WO2016174868A1 - 熱可塑性液晶ポリマーフィルム及び回路基板 - Google Patents

熱可塑性液晶ポリマーフィルム及び回路基板 Download PDF

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Publication number
WO2016174868A1
WO2016174868A1 PCT/JP2016/002205 JP2016002205W WO2016174868A1 WO 2016174868 A1 WO2016174868 A1 WO 2016174868A1 JP 2016002205 W JP2016002205 W JP 2016002205W WO 2016174868 A1 WO2016174868 A1 WO 2016174868A1
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Prior art keywords
liquid crystal
crystal polymer
polymer film
thermoplastic liquid
conductor layer
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PCT/JP2016/002205
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English (en)
French (fr)
Japanese (ja)
Inventor
砂本　辰也
崇裕 中島
健 ▲高▼橋
小野寺　稔
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株式会社クラレ
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Priority to CN201680024465.8A priority Critical patent/CN107531921A/zh
Priority to JP2017515392A priority patent/JPWO2016174868A1/ja
Publication of WO2016174868A1 publication Critical patent/WO2016174868A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Definitions

  • the present invention relates to a thermoplastic liquid crystal polymer film (hereinafter sometimes referred to as a thermoplastic liquid crystal polymer film or simply a liquid crystal polymer film) and a circuit board that form an optically anisotropic molten layer.
  • a thermoplastic liquid crystal polymer film hereinafter sometimes referred to as a thermoplastic liquid crystal polymer film or simply a liquid crystal polymer film
  • a circuit board that form an optically anisotropic molten layer.
  • Transmission loss of high-frequency signals involves dielectric loss in addition to conductor loss. Therefore, in order to suppress the transmission loss of high-frequency signals and improve the information processing speed, that is, the signal propagation speed, there is a demand for an electrically insulating substrate material having excellent dielectric characteristics.
  • thermocompression bonding using a thermoplastic liquid crystal polymer film having a dielectric loss smaller than that of a polyimide film as an insulating substrate has attracted attention. ing.
  • peel strength peel strength or adhesive strength
  • mechanical bonding which is an anchor effect due to the surface roughness of the conductor layer
  • the conductor layer surface treatment component A chemical bond, which is a resin bond, is conceivable.
  • the anchor effect is enhanced by forming irregularities on the conductor layer, and the treatment to ensure the peel strength when the conductor layer and the insulating layer are crimped is performed. Shape optimization has been studied.
  • Patent Document 1 International Publication WO2012 / 020818 Pamphlet
  • a metal-clad laminated substrate having a metal foil on one or both sides of a liquid crystal polymer layer the metal foil is roughened on the surface in contact with the liquid crystal polymer layer.
  • a metal-clad laminate having protrusions on the surface layer is disclosed.
  • the aspect ratio (H / L) represented by the ratio of the height H of the protrusion to the width L of the root portion of the protrusion is in the range of 3 to 20, and the height of the protrusion is 0.1 to It is disclosed that the liquid crystal polymer layer has a thickness of 10 to 2000 ⁇ m and a film thickness tolerance of less than 6%.
  • thermoplastic liquid crystal polymer film that can provide high peel strength even when laminated with a conductor layer having excellent high frequency characteristics and low surface roughness.
  • a first object of the present invention is to provide a thermoplastic liquid crystal polymer film having a specific toughness that gives high peel strength even when it is thermocompression bonded to an adherend such as a conductor layer having a low surface roughness. is there.
  • the second object of the present invention is to provide a thermoplastic liquid crystal having a specific toughness and a specific Young's modulus that gives a high peel strength even when it is thermocompression bonded to an adherend such as a conductor layer having a low surface roughness. It is to provide a polymer film.
  • a third object of the present invention is to provide a thermoplastic liquid crystal polymer film that maintains a specific toughness with a low rate of decrease in toughness even after thermocompression bonding with an adherend such as a conductor layer.
  • the fourth object of the present invention is to provide a circuit board formed by pressure-bonding the thermoplastic liquid crystal polymer film and an adherend such as a conductor layer.
  • thermoplastic liquid crystal polymer film that is thermocompression bonded to the conductor layer has a toughness after thermocompression bonding within a specific value range. If it is a film, for example, even when it is thermocompression bonded to an adherend such as a conductor layer with low surface roughness, it has been found that high peel strength can be achieved while maintaining good high frequency characteristics, and the present invention has been completed. It was.
  • thermoplastic liquid crystal polymer film having a specific toughness and a specific Young's modulus, for example, even when it is thermocompression bonded to an adherend such as a conductor layer having a low surface roughness. It has been found that higher peel strength can be achieved while maintaining high frequency characteristics, and the present invention has been completed.
  • thermoplastic liquid crystal polymer film having specific toughness, and adhere an adherend such as a conductor layer to the thermoplastic liquid crystal polymer film, and the toughness of the thermoplastic liquid crystal polymer film is within a specific range.
  • the present inventors have found that a high peel strength can be maintained even after thermocompression bonding by thermocompression bonding under conditions that do not change beyond the above, and the present invention has been completed.
  • the first configuration of the present invention is a thermoplastic liquid crystal polymer film, which is measured by a method according to ASTM D882 of a thermoplastic liquid crystal polymer film after thermocompression bonding of the thermoplastic liquid crystal polymer film to a conductor layer. It is a thermoplastic liquid crystal polymer film having a toughness of 30 MPa to 100 MPa.
  • thermoplastic liquid crystal polymer film whose Young's modulus measured by the method based on ASTM D882 standard is 2.0 GPa or more and 4.0 GPa or less may be sufficient.
  • thermoplastic liquid crystal in which the thermoplastic liquid crystal film has a toughness reduction rate of 30% or less after thermocompression bonding of the thermoplastic liquid crystal film to an adherend such as a conductor layer at a temperature of the melting point of the thermoplastic liquid crystal film of ⁇ 30 ° C. or lower. It may be a polymer film.
  • the second configuration of the present invention is a circuit board formed by laminating a thermoplastic liquid crystal polymer film and a conductor layer.
  • the circuit board may have a ten-point average roughness (Rz JIS ) measured by a method based on ISO 4287-1997 on the surface of the conductor layer of 3 ⁇ m or less.
  • Rz JIS ten-point average roughness
  • the third configuration of the present invention is a circuit board including a thermoplastic liquid crystal polymer film and a conductor layer laminated on the thermoplastic liquid crystal polymer film, after the conductor layer is peeled off from the thermoplastic liquid crystal polymer film. It is a circuit board whose toughness measured by the method based on ASTM D882 of the thermoplastic liquid crystal polymer film is 30 MPa or more and 100 MPa or less.
  • thermoplastic liquid crystal polymer film of the present invention has a conductor layer with a low surface roughness capable of maintaining good high-frequency characteristics, that is, the ten-point average roughness (Rz JIS ) of the conductor layer surface according to ISO 4287-1997 is 3 ⁇ m or less.
  • Rz JIS ten-point average roughness
  • thermoplastic liquid crystal polymer film of the present invention a conductor layer having a low surface roughness capable of maintaining good high frequency characteristics and a thermoplastic liquid crystal polymer film can be laminated with high peel strength. Therefore, in the case where the thermoplastic liquid crystal polymer film and the conductor layer are laminated without limiting the irregular shape on the surface of the conductor layer laminated with the thermoplastic liquid crystal polymer film, the distance between the irregularities or the like to a specific shape or value, etc. Therefore, both good high frequency characteristics and high peel strength can be achieved, and productivity can be improved and costs can be reduced.
  • thermoplastic liquid crystal polymer film of the present invention remarkably reflects the anchor effect of an adherend such as a conductor layer to be pressure-bonded to the thermoplastic liquid crystal polymer film, and thus the surface roughness of the conductor layer capable of maintaining good high frequency characteristics, that is, A conductor layer having a high surface roughness and a high anchoring effect within a range of 10 ⁇ m or less in average roughness (Rz JIS ) of 3 ⁇ m or less by a method based on ISO 4287-1997 on the surface of the conductor layer, and the thermoplastic liquid crystal polymer of the present invention By laminating in combination with a film, higher peel strength can be provided.
  • thermoplastic liquid crystal polymer film of the present invention has a low decrease in toughness even after thermocompression bonding, and can maintain a high peel strength even after being laminated with a conductor layer.
  • thermoplastic liquid crystal polymer film is used as an insulating base material layer of a unit circuit board having a conductor layer formed on one side or both sides, and a circuit board material for bonding to the conductor layer (hereinafter referred to as adhesive). It may also be referred to as a property material).
  • the circuit board material may be at least one selected from a bonding sheet and a coverlay, and may preferably be a bonding sheet.
  • thermoplastic liquid crystal polymer film is formed from a liquid crystal polymer that can be melt-molded.
  • the thermoplastic liquid crystal polymer is not particularly limited as long as it is a liquid crystalline polymer that can be melt-molded.
  • a thermoplastic liquid crystal polyester or a thermoplastic having an amide bond introduced therein is used. Examples thereof include liquid crystal polyester amide.
  • the thermoplastic liquid crystal polymer may be a polymer in which an aromatic polyester or aromatic polyester amide is further introduced with an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond.
  • an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond.
  • 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.
  • Aromatic or aliphatic dihydroxy compounds (see Table 1 for typical examples)
  • Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for typical examples)
  • a polymer containing p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid as at least a repeating unit is preferable.
  • 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.
  • the repeating unit (A) of p-hydroxybenzoic acid is used.
  • optically anisotropic molten layer (optical anisotropy at the time of melting) referred to in the present invention is, for example, a sample placed on a hot stage, heated and heated in a nitrogen atmosphere, and the transmitted light of the sample observed. Can be certified.
  • the thermoplastic liquid crystal polymer preferably has a melting point (hereinafter referred to as Tm 0 ) in the range of 260 to 360 ° C., more preferably Tm 0 of 270 to 350 ° C. Tm 0 is determined by measuring the temperature at which the main endothermic peak appears with a differential scanning calorimeter (Shimadzu Corporation DSC).
  • thermoplastic liquid crystal polymer a thermoplastic polymer such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyether ether ketone, fluororesin, etc., within the range not impairing the effect of the present invention, Various additives may be added, and a filler may be added as necessary.
  • thermoplastic liquid crystal polymer film used in the present invention can be obtained by extruding 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.
  • the inflation method and the laminate stretching method stress is applied not only in the film machining direction (hereinafter abbreviated as MD direction) but also in the direction perpendicular thereto (hereinafter abbreviated as TD direction).
  • MD direction film machining direction
  • TD direction direction perpendicular thereto
  • 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.
  • a predetermined draw ratio corresponding to a stretching ratio in the MD direction
  • a blow ratio corresponding to a stretching ratio in the TD direction
  • the draw 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 draw 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 respective stretching ratios in the MD direction and the TD direction may be, for example, 2.6 or less, preferably about 0.4 to 2.5.
  • thermoplastic liquid crystal polymer film may be stretched as necessary after being extruded.
  • 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.
  • a known uniaxial stretching machine, simultaneous biaxial stretching machine, sequential biaxial stretching machine or the like can be used.
  • thermoplastic liquid crystal polymer film may be known or conventional heat treatment 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.
  • 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.
  • thermoplastic liquid crystal polymer film of the present invention thus obtained can be suitably used as a circuit board material because it has excellent dielectric properties and low hygroscopicity.
  • thermoplastic liquid crystal polymer film its derived from rigid structure, generally high melt viscosity at low shear regions, e.g., the melt viscosity of the thermoplastic liquid crystal polymer film at 300 ° C. (shear rate 1000 sec - 1 ) may be, for example, 100 Pa ⁇ s or more, preferably about 200 to 100,000 Pa ⁇ s (eg about 150 to 100,000 Pa ⁇ s), more preferably about 200 to 10,000 Pa ⁇ s. There may be.
  • the melt viscosity can be measured using a viscoelastic rheometer (for example, AR 2000 manufactured by TA Instrucment Japan) under the conditions of a heating rate of 3 ° C./min, a frequency of 1 Hz, a strain of 0.1%, and a normal stress of 5N. it can.
  • a viscoelastic rheometer for example, AR 2000 manufactured by TA Instrucment Japan
  • the melting point (Tm) of the thermoplastic liquid crystal polymer film can be selected within the range of about 200 to 400 ° C., preferably about 250 to 360 ° C., for the purpose of obtaining the desired heat resistance and processability of the film. Preferably, it may be about 260 to 340 ° C.
  • the melting point of the film can be 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 to be completely melted, the melt was rapidly cooled to 50 ° C. at a rate of 50 ° C./min, and then again heated at a rate of 20 ° C./min. The position of the endothermic peak that appears later may be recorded as the melting point of the film.
  • the thermoplastic liquid crystal polymer film used in the present invention may have any thickness, and includes a plate or sheet of 5 mm or less. 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.
  • the film thickness is preferably in the range of 10 to 500 ⁇ m, more preferably in the range of 15 to 200 ⁇ m. 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 ⁇ m may be used.
  • thermoplastic liquid crystal polymer film to be thermocompression bonded to the conductor layer has a toughness measured by a method in accordance with ASTM D882 of the film after thermocompression bonding to the conductor layer is 30 MPa to 100 MPa.
  • it may be 35 MPa or more and 100 MPa or less, more preferably 50 MPa or more and 100 MPa or less, further preferably 60 MPa or more and 100 MPa or less, and particularly preferably 70 MPa or more and 90 MPa or less.
  • thermoplastic liquid crystal polymer film that has a toughness after thermocompression bonding with a conductor layer in this range, the peel strength when laminated with an adherend such as a conductor layer can be increased, and is high even after thermocompression bonding. Peel strength can be maintained.
  • thermoplastic liquid crystal polymer film of the present invention is obtained by superposing the film on a copper foil, using a vacuum hot press machine, setting the pressure bonding temperature (temperature of the heating plate) to the melting point Tm-35 ° C. of the film, and a pressure of 4 MPa.
  • the toughness of the film after peeling the copper foil is 30 MPa or more and 100 MPa or less.
  • a thermoplastic liquid crystal polymer film having a toughness of 30 MPa or more and 100 MPa or less is preferable regardless of the pressure bonding temperature set in the range of Tm-35 ° C. or higher and Tm-10 ° C. or lower under the above-described pressure bonding conditions.
  • a film with higher toughness reflects the anchor effect of the conductor layer more remarkably and gives higher peel strength.
  • a film with high toughness and a conductor layer having a high surface roughness and a high anchor effect are combined and bonded. Higher peel strength can be obtained.
  • the conductor layer surface roughness within a range that does not increase the transmission loss (for example, the 10-point average roughness (Rz JIS ) of 3 ⁇ m or less by a method based on ISO 4287-1997) of the conductor layer surface, good high frequency characteristics can be obtained. High peel strength can be achieved while maintaining.
  • thermoplastic liquid crystal polymer film having a toughness of less than 30 MPa In a thermoplastic liquid crystal polymer film having a toughness of less than 30 MPa, a large peel strength cannot be obtained when pressure-bonded to a conductor layer having a high surface roughness within a range that does not increase transmission loss, and the uneven shape of the surface of the conductor layer cannot be obtained. Since special processing such as specifying or limiting the distance between irregularities to a specific range is required, the process becomes complicated and the manufacturing conditions are limited.
  • the means for increasing the toughness of the thermoplastic liquid crystal polymer film is not particularly limited.
  • the toughness of the film may be increased by heat treatment.
  • the toughness imparted to the film can be adjusted by controlling the heat treatment temperature, heat treatment time, temperature rise rate, etc. during heat treatment. For example, if the heat treatment temperature is increased under certain temperature rise rate conditions, the thermoplasticity The toughness imparted to the liquid crystal polymer film also increases, and when the heat treatment time is lengthened, the toughness imparted to the thermoplastic liquid crystal polymer film tends to increase.
  • the conditions for the heat treatment temperature are not particularly limited. For example, even if the melting point (Tm) of the thermoplastic liquid crystal polymer film is ⁇ 30 ° C. or higher (eg, Tm ⁇ 20 ° C. to Tm + 10 ° C., preferably Tm to Tm + 10 ° C.). Good.
  • the conditions for the heat treatment time are not particularly limited, but may be, for example, about 1 to 20 hours (for example, about 5 to 15 hours, preferably about 6 to 10 hours).
  • the temperature raising rate is preferably, for example, 1 ° C./min to 6 ° C./min, more preferably 1 ° C./min to 3 ° C./min, from the viewpoint of increasing the toughness of the thermoplastic liquid crystal polymer film. Considering the above, 2 ° C./min is particularly preferable.
  • thermotropic liquid crystal polyester comprising 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 the diameter is 40 mm.
  • a thermoplastic liquid crystal polymer film having a melting point of 280 ° C. and a thickness of 50 ⁇ m formed by extrusion from an inflation die having a slit interval of 0.6 mm is heated in an oven in a nitrogen atmosphere at a rate of temperature rise of about 2 ° C./min and a heat treatment temperature of 280.
  • thermoplastic liquid crystal polymer film having a toughness of about 80 MPa can be obtained by performing a heat treatment at about 0 ° C. and a heat treatment time of about 6 hours.
  • the temperature rise rate is about 4 ° C./min
  • the heat treatment temperature is about 280 ° C.
  • the heat treatment time is 5 hours. It is possible to obtain a thermoplastic liquid crystal polymer film having a toughness of about 70 MPa by applying a heat treatment of about Can.
  • the toughness of the thermoplastic liquid crystal polymer film may be increased by the heat treatment as described above, and even after the film and the conductor layer are thermocompression bonded by setting the toughness of the thermoplastic liquid crystal polymer film high,
  • the toughness of the thermoplastic liquid crystal polymer film can be maintained at 30 MPa or more and 100 MPa or less, and good peel strength can be maintained even after thermocompression bonding.
  • the Young's modulus of the thermoplastic liquid crystal polymer film measured by a method based on the ASTM D882 standard is 2.0 GPa or more and 4.0 GPa. Or less, more preferably 2.5 GPa or more and 4 GPa or less, and further preferably 2.5 GPa or more and 3.5 GPa or less.
  • the means for adjusting the Young's modulus of the thermoplastic liquid crystal polymer film is not particularly limited.
  • the Young's modulus may be adjusted by heat treatment.
  • thermoplastic liquid crystal polymer film when the heat treatment temperature is increased, the Young's modulus imparted to the thermoplastic liquid crystal polymer film tends to decrease.
  • a thermotropic liquid crystal polyester comprising 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 the diameter is 40 mm.
  • a thermoplastic liquid crystal polymer film having a melting point of 280 ° C.
  • thermoplastic liquid crystal polymer film having a toughness of about 80 MPa and a Young's modulus of about 3.5 GPa can be obtained.
  • thermotropic liquid crystal polyester comprising 27 mol% of 6-hydroxy-2-naphthoic acid units and 73 mol% of p-hydroxybenzoic acid units is converted into a uniaxial
  • a thermoplastic liquid crystal polymer film having a melting point of 280 ° C. and a thickness of 50 ⁇ m formed by extrusion kneading at 280 to 300 ° C. using an extruder and extruding from an inflation die having a diameter of 40 mm and a slit interval of 0.6 mm is heated in an oven under a nitrogen atmosphere.
  • thermoplastic liquid crystal polymer film having a toughness of about 80 MPa and a Young's modulus of about 5.0 GPa is obtained.
  • the heat treatment temperature may be increased and the heat treatment time may be set shorter, or the heat treatment temperature may be lowered and the heat treatment time set longer. May be.
  • the Young's modulus of the thermoplastic liquid crystal polymer film tends to be affected, for example, by the heat treatment time. If the heat treatment time is long, the Young's modulus may increase. Therefore, the heat treatment takes into account the toughness of the thermoplastic liquid crystal polymer film and the Young's modulus.
  • the toughness and Young's modulus can be set to specific ranges by adjusting the temperature and heat treatment time.
  • the toughness and Young's modulus in a specific range can be imparted to the thermoplastic liquid crystal polymer film by appropriately setting the heat treatment temperature according to the heat treatment time condition such that the Young's modulus is in a specific range.
  • the toughness of the thermoplastic liquid crystal polymer film is in the range of 30 MPa to 100 MPa and the Young's modulus of the thermoplastic liquid crystal polymer film is in the range of 2.0 GPa to 4.0 GPa, the toughness of the film is high, and the Young's modulus The lower the value, the higher the peel strength when crimped to an adherend such as a conductor layer.
  • the conductor layer is formed of at least a conductive metal, and a circuit is formed on the conductor layer using a known circuit processing method.
  • a known method can be used as a method for forming a conductor layer on an insulating substrate made of a thermoplastic liquid crystal polymer film.
  • a metal layer may be deposited by electroless plating or electrolytic plating.
  • a metal layer may be formed.
  • a metal foil (for example, copper foil) may be pressure bonded to the surface of the thermoplastic liquid crystal polymer film by thermocompression bonding.
  • the metal foil that constitutes the conductor layer is preferably a metal foil used for electrical connection, and can include various metal foils such as gold, silver, nickel, and aluminum in addition to copper foil. In particular (for example, 98% by mass or more), an alloy foil composed of these metals may be included.
  • copper foil is preferably used.
  • the copper foil is not particularly limited as long as it is a copper foil that can be used in a circuit board, and may be a rolled copper foil or an electrolytic copper foil.
  • the conductor layer may have an oxidation resistant film formed on the surface of the conductor layer.
  • the unit circuit board preparation process includes a thermocompression bonding process in which a metal foil is thermocompression bonded to one or both sides of a thermoplastic liquid crystal polymer film, and an oxidation resistant film is formed on the thermocompressed metal foil surface. An oxidation-resistant film forming step.
  • the unit circuit board preparation step may further include a silane coupling agent attaching step for attaching a silane coupling agent to the surface of the conductor layer.
  • oxidation resistant film examples include an oxidation resistant alloy layer, an oxidation resistant plating layer, and a rust preventive layer such as benzotriazoles.
  • the oxidation resistant film may be formed either before or after circuit processing depending on the type of the conductor layer and the oxidation resistant film.
  • the oxidation-resistant alloy layer is preferably an alloy including at least a metal that forms the metal foil, for example, from the viewpoint of improving adhesion.
  • the metal foil constituting the conductor layer is a copper foil
  • the alloy layer may be an alloy containing at least copper.
  • the oxidation resistant alloy layer is preferably formed before circuit processing.
  • such an alloy layer may be formed by “FlatBOND GT” marketed by Mec Co., Ltd.
  • an alloy part that does not contain copper in the part away from the copper foil there may be an alloy part that does not contain copper in the part away from the copper foil.
  • examples of such an etchant include “Mekkuri Mover S-651A” (manufactured by MEC Co., Ltd.), “Espac H-150” (manufactured by Sasaki Chemical Co., Ltd.), and an aqueous solution containing an inorganic acid such as nitric acid. Is mentioned.
  • the surface roughness of the conductor layer is preferably 3 ⁇ m or less, more preferably 2.0 ⁇ m or less, and even more preferably 1.5 ⁇ m or less as a ten-point average roughness (Rz JIS ) according to a method based on ISO 4287-1997. It may be.
  • the lower limit of the ten-point average roughness (Rz JIS ) is not particularly limited, but may be, for example, 0.1 ⁇ m or more, 0.3 ⁇ m or more, or 0.5 ⁇ m or more.
  • the conductive layer on the surface to which the bonding sheet is not attached may be smooth when the laminate is formed.
  • the surface of the conductor which remains after circuit processing may be smooth.
  • the thickness of the conductor layer is preferably in the range of 1 to 50 ⁇ m, for example, and more preferably in the range of 5 to 20 ⁇ m.
  • a circuit board (preferably a multilayer circuit board) is used for adhering to one or more unit circuit boards made of a thermoplastic liquid crystal polymer film having a conductor layer formed on one side or both sides, and the conductor layer of the unit circuit board.
  • a circuit board having one or more circuit board materials made of a thermoplastic liquid crystal polymer film may be used, and the ten-point average roughness by a method based on ISO 4287-1997 on the surface of the conductor layer on the side to be bonded to the circuit board material ( Rz JIS ) may be 3 ⁇ m or less.
  • the circuit board of the present invention may be a circuit board having the following configuration.
  • a unit circuit board having an insulating layer (base material layer) made of a thermoplastic liquid crystal polymer film, a conductor layer formed on one or both sides of the film, and a bonding sheet A circuit board (multilayer circuit board) in which two or more unit circuit boards are stacked
  • the circuit board may be composed of a high-melting-point liquid crystal polymer film having high heat resistance and a low-melting-point liquid crystal polymer film having lower heat resistance, for example, selected from an insulating substrate, a bonding sheet, and a coverlay
  • the at least two kinds of circuit board materials may be composed of a high melting point liquid crystal polymer film having high heat resistance and a low melting point liquid crystal polymer film having lower heat resistance.
  • the difference in melting point between the high melting point liquid crystal polymer film and the low melting point liquid crystal polymer film is preferably about 0 to 70 ° C., more preferably about 0 to 60 ° C.
  • a bonding sheet 3 is interposed on a first unit circuit board 10 in which a conductor layer (copper foil) 4 is bonded to both surfaces of a thermoplastic liquid crystal polymer film 1 that is an insulating layer.
  • a laminated body (circuit board) 30 in which the second unit circuit board 20 having the conductor layer 4 formed on one surface (upper surface) of the thermoplastic liquid crystal polymer film 2 as an insulating layer is illustrated as an example.
  • the configuration does not limit the circuit board of the present invention.
  • the circuit board may have only two conductor layers, or may have four or more conductor layers.
  • the circuit board may be provided with a cover lay made of a liquid crystal polymer film in the outermost layer in order to cover the conductor layer.
  • the circuit board of the present invention may have, for example, an adhesive strength (peel strength) between the liquid crystal polymer film and the conductor layer of 0.6 kN / m or more (for example, 0.6 to 2 kN / m), preferably May be 0.8 kN / m or more, more preferably 1.0 kN / m or more.
  • This adhesive strength (peel strength) is obtained by applying an adhesive material made of a liquid crystal polymer film to a laminate of the liquid crystal polymer film and the conductor layer at a speed of 50 mm per minute by a method in accordance with JIS C5016-1994.
  • it may be a peel strength value measured by a method in accordance with a tensile tester [Nidec Sympo Co., Ltd., Digital Force Gauge FGP-2] while peeling in the direction of 90 °. .
  • the circuit board of the present invention uses a thermoplastic liquid crystal polymer having excellent dielectric properties as an insulating material, it can be suitably used particularly as a high-frequency circuit board.
  • a high-frequency circuit is not only a circuit that transmits only a high-frequency signal, but also a transmission path that converts a high-frequency signal to a low-frequency signal and outputs the generated low-frequency signal to the outside, and driving of high-frequency compatible components
  • a transmission line for transmitting a signal that is not a high-frequency signal, such as a transmission line for supplying power supplied for the purpose, is also included.
  • the relative dielectric constant ( ⁇ r ) of the circuit board may be, for example, 2.6 to 3.5, and more preferably 2.6 to 3.4.
  • the dielectric loss tangent (Tan ⁇ ) of the circuit board may be, for example, 0.001 to 0.01, and more preferably 0.001 to 0.008.
  • circuit board manufacturing method a method for manufacturing a circuit board according to the present invention will be described.
  • At least one unit circuit board having an insulating base layer made of a thermoplastic liquid crystal polymer film and a conductor layer formed on one or both sides of the base layer is prepared.
  • the thermoplastic liquid crystal polymer film and the conductor layer those having the structure described above can be used.
  • circuit board material for bonding to the conductor layer
  • circuit board material adhesive material
  • one or more circuit board materials for bonding to the conductor layer of the unit circuit board may be prepared separately from the unit circuit board.
  • the adhesive material may be a thermoplastic liquid crystal polymer film, and specific examples include at least one selected from a bonding sheet and a coverlay.
  • the melting point of the liquid crystal polymer film used as the adhesive material may be the same as the melting point of the base of the unit circuit board, but rather than the liquid crystal polymer film forming the unit circuit board, It is preferable to use one having a low melting point. In this case, the difference between the melting points of the two may be, for example, about 0 to 70 ° C., and more preferably about 0 to 60 ° C.
  • thermocompression bonding the thermoplastic liquid crystal polymer film and the conductor layer is not particularly limited.
  • a batch type vacuum heat press, a roll press, a double belt press, or the like can be used.
  • the roll press and the double belt press may be a roll-to-roll roll press or a double belt press.
  • thermoplastic liquid crystal polymer film and a conductor layer for example, metal foil
  • a vacuum hot press device When laminating a thermoplastic liquid crystal polymer film and a conductor layer (for example, metal foil) by batch-type vacuum hot press, for example, using a vacuum hot press device, it is cut into a predetermined size between the two heating plates.
  • the thermoplastic liquid crystal polymer film and the metal foil may be placed on top of each other and heat-pressed in a vacuum state (batch type vacuum hot press lamination method).
  • thermoplastic liquid crystal polymer film and a conductor layer for example, a metal foil
  • a single-sided metal-clad laminate in which a metal foil is bonded to one side of the film by introducing between a heated metal roll and a rubber roll in contact therewith, passing between the rolls and thermocompression bonding to form a laminate. It may be produced.
  • there may be a preheating step in which the film is placed along the rubber roll before passing between the rolls, and then the metal foil is temporarily bonded to the film, and the preheating step has an angle at which the film contacts the rubber roll.
  • a laminate is formed by laminating a conductor layer (for example, a metal foil) on both sides of a thermoplastic liquid crystal polymer film by a roll press to produce a double-sided metal-clad laminate
  • the metal foil is placed on both sides of the thermoplastic liquid crystal polymer film.
  • thermoplastic liquid crystal polymer film and a conductor layer for example, metal foil
  • a metal foil and the film are pressed by applying a pressure of about 5 to 500 bar at a temperature between the melting point of the thermoplastic liquid crystal polymer film and the deterioration point of the film to form a laminate. May be.
  • the pressure of the press may be about 5 to 100 bar, and the staying time during which the film is at a temperature higher than its melting point in the press may be 0.5 to 1000 seconds.
  • thermocompression bonding temperature at the time of thermocompression bonding of the thermoplastic liquid crystal polymer film and the conductor layer is preferably not more than the melting point Tm-30 ° C of the film, more preferably not more than Tm-35 ° C, and still more preferably Tm-40. It may be below °C.
  • the rate of decrease in toughness of the liquid crystal polymer film after thermocompression bonding of the thermoplastic liquid crystal polymer film and the conductor layer is preferably within 30%, more preferably within 25%, more preferably within 15%, and even more preferably within 5%. .
  • the toughness reduction rate of the liquid crystal polymer film after thermocompression bonding is within this range, higher peel strength can be maintained even after thermocompression bonding.
  • the pressure applied during the thermocompression bonding is that of the thermoplastic liquid crystal polymer film.
  • the pressure applied during the thermocompression bonding is that of the thermoplastic liquid crystal polymer film.
  • it can be selected from a wide range of 0.5 to 6 MPa, for example.
  • the pressing pressure is 5 MPa or less, particularly 4.5 MPa or less (for example, 0.5 MPa to 3 MPa, preferably 1 to 2.5 MPa), good adhesion between the liquid crystal polymer film and the conductor layer is possible. is there.
  • the adhesive strength (peel strength) measured according to JIS C5016-1994 between the thermoplastic liquid crystal polymer film and the conductor layer is preferably 0.6 kN / m or more, and 0.8 kN / M or more is more preferable, and 1.0 kN / m or more is more preferable.
  • surface treatment may be performed on the circuit board material as long as the effects of the present invention are not impaired.
  • the surface treatment can be performed by a known method such as ultraviolet irradiation, plasma irradiation, or physical polishing.
  • the toughness (MPa) of the thermoplastic liquid crystal polymer film after thermocompression bonding is determined by toughening the thermoplastic liquid crystal polymer film from the conductor layer after thermocompression bonding of the thermoplastic liquid crystal polymer film and the conductor layer. MPa).
  • the Young's modulus (GPa) of the thermoplastic liquid crystal polymer film was calculated from the following formula (2) by applying a tensile load to the film and determining the displacement by a method based on ASTM D882.
  • E ( ⁇ n + 1 ⁇ n ) / ( ⁇ n + 1 ⁇ n ) (2) (Where E: Young's modulus (GPa), ⁇ n + 1 - ⁇ n : change in tensile stress when the tensile load is varied, ⁇ n + 1 - ⁇ n : change in tensile strain when the tensile load is varied amount)
  • the surface roughness (Rz JIS ) is obtained by extracting the reference length in the direction of the average line from the roughness curve, and calculating the average value of the altitude of the highest peak to the fifth peak (convex vertex) and the deepest The difference from the average value of the altitude of the valley bottom (concave bottom point) from the fifth to the fifth is expressed in ⁇ m, and the ten-point average roughness is shown.
  • Adhesive strength peel strength (kN / m)
  • the adhesive material made of a liquid crystal polymer film is pulled at a rate of 50 mm per minute while peeling the adhesive material made of the liquid crystal polymer film and the conductor layer in the direction of 90 ° by a method according to JIS C5016-1994.
  • the peel strength was measured with a testing machine [Nidec Sympo Co., Ltd., Digital Force Gauge FGP-2], and the obtained value was defined as the adhesive strength (peel strength) (kN / m).
  • thermoplastic liquid crystal polymer film having a melting point of 335 ° C., a toughness of 80 MPa, and a Young's modulus of 3.5 GPa was prepared.
  • a rolled copper foil with a surface roughness Rz JIS of 2.5 ⁇ m (made by Mitsui Kinzoku Co., Ltd., SQ-VLP, thickness 12 ⁇ m) is superimposed on this thermoplastic liquid crystal polymer film as a conductor layer.
  • the heating plate was set to 300 ° C. (melting point Tm-35 ° C. of the thermoplastic liquid crystal polymer film), and thermocompression bonded for 10 minutes under a pressure of 4 MPa to prepare a laminate.
  • thermoplastic liquid crystal polymer film having a melting point of 325 ° C., a toughness of 68 MPa, and a Young's modulus of 3.0 GPa was prepared.
  • a rolled copper foil with a surface roughness Rz JIS of 2.5 ⁇ m (made by Mitsui Kinzoku Co., Ltd., SQ-VLP, thickness 12 ⁇ m) is superimposed on this thermoplastic liquid crystal polymer film as a conductor layer.
  • the heating plate was set at 295 ° C. (melting point Tm ⁇ 30 ° C. of the thermoplastic liquid crystal polymer film) and thermocompression bonded for 10 minutes under a pressure of 4 MPa to prepare a laminate.
  • thermoplastic liquid crystal polymer film having a melting point of 280 ° C., a toughness of 42 MPa, and a Young's modulus of 2.5 GPa was prepared.
  • a rolled copper foil with a surface roughness Rz JIS of 2.5 ⁇ m (made by Mitsui Kinzoku Co., Ltd., SQ-VLP, thickness 12 ⁇ m) is superimposed on this thermoplastic liquid crystal polymer film as a conductor layer.
  • the heating plate was set at 250 ° C. (melting point Tm ⁇ 30 ° C. of the thermoplastic liquid crystal polymer film), and thermocompression bonded under a pressure of 4 MPa for 10 minutes to prepare a laminate.
  • thermoplastic liquid crystal polymer film having a melting point of 335 ° C., a toughness of 80 MPa, and a Young's modulus of 3.5 GPa was prepared.
  • Rolled copper foil JX Nippon Mining & Metals Co., Ltd., BHY-X, thickness 12 ⁇ m
  • Rz JIS surface roughness
  • the heating platen was set at 300 ° C. (melting point Tm-35 ° C. of the thermoplastic liquid crystal polymer film), and thermocompression bonded under a pressure of 4 MPa for 10 minutes to produce a laminate.
  • thermoplastic liquid crystal polymer film having a melting point of 335 ° C., a toughness of 80 MPa, and a Young's modulus of 3.5 GPa was prepared.
  • Rolled copper foil JX Nippon Mining & Metals Co., Ltd., BHY-X, thickness 12 ⁇ m
  • Rz JIS surface roughness
  • the heating platen was set at 325 ° C. (melting point Tm ⁇ 10 ° C. of the thermoplastic liquid crystal polymer film), and thermocompression bonded under a pressure of 4 MPa for 10 minutes to produce a laminate.
  • thermoplastic liquid crystal polymer film having a melting point of 320 ° C., a toughness of 16 MPa, and a Young's modulus of 4.0 GPa was prepared.
  • a rolled copper foil with a surface roughness Rz JIS of 2.5 ⁇ m (made by Mitsui Kinzoku Co., Ltd., SQ-VLP, thickness 12 ⁇ m) is superimposed on this thermoplastic liquid crystal polymer film as a conductor layer.
  • the heating plate was set at 290 ° C. (melting point Tm ⁇ 30 ° C. of the thermoplastic liquid crystal polymer film), and thermocompression bonded under a pressure of 4 MPa for 10 minutes to prepare a laminate.
  • thermotropic liquid crystal polyester composed of 27 mol% of 6-hydroxy-2-naphthoic acid units and 73 mol% of p-hydroxybenzoic acid units is kneaded at 280 to 300 ° C. using a single screw extruder, and has a diameter of 40 mm and slits.
  • the film was extruded from an inflation die having a spacing of 0.6 mm to obtain a film having a thickness of 50 ⁇ m.
  • the film had a melting point Tm of 280 ° C. and toughness of 20 MPa.
  • thermoplastic liquid crystal polymer film As a conductor layer.
  • the heating plate was set at 250 ° C. (melting point Tm ⁇ 30 ° C. of the thermoplastic liquid crystal polymer film), and thermocompression bonded under a pressure of 4 MPa for 10 minutes to prepare a laminate.
  • thermotropic liquid crystal polyester composed of 27 mol% of 6-hydroxy-2-naphthoic acid units and 73 mol% of p-hydroxybenzoic acid units is kneaded at 280 to 300 ° C. using a single screw extruder, and has a diameter of 40 mm and slits.
  • the film was extruded from an inflation die having a spacing of 0.6 mm to obtain a film having a thickness of 50 ⁇ m.
  • the melting point Tm of this film was 280 ° C.
  • the obtained film was heat-treated. During the heat treatment, the temperature was not raised, and the film surface temperature was fixed at 260 ° C. for 4 hours, followed by heat treatment at 285 ° C. for 6 hours, and heat treatment was performed under two-stage temperature conditions.
  • the thermoplastic liquid crystal polymer film obtained had a melting point Tm of 350 ° C. and a toughness of 20 MPa.
  • thermotropic liquid crystal polyester composed of 27 mol% of 6-hydroxy-2-naphthoic acid units and 73 mol% of p-hydroxybenzoic acid units is kneaded at 280 to 300 ° C. using a single screw extruder, and has a diameter of 40 mm and slits.
  • the film was extruded from an inflation die having a spacing of 0.6 mm to obtain a film having a thickness of 50 ⁇ m.
  • the melting point Tm of this film was 280 ° C.
  • the obtained film was heat-treated. During the heat treatment, the temperature was not raised, and the film surface temperature was fixed at 260 ° C. for 4 hours, followed by heat treatment at 300 ° C. for 6 hours, and heat treatment was performed under two stages of temperature conditions.
  • the thermoplastic liquid crystal polymer film obtained had a melting point Tm of 335 ° C. and a toughness of 18 MPa.
  • the toughness of the thermoplastic liquid crystal polymer films of Comparative Examples 1 to 4 is less than 30 MPa, and the films having low toughness such as Comparative Examples 1 to 4 have a peel strength of 0.6 kN / m or less between the copper foil and the film. There is a low value.
  • Example 4 When Example 4 and Example 5 are compared, in Example 4, the thermoplastic liquid crystal polymer film and the copper foil are pressure-bonded at a temperature of the melting point (Tm) -35 ° C. of the thermoplastic liquid crystal polymer film. It can be seen that the toughness of the film after pressure bonding is 80 MPa, and there is no decrease in toughness after thermocompression bonding, which gives a high peel strength of 1.2 kN / m. On the other hand, in Example 5, since the thermoplastic liquid crystal polymer film and the copper foil were pressure-bonded at a temperature of Tm-10 ° C., the toughness of the film after thermo-compression was 50 MPa, and the reduction rate was 37.5%. As a result, the peel strength is 0.8 kN / m, and a better result is obtained in Example 4 in which the rate of decrease in toughness after thermocompression bonding is kept low.
  • Tm melting point

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US20210070927A1 (en) * 2019-09-10 2021-03-11 Ticona Llc Polymer Composition and Film for Use in 5G Applications
JPWO2021177402A1 (zh) * 2020-03-06 2021-09-10
WO2021193385A1 (ja) * 2020-03-26 2021-09-30 株式会社クラレ 多層回路基板の製造方法
US20230042016A1 (en) * 2021-07-30 2023-02-09 Fujifilm Corporation Laminate
KR20230032878A (ko) 2021-08-31 2023-03-07 후지필름 가부시키가이샤 액정 폴리머 필름, 적층체
US11840602B2 (en) 2019-12-23 2023-12-12 Chang Chun Plastics Co., Ltd. Laminate, circuit board, and liquid crystal polymer film applied to the same
US11917753B2 (en) 2019-09-23 2024-02-27 Ticona Llc Circuit board for use at 5G frequencies
JP7526622B2 (ja) 2018-11-08 2024-08-01 株式会社クラレ 熱可塑性液晶ポリマーフィルムの製造方法、熱可塑性液晶ポリマーフィルム、並びにそれを用いた金属張積層体および回路基板

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KR20210084475A (ko) * 2018-10-29 2021-07-07 파나소닉 아이피 매니지먼트 가부시키가이샤 금속장 적층판 및 금속장 적층판의 제조 방법
CN112566364B (zh) * 2020-11-24 2022-12-30 中国科学技术大学 无胶粘层热塑性液晶聚合物高频基板及其制备方法和应用
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JP7526622B2 (ja) 2018-11-08 2024-08-01 株式会社クラレ 熱可塑性液晶ポリマーフィルムの製造方法、熱可塑性液晶ポリマーフィルム、並びにそれを用いた金属張積層体および回路基板
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WO2021193385A1 (ja) * 2020-03-26 2021-09-30 株式会社クラレ 多層回路基板の製造方法
US20230042016A1 (en) * 2021-07-30 2023-02-09 Fujifilm Corporation Laminate
KR20230032878A (ko) 2021-08-31 2023-03-07 후지필름 가부시키가이샤 액정 폴리머 필름, 적층체

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