side of the thermoplastic liquid crystal polymer film that forms a laminate. A method for producing a single-sided metal-clad laminate obtained by bonding, wherein the temperature of a roll in contact with the thermoplastic liquid crystal polymer film among the rolls is such that the compression modulus (G ′) of the thermoplastic liquid crystal polymer film is 1 It may be a method for producing a single-sided metal-clad laminate, wherein the temperature is adjusted to 10 ⁷ Pa or higher.

  Moreover, the said manufacturing method is the single-sided metal-clad laminated board whose temperature of the roll which touches a metal sheet in the said thermocompression bonding is a temperature 5-100 degreeC lower than melting | fusing point of the said thermoplastic liquid crystal polymer film. It may be a manufacturing method.

  Moreover, the said manufacturing method may be a manufacturing method of the single-sided metal laminated board whose roll which touches a thermoplastic liquid crystal polymer film among the said rolls at the time of the said thermocompression bonding is a resin-coated metal roll.

  Moreover, the manufacturing method of the single-sided metal laminated plate which is preferably a resin-coated metal roll in which the resin-coated metal roll is provided with a resin layer having a thickness of 7 mm to 40 mm on the surface of the metal roll may be used.

  The manufacturing method of the present invention may be a method for manufacturing a single-sided metal-clad laminate in which the means for thermocompression bonding is a double belt press.

  Moreover, the manufacturing method of this invention may be a manufacturing method of the single-sided metal clad laminated body whose melting | fusing point of a thermoplastic liquid crystal polymer film is 270 degreeC or more and 345 degrees C or less.

  The single-sided metal-clad laminate of the present invention is excellent in laminating the single-sided metal-clad laminate with other materials because the surface roughness of the thermoplastic liquid crystal polymer film is maintained even after thermocompression bonding. High peel strength can be imparted. Further, the single-sided metal-clad laminate itself has a good appearance and solder heat resistance because the thermoplastic liquid crystal polymer and the metal sheet are bonded with high peel strength.

  In addition, the single-sided metal-clad laminate of the present invention does not use a release material such as polyimide in the thermocompression bonding step, and thus can be manufactured with high production efficiency and low cost.

It is the figure which showed typically the manufacturing method of the single-sided metal clad laminated board of this invention, and is a schematic diagram at the time of using a roll press as a thermocompression-bonding means.

  The thermoplastic liquid crystal polymer film constituting the film body is formed from a liquid crystalline polymer that can be melt-molded. The thermoplastic liquid crystal polymer is a polymer that can form an optically anisotropic melt phase, and is not particularly limited in terms of its chemical configuration as long as it is a liquid crystal polymer that can be melt-molded. , Thermoplastic liquid crystal polyester, or thermoplastic liquid crystal polyester amide having an amide bond introduced therein.

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

  Specific examples of the thermoplastic liquid crystal polymer used in the present invention include known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides derived from the compounds (1) to (4) listed below 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 melt phase.

(1) Aromatic or aliphatic dihydroxy compounds (see Table 1 for typical examples)

(2) Aromatic or aliphatic dicarboxylic acids (see Table 2 for typical examples)

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

(4) Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for typical examples)

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

  Among these copolymers, a polymer containing at least p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid as a repeating unit is preferable. In particular, (i) p-hydroxybenzoic acid and 6-hydroxy- A polymer containing a repeating unit with 2-naphthoic acid, (ii) at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and 4,4 ′ A repeating unit of at least one aromatic diol selected from the group consisting of dihydroxybiphenyl and hydroquinone and at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid Polymers containing are preferred.

  For example, in the polymer (i), when the thermoplastic liquid crystal polymer contains at least repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, p-hydroxybenzoic acid of the repeating unit (A) And the molar ratio (A) / (B) of 6-hydroxy-2-naphthoic acid of the repeating unit (B) is about (A) / (B) = 10/90 to 90/10 in the liquid crystal polymer. It is desirable that (A) / (B) = about 50/50 to 85/15, more preferably (A) / (B) = about 60/40 to 80/20. It may be.

  In the case of the polymer (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′-dihydroxy At least one aromatic diol (D) selected from the group consisting of biphenyl and hydroquinone, and at least one aromatic dicarboxylic acid (E) selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. The molar ratio of each repeating unit in the liquid crystal polymer is about aromatic hydroxycarboxylic acid (C): aromatic diol (D): aromatic dicarboxylic acid (E) = about 30-80: 35-10: 35-10. More preferably, (C) :( D) :( E) = 35 to 75: 32.5 to 12.5: 3 May be about .5～12.5, more preferably, (C) :( D) :( E) = 40~70: it may be about 30 to 15: 30-15.

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

  The optical anisotropy at the time of melting referred to in the present invention can be recognized by, for example, placing a sample on a hot stage, heating and heating in a nitrogen atmosphere, and observing the transmitted light of the sample.

  Further, as the thermoplastic liquid crystal polymer, those having a melting point in the range of about 200 to about 400 ° C., particularly in the range of about 250 to about 350 ° C., for the purpose of obtaining the desired heat resistance and processability of the film. Although preferred, those having a relatively low melting point are preferred from the viewpoint of film production.

  The thermoplastic liquid crystal polymer may be a thermoplastic polymer such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyether ether ketone, and fluororesin within a range not impairing the effects of the present invention. Various additives may be added. Moreover, you may add a filler as needed.

  The thermoplastic liquid crystal polymer film used in the present invention is obtained by extrusion molding of a thermoplastic liquid crystal polymer. Any extrusion molding method can be applied as long as the direction of the rigid rod-like molecules of the thermoplastic liquid crystal polymer can be controlled, but the known T-die method, laminate stretching method, inflation method and the like are industrially advantageous. In particular, in the inflation method and the laminate stretching method, stress is applied not only to the machine axis direction of the film (or machine processing direction: hereinafter abbreviated as MD direction) but also to the direction orthogonal to this (hereinafter abbreviated as TD direction). Thus, a film in which the molecular orientation in the MD direction and the TD direction, the dielectric properties, etc. are controlled can be obtained.

  In extrusion molding, it is preferable to accompany a stretching process in order to control the orientation. For example, in extrusion molding by the T-die method, the melt sheet extruded from the T-die is not only in the MD direction of the film but also in the TD. The melt sheet extruded from the T-die may be stretched in the MD direction and then stretched in the TD direction.

  In addition, in the extrusion molding by the inflation method, a predetermined draw ratio (corresponding to a stretching ratio in the MD direction) and a blow ratio (corresponding to a stretching ratio in the TD direction) with respect to a cylindrical sheet melt-extruded from a ring die. May be stretched.

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

  The ratio of the stretching ratios in the MD direction and the TD direction (TD direction / MD direction) may be, for example, 2.6 or less, preferably about 0.4 to 2.5.

  The thermoplastic liquid crystal polymer film may be stretched as necessary after extrusion. The stretching method itself is known, and either biaxial stretching or uniaxial stretching may be adopted, but biaxial stretching is preferred because it is easier to control the degree of molecular orientation. For stretching, a known uniaxial stretching machine, simultaneous biaxial stretching machine, sequential biaxial stretching machine or the like can be used.

Further, if necessary, known or conventional heat treatment may be performed to adjust the melting point and / or the 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 liquid crystal polymer is −10 ° C. or higher (for example, about Tm ₀ −10 to Tm ₀ + 30 ° C., preferably about Tm ₀ to Tm ₀ + 20 ° C.). The melting point (Tm) of the thermoplastic liquid crystal polymer film may be increased by heating for several hours.

  The thermoplastic liquid crystal polymer film thus obtained has excellent dielectric properties, gas barrier properties, low hygroscopicity, and the like, and therefore can be suitably used as a circuit board material.

  The melting point of the thermoplastic liquid crystal polymer film can be selected within a range of about 200 to 400 ° C., preferably about 250 to 360 ° C., more preferably 260 for the purpose of obtaining desired heat resistance and processability of the film. About 350 degreeC (for example, 270-345 degreeC) may be sufficient.

  The thermoplastic liquid crystal polymer film used in the present invention may have any thickness. However, when used for a high-frequency transmission line, the transmission loss decreases as the thickness increases, so it is preferable to increase the thickness as much as possible. When a thermoplastic liquid crystal polymer film is used as the electrical insulating layer, the film thickness is preferably in the range of 10 to 500 μm, more preferably in the range of 10 to 300 μm, still more preferably 10 to 200 μm (for example, 15 to 150 μm) is more preferable. When the thickness of the film is too thin, the rigidity and strength of the film are reduced. Therefore, a method of obtaining an arbitrary thickness by laminating films having a film thickness in the range of 10 to 200 μm may be used.

  The thermoplastic liquid crystal polymer film may have a surface subjected to a roughening treatment. The means for the roughening treatment is not particularly limited, and for example, physical polishing or ultraviolet irradiation may be used, or solution treatment or plasma treatment may be used.

  When a thermoplastic liquid crystal polymer is formed and formed into a thermoplastic liquid crystal polymer film, a hard skin layer may be formed on the surface. This hard skin layer is applied to a thermoplastic liquid crystal polymer film and a metal sheet. When a laminated body is bonded to the body, good pressure bonding may be hindered and the peel strength of the laminated body may be reduced. Therefore, the surface of the thermoplastic liquid crystal polymer film after film formation may be polished in order to remove the hard skin layer that hinders the improvement in peel strength. However, when the surface of the thermoplastic liquid crystal polymer film is polished in this way to remove the hard skin layer and the soft layer inside the film is exposed on the film surface, the surface is coated with the thermoplastic liquid crystal polymer film subjected to surface polishing. When the body is thermocompression bonded, the thermocompression bonding means and the thermoplastic liquid crystal polymer film may be more easily fused. In the production method of the present invention, even when the thermoplastic liquid crystal polymer film and the metal sheet having such a surface polished to remove the hard skin layer are heat-bonded, the film and the heat-bonding means are fused. It is possible to manufacture a single-sided metal-clad laminate that is pressed with a good peel strength.

  Examples of the physical polishing method include brush polishing, blast polishing, belt polishing, and barrel polishing, and the surface layer of the liquid crystal polymer film is removed by these polishings.

More specifically, in brush polishing, the surface of a liquid crystal polymer can be polished by rotating a brush of a wire rod such as a brass wire, nylon wire, or steel wire containing an abrasive at high speed and rubbing the processed surface of the liquid crystal polymer film. .
In blast polishing, the surface of the liquid crystal polymer can be polished by spraying a solid metal, mineral or vegetable abrasive on the processed surface of the liquid crystal polymer film at high speed together with compressed air.
In belt polishing, the surface of the liquid crystal polymer can be polished by rubbing a belt with an abrasive (endless belt sandpaper) against the processed surface of the liquid crystal polymer film.
In barrel polishing, the target object, abrasive and water are mixed and filled in the polishing tank, and the movement (rotation and vibration) is applied to the polishing tank, and the target object and the abrasive in the tank rub against each other to rub the surface of the liquid crystal polymer. Can be polished.

  By this polishing method, the hard skin layer (especially the surface skin layer) present on the surface of the liquid crystal polymer film can be removed, and the relatively soft core layer inside the liquid crystal polymer film can be exposed. Can be improved. In physical polishing, it is preferable to remove a thickness of about 0.01 to 1 μm from the film surface, and more preferably, a surface layer may be removed with a thickness of about 0.1 to 0.9 μm.

  On the other hand, since the skin layer existing in the liquid crystal polymer film can be broken and the hardness of the film surface can be softened even by ultraviolet irradiation, the adhesiveness by thermocompression bonding can be improved. The ultraviolet irradiation is not particularly limited as long as a predetermined hardness can be imparted to the liquid crystal polymer film surface, but it is preferable to simultaneously irradiate ultraviolet rays having wavelengths of 185 nm and 254 nm.

  Further, from the viewpoint of promptly destroying only the surface layer, it is preferable to reduce the distance between the irradiation surface and the light source and to irradiate with high irradiation energy for a short time. For example, the distance between the irradiation surface and the light source may be about 0.3 cm to 5 cm, preferably about 0.4 to 2 cm. Moreover, although processing time can be suitably set according to the distance of an irradiation surface and a light source, it may be about 20 seconds-5 minutes, for example, Preferably it may be about 30 seconds-3 minutes.

As for the surface roughness of the thermoplastic liquid crystal polymer film, the arithmetic average roughness (Ra) measured by a method according to ISO 4287-1997 is preferably 0.1 to 0.5 μm, more preferably 0.1 to 0.4 μm. 0.1 to 0.3 μm is more preferable. Further, preferably ten-point average roughness as measured by a method in accordance with ISO4287-1997 _{(Rz JIS)} is 0.5 to 2.0 [mu] m, 0.7～1.8Myuemu more preferably, 0.8 More preferably, ˜1.5 μm.

  The material of the metal sheet used in the present invention is selected from metals used for electrical connection, and examples thereof include gold, silver, copper, nickel, and aluminum. Among these, copper is particularly preferable. As copper, any copper produced by a rolling method or an electrolysis method can be used, but copper having a large surface roughness produced by an electrolysis method is preferred. The metal sheet may be subjected to chemical surface treatment such as acid cleaning usually applied to the copper foil as long as the effects of the present invention are not impaired. As thickness of a metal sheet, the range of 7-100 micrometers is preferable, and the inside of the range of 9-75 micrometers is more preferable.

The single-sided metal-clad laminate of the present invention has an arithmetic average roughness (Ra) measured by a method based on ISO 4287-1997 on the surface of the laminate not joined to the metal sheet of the thermoplastic liquid crystal polymer film. Is 0.1 to 0.5 μm, 10-point average roughness (Rz _JIS ) is 0.5 to 2.0 μm, and arithmetic average roughness (Ra) is preferably 0.1 to 0.4 μm. 1 to 0.3 μm is more preferable. Further, the ten-point average roughness (Rz _JIS ) measured by a method based on ISO4287-1997 is preferably 0.7 to 1.8 μm, and more preferably 0.8 to 1.5 μm. When the surface roughness is within this range, even when the single-sided metal-clad laminate is laminated with another material in a later step, it can be bonded with good peel strength.

When the arithmetic average roughness (Ra) of the thermoplastic liquid crystal polymer film in the single-sided metal-clad laminate is less than 0.1 μm or the ten-point average roughness (Rz _JIS ) is less than 0.5 μm, the single-sided metal-clad laminate When the thermoplastic liquid crystal polymer film surface of the plate is laminated with another material, there arises a problem that high peel strength cannot be obtained.

In addition, when the arithmetic average roughness (Ra) of the thermoplastic liquid crystal polymer film in the single-sided metal-clad laminate exceeds 0.5 μm or the ten-point average roughness (Rz _JIS ) exceeds 2.0 μm, this single side When the thermoplastic liquid crystal polymer film surface of a metal-clad laminate is pressure bonded to a conductive layer of another circuit board material, the surface roughness of the thermoplastic liquid crystal polymer film deteriorates the surface roughness of the conductive layer of the other circuit board material. As a result, problems such as deterioration of the high frequency characteristics of the conductive layer occur.

In order to make the arithmetic average roughness (Ra) and ten-point average roughness (Rz _JIS ) of the thermoplastic liquid crystal polymer film in the single-sided metal-clad laminate of the present invention within the above ranges, the film and the metal sheet are When heating and pressing, it is important that no release material is interposed between the thermocompression bonding means and the film.

The means for thermocompression bonding the thermoplastic liquid crystal polymer film and the metal sheet to bring the arithmetic average roughness (Ra) and ten-point average roughness (Rz _JIS ) of the thermoplastic liquid crystal polymer film into the above ranges is not particularly limited. For example, it may be a batch type heat press, or a roll-to-roll type roll press or a double belt press. In particular, a roll press or a double belt press is preferable from the viewpoint of productivity.

In the present invention, when the thermoplastic liquid crystal polymer film and the metal sheet are heat-bonded, the temperature of the thermoplastic liquid crystal polymer film is such that the compressive elastic modulus (G ′) of the thermoplastic liquid crystal polymer film is 1 × 10 ⁷ Pa or more. The temperature at which the compression modulus (G ′) is 2 × 10 ⁷ Pa or more is more preferable, and the temperature at which the compression modulus (G ′) is 4 × 10 ⁷ Pa or more is further preferable. preferable. Further, from the viewpoint of preventing fusion between the thermoplastic liquid crystal polymer film and the thermocompression bonding means during thermocompression bonding, the upper limit of the compression elastic modulus (G ′) of the thermoplastic liquid crystal polymer film during thermocompression bonding is It may be equal to or less than the value of the compressive elastic modulus (G ′) at room temperature (for example, 25 ° C.) of the plastic liquid crystal polymer film, and may be, for example, 1 × 10 ⁹ Pa or less.

  When the temperature condition of the thermoplastic liquid crystal polymer film at the time of thermocompression bonding between the thermoplastic liquid crystal polymer film and the metal sheet satisfies the above conditions, a release material is not interposed between the thermoplastic liquid crystal polymer film and the thermocompression bonding means. However, it is possible to prevent the thermoplastic liquid crystal polymer film and the pressure bonding means from being fused, and to bond the thermoplastic liquid crystal polymer film and the metal sheet with good peel strength.

The temperature condition of the thermoplastic liquid crystal polymer film at the time of thermocompression bonding between the thermoplastic liquid crystal polymer film and the metal sheet is outside the above range, and the compression elastic modulus (G ′) of the thermoplastic liquid crystal polymer film at the time of thermocompression bonding is 1 ×. When the pressure is less than 10 ⁷ Pa, the thermoplastic liquid crystal polymer film is fused to the thermocompression bonding means that comes into contact with the thermoplastic liquid crystal polymer film during thermocompression bonding, and the thermocompression bonding means is soiled. This may cause problems during use, poor appearance of the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate after crimping, mixing of foreign substances, and wrinkling or tearing of the single-sided metal-clad laminate.

In controlling the temperature of the thermocompression bonding means at the time of thermocompression bonding, the compression modulus (G ′) of the thermoplastic liquid crystal polymer film is 1 × 10 ⁷ Pa before thermocompression bonding of the thermoplastic liquid crystal polymer film and the metal sheet. You may measure the temperature used as the above and control the temperature of a thermocompression-bonding means so that it may become in the temperature range.

  Regarding the relationship between the compression modulus (G ′) and temperature of the thermoplastic liquid crystal polymer film, the compression modulus (G ′) was measured at regular intervals while raising the temperature of the thermoplastic liquid crystal polymer film at a constant temperature. The relationship between the temperature of the thermoplastic liquid crystal polymer film and the compression modulus (G ′) may be measured.

In the case of a thermoplastic liquid crystal polymer film, the compression elastic modulus (G ′) of the film decreases as the temperature of the thermoplastic liquid crystal polymer film increases, but the temperature at which the compressive elastic modulus (G ′) becomes 1 × 10 ⁷ Pa is However, a thermoplastic liquid crystal polymer film having a high melting point is not necessarily higher than a thermoplastic liquid crystal polymer film having a low melting point, and the temperature at which the compression modulus (G ′) is 1 × 10 ⁷ Pa is a thermoplastic liquid crystal polymer. It is speculated that it depends on the crystal structure of the film.

Next, the method for producing a single-sided metal-clad laminate of the present invention will be described with reference to the drawings, taking as an example the case where a roll press is used as the thermocompression bonding means.
The embodiment of the present invention is not limited to this example.

  FIG. 1 is a view schematically showing a method for producing a single-sided metal-clad laminate of the present invention, in which a thermoplastic liquid crystal polymer film 1 and a metal sheet 2 are in contact with a thermoplastic liquid crystal polymer film 1; The process of introducing between the metal sheet 2 and the heating roll 4 in contact with the metal sheet 2 and thermocompression bonding to form a single-sided metal-clad laminate 5 is shown. At the time of thermocompression bonding, for example, the temperature of the roll 3 is controlled by the temperature control means 6.

  Although it does not specifically limit as a roll material of the said heating roll 4, For example, a rubber roll, a metal roll, and a resin-coated metal roll may be sufficient. In particular, a metal roll is preferable from the viewpoint that pressure can be uniformly applied during thermocompression bonding.

  When the thermoplastic liquid crystal polymer film 1 and the metal sheet 2 are run and thermocompression bonded, the surface of the heating roll 4 in contact with the metal sheet 2 is heated by some means. The heating means is not particularly limited, but for example, a heating mechanism may be provided inside the heating roll 4 to heat the surface of the heating roll 4. The surface temperature of the heating roll 4 is preferably lower in the range of 5 to 100 ° C. than the melting point of the liquid crystal polymer film 1, and more preferably 5 to 70 ° C. lower than the melting point of the liquid crystal polymer film 1. By making the surface temperature of the heating roll 4 100 ° C. lower than the melting point of the liquid crystal polymer film 1, the liquid crystal polymer film 1 and the metal sheet 2 can be sufficiently bonded. When the temperature is 5 ° C. or lower than the melting point of the liquid crystal polymer film 1, the flow of the liquid crystal polymer film 1 at the time of thermocompression bonding can be suppressed, and the single-sided metal-clad laminate 5 having a good appearance can be manufactured.

In the present invention, when a roll is used as the thermocompression bonding means, when the thermoplastic liquid crystal polymer film 1 and the metal sheet 2 are thermocompression bonded, the temperature of the roll 3 on the side in contact with the thermoplastic liquid crystal polymer film 1 is set to the thermoplastic liquid crystal. It is important to control the temperature so that the compression elastic modulus (G ′) of the polymer film 1 is 1 × 10 ⁷ Pa or more.

  By controlling the temperature of the roll 3 on the side in contact with the thermoplastic liquid crystal polymer film 1 as described above, fusion between the thermoplastic liquid crystal polymer film 1 and the roll 3 at the time of thermocompression bonding can be prevented. Between the roll 3 and the thermoplastic liquid crystal polymer film 1, the thermoplastic liquid crystal polymer film 1 and the metal sheet 2 can be pressure-bonded with good peel strength without using a release material such as a polyimide film.

  By keeping the compression modulus (G ′) of the thermoplastic liquid crystal polymer film high, the adhesiveness with the roll can be lowered, and the adhesion of the thermoplastic liquid crystal polymer film to the thermocompression bonding means such as the roll is suppressed. be able to.

  The roll 3 on the side in contact with the thermoplastic liquid crystal polymer film 1 is in contact with the heating roll 4 and is heated by transferring the heat of the heating roll 4 to the surface of the roll 3.

When no means for controlling the temperature of the surface of the roll 3 on the side in contact with the thermoplastic liquid crystal polymer film 1 is applied, the temperature of the surface of the roll 3 rises to near the temperature of the surface of the heating roll 4 in the process of thermocompression bonding. When the temperature of the surface of the roll 3 reaches a temperature at which the compression modulus (G ′) of the thermoplastic liquid crystal polymer film 1 is less than 1 × 10 ⁷ Pa, the thermoplastic liquid crystal polymer film 1 and the roll 3 described above Temperature control for controlling the temperature of the surface of the roll 3 within a temperature range in which the compression modulus (G ′) of the thermoplastic liquid crystal polymer film 1 is 1 × 10 ⁷ Pa or more. Means 6 are required.

If the temperature control means 6 of the roll 3 on the side in contact with the thermoplastic liquid crystal polymer film 1 can be controlled to a temperature at which the compression modulus (G ′) of the thermoplastic liquid crystal polymer film 1 in contact with the roll 3 is 1 × 10 ⁷ Pa or more. Although not particularly limited, for example, it may be an air cooling system, a heat medium circulation system, or a line speed for running the thermoplastic liquid crystal polymer film 1 and the metal sheet 2 or a rotation speed of a roll, or these temperature control means It may be a combination.

  According to the present invention, in order to obtain a single-sided metal-clad laminate having a good appearance and excellent adhesion, the thermoplastic liquid crystal polymer film 1 and the metal sheet 2 are used from the viewpoint of temperature control of the roll 3 in contact with the thermoplastic liquid crystal polymer film. Is preferably 30 m / min or less in terms of the linear velocity of the outer periphery, and the heat transfer to the metallic sheet 2 In order to make it easy, it is more preferable to set it as 20 m / min or less. The lower limit of the rotation speed of the heating roll 4 is not particularly limited. However, if the rotation speed is too low, production efficiency is reduced. Therefore, it is preferable that the rotation speed is not lower than 0.1 m / min industrially. More than minutes are more preferable.

  Although the material of the roll 3 which contacts the said thermoplastic liquid crystal polymer film is not specifically limited, For example, a rubber roll, a metal roll, and a resin-coated metal roll may be sufficient, and a resin-coated metal roll is especially preferable.

  By using the resin-coated metal roll, when the thermoplastic liquid crystal polymer film 1 and the metal sheet 2 are thermocompression bonded, the shearing force can be suppressed by the buffering effect of the resin-coated metal roll in contact with the thermoplastic liquid crystal polymer film 1. Moreover, since the resin-coated metal roll sufficiently diffuses the heat from the heating roll 4 side, the surface temperature in contact with the thermoplastic liquid crystal polymer film 1 can be controlled more easily.

  As the material of the resin layer coated on the surface of the metal roll of the resin-coated metal roll, a material containing rubber is preferable. For example, a material containing fluorine rubber, silicon rubber, polyimide, or the like is used from the viewpoint of heat resistance and elasticity. preferable.

  The thickness of the resin layer coated on the surface of the metal roll of the resin-coated metal roll is preferably in the range of 7 mm to 40 mm, and more preferably in the range of 10 mm to 25 mm. When the thickness of the resin layer coated on the surface of the metal roll is in the above range, heat transfer from the heating roll 4 and cooling are facilitated, and temperature control of the surface of the roll 3 can be easily performed.

  The hardness of the resin layer coated on the surface of the metal roll is in the range of 60 to 95 degrees in terms of the spring hardness (JIS A) based on the A-type spring hardness test according to JIS K6301 from the viewpoint of applying pressure uniformly. There may be.

  Although the diameter of the roll 3 which contacts the metal roll 4 and the thermoplastic liquid crystal polymer film 1 used in the present invention is not particularly limited, a range of 35 to 45 cm is preferable from the viewpoint of facilitating the temperature control of the roll.

  Further, the pressure applied to the thermoplastic liquid crystal polymer film 1 and the metal sheet 2 between the heating roll 4 and the roll 3 in contact with the thermoplastic liquid crystal polymer film 1 is a combination of rolls that do not substantially deform at the pressurization site. If it is, it is preferably 5 kg / cm or more in terms of linear pressure in order to develop sufficient adhesive force.

When the heating roll 4 has a rubber coating layer on the surface, the coating layer is deformed at the time of pressurization due to the rubber material of the coating layer, the force applied to the heating roll, etc., so that the thermoplastic liquid crystal polymer film 1 and The pressure applied to the metal sheet 2 is preferably 20 kg / cm ² or more in terms of surface pressure. In such a case, the occurrence of poor appearance such as spots can be suppressed and sufficient adhesive force can be expressed.

The upper limit of the pressure is not particularly limited, but the adhesive force of the single-sided metal-clad laminate 5 is sufficiently developed in a state where there is no flow when the thermoplastic liquid crystal polymer film 1 is pressed and no protrusion from the metal sheet 2. For this, it is desirable that the pressure does not exceed 400 kg / cm 2 in terms of linear pressure, or 200 kg / cm ^{2 in} terms of the surface pressure.

Needless to say, when the surface temperature of the heating roll 4 is in a low temperature range, the flow of the thermoplastic liquid crystal polymer film 1 and the metal sheet do not protrude even when the pressure is exceeded.
The linear pressure of the heating roll 4 is a value obtained by dividing the force (crimp load) applied to the heating roll 4 by the effective width of the heating roll 4. Moreover, said surface pressure is the value which remove | divided the crimping | compression-bonding load by the area of the pressurization surface formed by the deformation | transformation of the heating roll 4 at the time of crimping | compression-bonding.

  According to the production method of the present invention, the film can be bonded without causing the fusion between the film and the thermocompression bonding means without using a release material between the thermoplastic liquid crystal polymer film and the thermocompression bonding means. The surface roughness of the film can be maintained even in a single-sided metal-clad laminate after pressure bonding.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not restrict | limited at all by this. In the following examples and comparative examples, the measurement or evaluation of the melting point of the thermoplastic liquid crystal polymer film, the adhesive strength of the single-sided metal-clad laminate, and the appearance was performed as follows.

(Melting point (℃))
The film was obtained by observing the thermal behavior of the film using a differential scanning calorimeter. That is, after the sample film was heated at a rate of 20 ° C./min and completely melted, the melt was quenched at a rate of 50 ° C./min at 50 ° C./min, and again at a rate of 20 ° C./min. The position of the endothermic peak that appears when the temperature was raised was recorded as the melting point (° C.) of the film.

(Surface roughness: arithmetic average roughness (Ra) (μm) and ten-point average roughness (Rz _JIS ) (μm) measurement method)
Arithmetic average roughness of the surface of the single-sided metal-clad laminate that is not joined to the metal sheet of the thermoplastic liquid crystal polymer film using a contact surface roughness meter (Mitutoyo Co., Ltd., model SJ-201) (Ra) and ten-point average roughness (Rz _JIS ) were measured. The measurement was performed by the method based on ISO4287-1997. More specifically, Ra indicates the average value of the absolute value deviation from the average line, and the surface roughness (Rz _JIS ) is obtained by extracting the reference length from the roughness curve in the direction of the average line, The difference between the average value of the altitude at the top (convex apex) from the 5th to the 5th and the average value of the altitude at the bottom (concave bottom) from the deepest to the 5th is expressed in μm. The roughness is shown.

(Compressive modulus (G ') (Pa))
The compression elastic modulus (G ′) was measured using a rotational rheometer ARES-2KFRT-N1 (TA Instruments).
(Measurement conditions: frequency 1 Hz, temperature increase rate 4 ° C./min, measured every 20 seconds, temperature: 200 ° C. to 350 ° C., strain 1%)

(Fusion between film and roll)
The roll on the side in contact with the thermoplastic liquid crystal polymer after thermocompression bonding was visually confirmed, and the presence or absence of fusion of the thermoplastic liquid crystal polymer film to the roll was examined.

(Peel strength (kN / m))
A 1.0 cm wide peel test piece was prepared from a single-sided metal-clad laminate, the film layer was fixed to a flat plate with a double-sided adhesive tape, and a metal sheet was fed at a speed of 50 mm / min according to JIS C5016 by the 180 ° method. The strength when peeled with was measured.

(appearance)
A single-sided metal-clad laminate is visually observed. When the length is 200 m or more, no wrinkle, streak, or deformation is observed, and less than 1 wrinkle, streak, or deformation is observed per 1 m length. A case where one or more wrinkles, streaks, deformations, unattached portions were observed per 1 m was evaluated as x.

(Solder heat resistance)
The crimped single-sided copper-clad laminate was formed into a 30 mm × 30 mm square, then floated in a 320 ° C. solder bath for 60 seconds, and then visually checked for swelling and deformation. In the case where no blistering or deformation was observed in the appearance, it was marked as ◯, and when it was observed as x.

[Reference Example 1]
A thermoplastic safe liquid crystal polymer having a melting point of 280 ° C., which is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, is melt-extruded at a discharge rate of 20 kg / hour, and a transverse draw ratio is 4.77 times. Inflation was formed under the condition of a longitudinal draw ratio of 2.09 times. A thermoplastic liquid crystal polymer film having an average film thickness of 50 μm and a film thickness distribution of ± 7% was obtained.

About the obtained thermoplastic liquid crystal polymer film, high-speed rotational polishing was performed on one surface at a rotational speed of 2000 rpm and a film conveyance speed of 1 m / min using 1000 mesh buffalo with silicon carbide abrasive adhered to nylon fibers. Was done. The surface of the thermoplastic liquid crystal polymer film having a film thickness of 49.7 μm before polishing was removed, and the film thickness of the film after polishing was 49.2 μm. This thermoplastic liquid crystal polymer film had an arithmetic average roughness (Ra) of 0.18 μm and a ten-point average roughness (Rz _JIS ) of 1.4 μm as measured by a method according to ISO 4287-1997. .

The compression modulus (G ′) of this thermoplastic liquid crystal polymer film was measured every 20 seconds at a temperature increase rate of 4 ° C./min in the temperature range of 200 ° C. to 350 ° C. When the temperature of the thermoplastic liquid crystal polymer film is less than 250 ° C., the compression modulus (G ′) is 1 × 10 ⁷ Pa or more. When the temperature of the thermoplastic liquid crystal polymer film is 250 ° C. or more, the compression elasticity of the film The rate (G ′) was less than 1 × 10 ⁷ Pa.

[Reference Example 2]
(1) A thermotropic liquid crystal polyester composed of 27 mol% of 6-hydroxy-2-naphthoic acid units and 73 mol% of p-hydroxybenzoic acid units is heated and kneaded at 280 to 300 ° C. using a single screw extruder, and has a diameter of 40 mm. The film was extruded from an inflation die having a slit interval of 0.6 mm to obtain a film having a thickness of 50 μm. The film had a melting point Tm of 280 ° C. and a heat distortion temperature Tdef of 230 ° C.

(2) A 18 μm thick copper foil (1/2 ounce copper foil by electrolytic method) was used as the adherend, and this was heat-pressed to the above film at 260 ° C. to obtain a laminate.

(3) In order to measure the melting point of the film which is changed by the heat treatment of the laminate, the laminate is heat treated at 260 ° C. in a nitrogen atmosphere, and the melting peak temperature of the film layer by DSC (differential scanning calorimeter) in 1 hour unit. TA was measured. As a result, the temperature rises to 280 ° C. for untreated, 285 ° C. for 1 hour, 296 ° C. for 2 hours, and 306 ° C. for 4 hours. The heat distortion temperature Tdef of the film after the heat treatment for 4 hours was 275 ° C. Thus, if the heat treatment time of the film is lengthened, its TA increases sequentially. It can be understood that the thermal deformation temperature Tdef can be increased accordingly.

(4) On the other hand, 70 parts by weight of a thermotropic liquid crystal polyester composed of 20 mol% of 6-hydroxy-2-naphthoic acid units and 80 mol% of p-hydroxybenzoic acid units and 35 parts by weight of activated carbon powder having a benzene adsorption capacity of 85% The mixture was heated and kneaded at 320 to 340 ° C. using a shaft extruder, and extruded from an inflation die having a diameter of 40 mm and a slit interval of 0.6 mm to obtain an activated carbon-containing molded body having a thickness of 50 μm. The molded article had a benzene adsorption capacity of 35%.

(5) Next, the laminate obtained in the above (2) and the activated carbon-containing molded product obtained in the above (4) were overlapped and rolled up tightly so that there was no apparent gap. After this roll was installed in a hot air drier in an air atmosphere, temperature increase was started. First, heat treatment was performed at 260 ° C. for 4 hours, and then the temperature was raised to 285 ° C. and heat treatment was performed for 6 hours. The laminate and the activated carbon-containing molded body were separated from the roll after the heat treatment. Next, the metal foil was removed from the laminate by a chemical etching method to obtain a thermoplastic liquid crystal polymer film having a melting point of 335 ° C.

About the obtained thermoplastic liquid crystal polymer film, high-speed rotational polishing was performed on one surface at a rotational speed of 2000 rpm and a film conveyance speed of 1 m / min using 1000 mesh buffalo with silicon carbide abrasive adhered to nylon fibers. Was done. The surface of the thermoplastic liquid crystal polymer film having a film thickness of 51.4 μm before polishing was removed, and the film thickness of the film after polishing was 51.0 μm. This thermoplastic liquid crystal polymer film had an arithmetic average roughness (Ra) of 0.13 μm and a ten-point average roughness (Rz _JIS ) of 1.5 μm as measured by a method according to ISO 4287-1997. .

The compression modulus (G ′) of this thermoplastic liquid crystal polymer film was measured every 20 seconds at a temperature increase rate of 4 ° C./min in the temperature range of 200 ° C. to 350 ° C. When the temperature of the thermoplastic liquid crystal polymer film is less than 230 ° C., the compression modulus (G ′) is 1 × 10 ⁷ Pa or more. When the temperature of the thermoplastic liquid crystal polymer film is 230 ° C. or more, the compression elasticity of the film The rate (G ′) was less than 1 × 10 ⁷ Pa.

[Example 1]
Resin-coated metal roll as a roll 3 in contact with the thermoplastic liquid crystal polymer film 1 using the thermoplastic liquid crystal polymer film 1 obtained in Reference Example 1 and an electrolytic copper foil having a thickness of 18 μm (surface roughness 7 μm) as the metal sheet 2 (Super Tempex: Yuri Roll Machine Co., Ltd., resin thickness 1.7 cm) was used. As shown in FIG. 1, a thermoplastic liquid crystal polymer film 1 was disposed on the resin-coated metal roll 3 side, and an electrolytic copper foil 2 was disposed on the opposite surface. A metal roll 4 and a resin-coated metal roll 3 each having a diameter of 40 cm were used. The surface temperature of the metal roll 4 was set to be 20 ° C. lower than the melting point of the thermoplastic liquid crystal polymer film 1. The surface temperature of the resin-coated metal roll 3 at the position A before the resin-coated metal roll 3 contacts the metal roll 4 and the surface temperature of the resin-coated metal roll 3 at the position B immediately after contact with the heating roll are measured with a radiation thermometer. Measured using. A cold air device is installed in the resin-coated metal roll 3 as the temperature control means 6, and the temperature of the resin-coated metal roll 3 at the position B is such that the compression modulus (G ′) of the thermoplastic polymer film 1 is 1 × 10 ⁷ Pa or more. The air volume of the cool air device 3 was adjusted so as to be a temperature (150 ° C. at the position B). At this time, the temperature of the resin-coated metal roll at position A was 100 ° C. The line speed was adjusted to 3 m / min. The pressure applied to the thermoplastic liquid crystal polymer film 1 and the electrolytic copper foil 2 between the rolls is 120 kg / cm ² in terms of surface pressure. Under the above conditions, the thermoplastic liquid crystal polymer film 1 is aligned with the resin-coated metal roll 3. Then, the electrolytic copper foil 2 was temporarily bonded to the film 1. Later, both were introduced between the metal roll 4 and the resin-coated metal roll 3 and pressed to obtain a single-sided metal-clad laminate 5. In the obtained single-sided metal-clad laminate 5, the surface roughness of the side not joined to the metal sheet of the thermoplastic liquid crystal polymer film was measured. The results are shown in Table 7.

[Example 2]
The air volume of the cool air device 6 installed on the resin-coated metal roll 3 is adjusted so that the surface temperature of the resin-coated metal roll 3 at position A is 170 ° C. and the surface temperature of the resin-coated metal roll 3 at position B is 220 ° C. The conditions were the same as in Example 1 except for the setting. The results are shown in Table 7.

[Example 3]
Using the thermoplastic liquid crystal polymer film obtained in Reference Example 2 as the thermoplastic liquid crystal polymer film 1, the temperature of the metal roll 4 is set to 45 ° C. lower than the melting point of the thermoplastic liquid crystal polymer film 1, and the resin at position B The air volume of the cool air device 3 was adjusted so that the temperature of the coated metal roll 3 became a temperature (210 ° C. at the position B) at which the compression modulus (G ′) of the thermoplastic polymer film 1 was 1 × 10 ⁷ Pa or more. The conditions were the same as in Example 1 except for the above. The results are shown in Table 7.

[Example 4]
The line speed is adjusted to 8 m / min, and the temperature of the resin-coated metal roll 3 at the position B is a temperature at which the compression elastic modulus (G ′) of the thermoplastic polymer film 1 is 1 × 10 ⁷ Pa or more (220 at the position B). The conditions were the same as in Example 3 except that the air volume of the cool air device 3 was adjusted so that the air flow rate was 3 ° C.). The results are shown in Table 7.

[Comparative Example 1]
The temperature of the resin-coated metal roll 3 at the position B is changed so that the compression elastic modulus (G ′) of the thermoplastic polymer film 1 is 1 × 10 ⁷ Pa by changing the air volume of the cold air device 6 installed on the resin-coated metal roll 3. It was performed under the same conditions as in Example 1 except that the temperature was set to be lower (250 ° C. at position B). The results are shown in Table 7.

[Comparative Example 2]
The temperature of the metal roll 4 is set to a temperature 5 ° C. lower than the melting point of the thermoplastic liquid crystal polymer film 1, the line speed is 5 m / min, and the temperature of the resin-coated metal roll 3 at the position B is the thermoplastic polymer film 1 This was performed under the same conditions as in Example 1, except that the compression elastic modulus (G ′) was set to a temperature (255 ° C. at position B) that was less than 1 × 10 ⁷ Pa. The results are shown in Table 7.

[Comparative Example 3]
The temperature of the resin-coated metal roll 3 at the position B is changed so that the compression elastic modulus (G ′) of the thermoplastic polymer film 1 is 1 × 10 ⁷ Pa by changing the air volume of the cold air device 6 installed on the resin-coated metal roll 3. It was performed under the same conditions as in Example 3 except that the temperature was set to be lower (260 ° C. at position B). The results are shown in Table 7.

[Comparative Example 4]
The process was performed under the same conditions as in Example 1 except that a polyimide sheet was interposed as a release material between the thermoplastic liquid crystal polymer film 1 and the resin-coated metal roll 3 during thermocompression bonding. The results are shown in Table 7.

In Examples 1 and 2, the temperatures at position B of the resin-coated metal roll 3 are 150 ° C. and 220 ° C., respectively, and the compression modulus (G ′) of the thermoplastic liquid crystal polymer film 1 having a melting point of 280 ° C. is 1. Since the temperature is lower than × 10 ⁷ Pa (250 ° C.), fusion of the film to the resin-coated metal roll does not occur, and both the examples 1 and 2 are used in the thermoplastic liquid crystal polymer film in the metal-clad laminate. Good arithmetic average roughness (Ra) and ten-point average roughness (Rz _JIS ) are obtained. Moreover, the single-sided metal-clad laminate excellent in peel strength, appearance, and solder heat resistance has been obtained.

In Example 3 and Example 4, the temperature at the position B of the resin-coated metal roll 3 is 210 ° C. and 220 ° C., respectively, and the compression modulus (G ′) of the thermoplastic liquid crystal polymer film 1 having a melting point of 335 ° C. is 1. Since the temperature is lower than 10 ⁷ Pa (230 ° C.), fusion of the film to the resin-coated metal roll does not occur, and both the examples 1 and 2 are used in the thermoplastic liquid crystal polymer film in the metal-clad laminate. Good arithmetic average roughness (Ra) and ten-point average roughness (Rz _JIS ) are obtained. Moreover, the single-sided metal-clad laminate excellent in peel strength, appearance, and solder heat resistance has been obtained.

In Comparative Example 1 and Comparative Example 2, the temperatures at position B of the resin-coated metal roll 3 are 250 ° C. and 255 ° C., respectively, and the compression modulus (G ′) of the thermoplastic liquid crystal polymer film 1 having a melting point of 280 ° C. is 1. Since the temperature is lower than × 10 ⁷ Pa (250 ° C.) or higher, the film is fused to the resin-coated metal roll, the appearance is deteriorated, and the arithmetic operation of the thermoplastic liquid crystal polymer film in the metal-clad laminate is performed. The average roughness (Ra) is larger than 0.5 μm and the ten-point average roughness (Rz _JIS ) is larger than 2.0 μm. In such a case, the heat of this single-sided copper-clad laminate is When the surface of the plastic liquid crystal polymer film is pressure-bonded to a conductive layer of another circuit board material, the surface roughness of the thermoplastic liquid crystal polymer film deteriorates the surface roughness of the conductive layer of the other circuit board material. It caused problems such as the high-frequency characteristic falls of.

In Comparative Example 3, the temperature at the position B of the resin-coated metal roll 3 is 260 ° C., and the temperature at which the compression modulus (G ′) of the thermoplastic liquid crystal polymer film 1 having a melting point of 335 ° C. is less than 1 × 10 ⁷ Pa. Higher than (250 ° C.), the film is fused to the resin-coated metal roll, the appearance is deteriorated, and the arithmetic average roughness (Ra) of the thermoplastic liquid crystal polymer film in the metal-clad laminate is 0. .5 μm is large, and the ten-point average roughness (Rz _JIS ) is larger than 2.0 μm. In such a case, the thermoplastic liquid crystal polymer film surface of this single-sided copper-clad laminate is bonded to another surface. When pressure-bonding to a conductive layer of a circuit board material, the surface roughness of the thermoplastic liquid crystal polymer film deteriorates the surface roughness of the conductive layer of another circuit board material, resulting in a problem that the high-frequency characteristics of the conductive layer are lowered. That. Moreover, the solder heat resistance is also poor.

In Comparative Example 4, during thermocompression bonding, the thermoplastic liquid crystal polymer film 1 and the resin-coated metal roll 3 are thermocompression bonded via a polyimide sheet as a release material. The surface roughness is transferred, and the arithmetic average roughness (Ra) of the surface of the thermoplastic liquid crystal polymer film in the metal-clad laminate not joined to the metal sheet is less than 0.1 μm, and the ten-point average The roughness (Rz _JIS ) is smaller than 0.5 μm. In such a case, the peel strength is lowered when the surface of the thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate is laminated with another material. Problems arise.

DESCRIPTION OF SYMBOLS 1 ... Thermoplastic liquid crystal polymer film 2 ... Metal sheet 3 ... Roll 4 in contact with a thermoplastic liquid crystal polymer film ... Heating roll 5 ... Single-sided metal-clad laminate 6 ... Temperature control means

Claims (4)

Single-sided metal-clad laminate in which a metal sheet is bonded to one side of a film made of a thermoplastic polymer capable of forming an optically anisotropic melt phase (hereinafter sometimes referred to as a thermoplastic liquid crystal polymer film). An arithmetic average roughness (Ra) measured by a method according to ISO 4287-1997 on the surface of the single-sided metal-clad laminate that is not bonded to the metal sheet of the thermoplastic liquid crystal polymer film. A single-sided metal-clad laminate having 0.1 to 0.5 μm and a ten-point average roughness (Rz _JIS ) of 0.5 to 2.0 μm. A method for producing a single-sided metal-clad laminate in which a thermoplastic liquid crystal polymer film and a metal sheet are thermocompression bonded to form a laminate, and the metal sheet is bonded to one side of the thermoplastic liquid crystal polymer film. A release material is not interposed between the pressure bonding means and the thermoplastic liquid crystal polymer film, and ISO 4287-1997 on the surface of the single-sided metal-clad laminate that is not joined to the metal sheet of the thermoplastic liquid crystal polymer film. Single-sided metal-clad laminate having an arithmetic average roughness (Ra) of 0.1 to 0.5 μm and a ten-point average roughness (Rz _JIS ) of 0.5 to 2.0 μm measured by a method based on the Manufacturing method. The temperature of the thermoplastic liquid crystal polymer film during thermocompression bonding is adjusted to a temperature at which the compression modulus (G ′) of the thermoplastic liquid crystal polymer film is 1 × 10 ⁷ Pa or more. Method for producing a single-sided metal-clad laminate. A thermoplastic liquid crystal polymer film and a metal sheet are run, passed between heated rolls while being combined, thermocompression bonded, and a metal sheet is bonded to one side of the thermoplastic liquid crystal polymer film to form a laminate. In the method for producing a laminated board, the temperature of the roll in contact with the thermoplastic liquid crystal polymer film among the rolls is such that the compressive elastic modulus (G ′) of the thermoplastic liquid crystal polymer film is 1 × 10 ⁷ Pa or more. It adjusts to temperature, The manufacturing method of the single-sided metal-clad laminated board of Claim 2 or 3 characterized by the above-mentioned.

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