Metal laminate and method for manufacturing metal laminate

Abstract

Provided are: a polyarylene sulfide resin film that can form a metal layer having both smoothness and adhesiveness; a metal layered product; a production method for the polyarylene sulfide resin film; and a production method for the metal layered product. In this polyarylene sulfide resin film, oxygen atoms detected on at least one surface thereof by analysis using X-ray photoemission spectroscopy (XPS) account for 10-17 atomic%, and the atomic ratio O / C of oxygen atoms to carbon atoms is 0.10-0.25.

Description

Technical Field

[0001] The present invention relates to a polyarylene sulfide resin film, a metal laminate, a method for producing a polyarylene sulfide resin film, and a method for producing a metal laminate, which can be suitably used for applications such as wiring boards and circuit materials.

Background Art

[0002] With the development of communication technology and information processing technology, the electrical signals handled in the information communication field have been increasingly becoming faster and larger in capacity in recent years. In order to achieve higher speed and larger capacity of communication, the electrical signals are becoming higher in frequency. However, since high-frequency electrical signals are likely to have large transmission losses, a circuit board compatible with high-frequency electrical signals is required. Transmission loss can be separated into conductor loss and dielectric loss, and reduction of each loss is necessary.

[0003] Dielectric loss is derived from the insulator layer of the circuit board, and it is known that the dielectric loss becomes smaller when the dielectric constant and the dielectric tangent of the insulator layer are smaller. Also, since it is proportional to the frequency, it is more likely to be affected as the frequency increases. Therefore, as a material suitable for a high-frequency compatible circuit board, a resin with a small dielectric constant and a small dielectric tangent has attracted attention, and for example, circuit boards using films with a small dielectric constant and a small dielectric tangent such as fluorine films and LCPs have been developed (Patent Document 1).

[0004] On the other hand, since conductor loss depends on the resistance value of the conductor, silver or copper with a small resistance value is preferably used as the conductor layer for forming the wiring. For these conductor layers, in addition to the method of bonding a metal foil to an insulator, a method of forming a thin metal layer on a smooth resin by sputtering to form the conductor layer of the circuit board is also known. Since the conductor layer formed by sputtering is very thin, several hundred nm or less, the conductor is thickened by electrolytic copper plating or the like on the sputtering layer for wiring processing to form a circuit board (Patent Document 2).

[0005] Typical methods of wiring processing include the subtractive method and the semi-additive method. The subtractive method is a process where, after thickening the entire surface of a thin metal layer through electrolytic copper plating, a resist is applied only to the pattern desired for the wiring so that the metal layer remains, and the unnecessary areas are etched with a chemical solution. The semi-additive method involves exposing the metal portions of the wiring pattern to be processed on a thin metal layer, covering the other areas with a resist, applying electrolytic plating to the wiring pattern portion to thicken the conductor layer, and then removing the thin metal layer in the areas other than the wiring covered with the resist by soft etching. In both methods, etching is essential for forming the wiring. When attempting to accurately form a fine pattern using these methods, etching variations in the wiring portion become an issue, so the surface of the conductor layer is required to have smoothness.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] Conventionally, polyimide films have been used for circuit boards due to their high heat resistance. However, polyimide has poor dielectric properties for use in the high-frequency band, and there are concerns that its dielectric properties change due to moisture absorption. Recently, fluorine films with good dielectric properties have attracted attention as circuit boards compatible with high frequencies. However, fluorine films have high releasability due to their composition and poor adhesion to conductors. Therefore, in Patent Document 1, in order to directly adhere a fluorine-based resin electrical insulation layer and a conductive metal foil with sufficient adhesion, fine protrusions are formed on the surface of the fluorine-based resin electrical insulation layer, and one surface of the conductive metal foil is roughened to produce a laminate. However, as described above, since surface smoothness is required to accurately form fine patterns, it has been difficult to obtain sufficient performance. In addition, when attempting to form a circuit by the semi-additive method, etching is often performed in a short time to etch only a thin metal layer. If the smoothness is poor, there is a problem that copper residue occurs due to variations in roughness. Furthermore, it is known that the current flowing through a conductor is transmitted only in the very surface layer due to the skin effect. When the roughness of the conductor surface is large, it is known that the transmission length increases, resulting in resistance and increased transmission loss. Therefore, there has been a problem that if the interface between the film and copper is roughened to improve adhesion, the transmission loss increases, leading to a decrease in performance.

[0008] Therefore, as a material with good dielectric properties, attention was paid to a polyarylene sulfide-based resin film typified by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS). However, polyarylene sulfide-based resins also have few surface functional groups, and there is room for improvement in adhesion to metal layers. A method for improving adhesion while maintaining smoothness was necessary.

Means for Solving the Problems

[0009] A preferred embodiment of the polyarylene sulfide-based resin film of the present invention is a polyarylene sulfide-based resin film in which the oxygen atoms detected by analysis by X-ray photoelectron spectroscopy (XPS) on at least one surface are 10 atomic% or more and 17 atomic% or less, and the atomic ratio O / C of oxygen atoms to carbon atoms is 0.10 or more and 0.25 or less.

[0010] A preferred embodiment of the metal laminate of the present invention is a metal laminate having a metal layer in contact with a polyarylene sulfide resin film on the polyarylene sulfide resin film, and the metal atoms detected by XPS analysis of the surface (α surface) of the metal layer that was in contact with the polyarylene sulfide resin film and peeled off from the polyarylene sulfide resin film under the following conditions are 10 atomic% or less.

[0011] Condition: Fix the polyarylene sulfide resin film side of a strip-shaped metal laminate with a metal layer thickness of 9 μm and a width of 10 mm to a flat plate, and under an environment of room temperature 23°C and humidity 50%, hold the metal layer and peel it at a peeling speed of 100 mm / min at an angle of 180°.

[0012] A preferred embodiment of the method for producing a polyarylene sulfide resin film of the present invention is a method for producing a polyarylene sulfide resin film, which includes a step of performing plasma treatment at a treatment power density of 0.1 kW·min / m 2 or more and 50 kW·min / m 2 or less in an atmosphere of 0.1 Pa or more and 100 Pa or less.

[0013] A preferred embodiment of the method for producing a metal laminate of the present invention is a method for producing a metal laminate, which includes a step of performing plasma treatment on a polyarylene sulfide resin film at a treatment power density of 0.1 kW·min / m 2 or more and 50 kW·min / m 2 or less in an atmosphere of 0.1 Pa or more and 100 Pa or less, and then laminating a metal by a vapor deposition method or a method of bonding a metal foil.

Advantages of the Invention

[0014] According to the present invention, a metal laminate that achieves both smoothness and adhesion can be obtained, and a circuit board with excellent performance can be obtained.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0016] Hereinafter, with reference to the drawings and the like, the polyarylene sulfide-based resin film and the metal laminate of the present invention will be described in more detail.

[0017] The polyarylene sulfide-based resin film of the present invention is a film mainly composed of a polyarylene sulfide-based resin. The main component means occupying 80% by mass or more of the raw materials constituting the film. The polyarylene sulfide-based resin film may be a single layer or two or more layers may be laminated. The polyarylene sulfide-based resin is a homopolymer or copolymer having a repeating unit of -(Ar-S)-. Examples of Ar include units represented by the following formulas (1) to (11).

[0018]

Chemical formula

[0019] (R1 and R2 are substituents selected from a hydrogen atom, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different) As the repeating unit of the polyarylene sulfide resin used in the present invention, the p-arylene sulfide unit represented by the above formula (1) is preferable. Representative examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers thereof, and mixtures thereof. As the particularly preferable p-arylene sulfide unit, from the viewpoints of film physical properties and economy, the p-phenylene sulfide unit is preferably exemplified. In the present invention, from the viewpoints of durability, dimensional stability, etc., the p-phenylene sulfide unit represented by the structural formula of the following formula (12) preferably occupies 75 mol% or more, more preferably 80 mol% or more, and still more preferably 85 mol% or more of all the repeating units.

[0020] [Chemical formula]

[0021] The polyarylene sulfide resin film of the present invention preferably has a melting point of 275°C or lower on at least one surface layer, more preferably 220°C or higher and 275°C or lower, and still more preferably 245°C or higher and 265°C or lower. Here, the surface layer refers to the layer located in the outermost layer when the polyarylene sulfide resin film has two or more layers. When the polyarylene sulfide resin film is a single layer, the single layer is used as the surface layer.

[0022] When the melting point of the surface layer is set to 275°C or lower, in order to maintain the heat resistance of the entire polyarylene sulfide resin film, it may be laminated in two or more layers. By setting the melting point to 275°C or lower, the adhesion to the metal layer can be improved, and peeling of the metal layer during subsequent circuit processing can be reduced. From the same perspective, it is more preferable that the melting point is 265°C or lower. Also, in the lamination of the metal layer, it can be processed at a low temperature, suppressing problems due to oxidation of the resin or metal, and suppressing the film from warping due to the remaining stress caused by the difference in the thermal expansion coefficients of the resin and the metal. Further, when the melting point is 220°C or higher, the crystallinity of the polyarylene sulfide resin can be made sufficient, the heat resistance can be made sufficient, and the hygroscopicity can be lowered. From the same perspective, it is more preferable that the melting point is 245°C or higher. The melting point can be measured from the peak temperature of the endothermic melting peak of the DSC chart obtained using a differential scanning calorimeter in accordance with JIS K7121-1987 for a sample obtained by scraping off the surface layer. When multiple peak temperatures are observed, the peak temperature on the low-temperature side is taken as the melting point.

[0023] As the polyarylene sulfide resin for setting the melting point of the surface layer to 275°C or lower, it is preferably copolymerized with a copolymer unit in the range of 2 to 25 mol%, more preferably 2 to 15 mol%, per 100 mol% of the repeating unit of the above polyarylene sulfide resin. By having 2 mol% or more of such a copolymer unit, it becomes possible to set the melting point of the polyarylene sulfide resin within the aforementioned range, and the processability can be made sufficient. Also, when the copolymer unit is 25 mol% or less, the degree of polymerization of the polyarylene sulfide resin can be made sufficiently high and the mechanical properties are improved.

[0024] Preferred copolymer units are represented by the following formulas (13) to (17).

[0025]

Chemical formula

[0026] [Chemistry]

[0027] [Chemistry]

[0028] (Here, X represents an alkylene, CO, or SO2 unit.)

[0029] [Chemistry]

[0030] [Chemistry]

[0031] (Here, R represents an alkyl, nitro, phenylene, or alkoxy group.) Particularly preferred copolymer units are m-phenylene sulfide units. The mode of copolymerization with the copolymer component is not particularly limited, but a random copolymer is preferred. The composition of the polyarylene sulfide resin may contain various additives such as antioxidants, heat stabilizers, antistatic agents, and antiblocking agents within a range that does not impair the effects of the present invention.

[0032] The polyarylene sulfide resin film of the present invention may include a layer made of another resin. Examples of the resin constituting the laminate include, but are not limited to, polyimide resin, polyamide resin, polyether ether ketone, polyether imide, polyamide imide resin, polyolefin resin such as polyethylene and polypropylene, polystyrene, polycarbonate, acrylic resin, urethane resin, fluororesin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyketone, and epoxy resin. Also, two or more selected from the above and polyarylene sulfide resin can be blended and used.

[0033] The thickness of the polyarylene sulfide resin film of the present invention is not particularly limited, but from the viewpoints of film-forming property and processability, it is preferably 2 μm or more and 300 μm or less, more preferably 5 μm or more and 180 μm or less, and even more preferably 25 μm or more and 150 μm or less.

[0034] The surface roughness Ra of at least one surface of the polyarylene sulfide resin film of the present invention is preferably 0.01 μm or more and 0.20 μm or less, and more preferably 0.01 μm or more and 0.12 μm or less. The surface roughness Ra is the arithmetic mean roughness defined in JIS B 0601-1994. When the surface roughness is 0.01 μm or more, the film can slide appropriately when wound into a roll shape, and the occurrence of scratches and wrinkles can be suppressed. When it is 0.20 μm or less, it is possible to reduce the pattern of the metal layer forming the circuit from becoming unclear due to the surface roughness, suppress the occurrence of copper residue in the etching process, and suppress the increase in transmission loss due to the skin effect.

[0035] Since the polyarylene sulfide resin has few surface functional groups and there is room for improvement in adhesion, it is necessary to increase the interaction with the metal layer to be laminated. As a result of intensive studies by the inventors, the surface of the polyarylene sulfide resin film was modified, and a state of surface functional groups capable of improving adhesion was found. This will be specifically described below.

[0036] In a preferred embodiment of the polyarylene sulfide resin film of the present invention, the oxygen atoms detected by X-ray photoelectron spectroscopy (XPS) on at least one surface are 10 atomic% or more and 17 atomic% or less, and the atomic ratio O / C of oxygen atoms to carbon atoms is 0.10 or more and 0.25 or less. XPS irradiates the sample surface with soft X-rays in ultra-high vacuum and detects the photoelectrons emitted from the surface with an analyzer, obtaining elemental information on the surface from the binding energy values of the bound electrons in the substance, obtaining information on the bonding state from the energy shift of each peak, and further performing quantification using the peak area ratio. Since XPS analyzes the depth region corresponding to the length (mean free path) that photoelectrons can travel in the substance, surface information on the measurement surface can be obtained. The oxygen atoms detected by XPS analysis of the film surface are preferably 10 atomic% or more and 17 atomic% or less, more preferably 11 atomic% or more and 15 atomic% or less. By setting the oxygen atoms to 10 atomic% or more, functional groups contributing to adhesion can be ensured, and the effect of improving adhesion to the metal layer can be obtained. From the same viewpoint, the oxygen atoms are more preferably 11 atomic% or more. Also, by setting the oxygen atoms to 17 atomic% or less, a decrease in adhesion due to excessive oxidation of the resin and oxidation of the directly contacting metal layer can be suppressed. From the same viewpoint, the oxygen atoms are more preferably 15 atomic% or less. The atomic ratio O / C of oxygen atoms to carbon atoms on the film surface is preferably 0.10 or more and 0.25 or less, more preferably 0.15 or more and 0.23 or less. By setting the atomic ratio O / C to 0.10 or more, necessary functional groups can be introduced. From the same viewpoint, the atomic ratio O / C is more preferably 0.15 or more. Also, by setting the atomic ratio O / C to 0.25 or less, surface layer weakening due to excessive oxidation can be suppressed, and the adhesive strength can be increased. From the same viewpoint, the atomic ratio O / C is more preferably 0.23 or less.

[0037] The polyarylene sulfide-based resin film of the present invention preferably has an atomic ratio S / C of sulfur atoms to carbon atoms detected by X-ray photoelectron spectroscopy (XPS) on at least one surface in the range of 0.10 or more and 0.16 or less, more preferably 0.12 or more and 0.16 or less. When introducing oxygen atoms into the polyarylene sulfide-based resin film, it is considered to be accompanied by the desorption of sulfur atoms. Therefore, by setting the atomic ratio S / C of sulfur atoms to carbon atoms to 0.10 or more, it is possible to suppress the surface layer from becoming fragile due to a significant decrease in sulfur caused by molecular chain cleavage and prevent a decrease in adhesion to the metal layer. By setting it to 0.16 or less, the number of functional groups becomes sufficient and the adhesion can be improved.

[0038] The polyarylene sulfide-based resin film of the present invention preferably has a peak area attributed to sulfur oxides in the range of 5% or more and 20% or less, more preferably 5% or more and 15% or less, when the peak area attributed to S2p of sulfur atoms detected by X-ray photoelectron spectroscopy (XPS) on at least one surface is set to 100%. In the process of modifying the polyarylene sulfide-based resin film, surface oxidation often proceeds simultaneously with the modification. Not only is oxygen introduced into the skeletal ends of the polyarylene sulfide-based resin, but sulfur, which is a relatively reactive site, is also oxidized. However, since sulfur oxides do not necessarily all contribute to metal adhesion, if surface oxidation progresses more than necessary, it may lead to resin deterioration and be disadvantageous for adhesion. By having a peak area attributed to sulfur oxides of 5% or more, functional groups that contribute to adhesion can be ensured. By setting it to 20% or less, resin deterioration due to oxidation can be suppressed and adhesion to the metal can be ensured.

[0039] Analysis of the polyarylene sulfide-based resin film by XPS uses monochromatic Al Kα 1.2 rays, measures with an X-ray diameter of 1 mm and a photoelectron detection angle of 90°. The obtained spectrum is smoothed by 11-point smoothing, C1s (CH x, the horizontal axis is corrected with (C-C) being 284.6 eV, and the composition ratio is calculated from the peak area. For sulfur oxides, with the peak area in the range of 174 - 160 eV attributed to S2p taken as 100%, it is divided into Group 1 (C-S, S-S), Group 2 (SO), Group 3 (satellite peak, SO x (2 ≤ x ≤ 4)), Group 4 (S 2- ). Among these, the sum of Group 2 and Group 3 is taken as sulfur oxides to calculate the ratio.

[0040] As for the method of modifying the surface of the polyarylene sulfide resin film to the above preferable surface state, from the viewpoints of being easy to uniformly process in-plane and easy to adjust the surface state depending on conditions, the method by plasma treatment can preferably be adopted.

[0041] Plasma treatment is a method of modifying the surface by exposing a polyarylene sulfide-based resin film, which is a material to be treated, to a discharge obtained by applying a high DC or AC voltage between a high-voltage application electrode and a counter electrode. Polyarylene sulfide-based resin films have problems such as low polarity, where the coating film peels off and cannot cover the entire surface, or poor adhesion, and various surface treatments have been conventionally utilized. The aim of conventional surface treatments has been to increase the polarity of the film surface and improve wettability, targeting the introduction of a large number of oxygen atoms through corona treatment or ozone treatment in the atmosphere. However, when laminating a metal to improve adhesion, if the film surface is excessively oxidized, the metal may be oxidized from the interface and the performance may deteriorate. In addition, in order to increase the functional groups introduced onto the film surface, it is effective to cut a part of the bonds of the polyarylene sulfide-based resin film and introduce oxygen. However, according to the inventors' studies, if the molecular chain cleavage progresses too far in the film surface layer, when a metal laminate is formed, a force is applied to the interface between the metal with different physical properties and the film, and it has been found that the weakened film undergoes cohesive failure and it becomes difficult to obtain sufficient adhesion. That is, the inventors have clarified that there are problems with adhesion to the metal layer because the surface state has not been sufficiently controlled or the film has been embrittled by the conventional treatment methods. Therefore, as a result of intensive studies, the inventors have found a method to effectively obtain functional groups that are easily bonded to the metal while suppressing the embrittlement of the polyarylene sulfide-based resin film and appropriately cutting the bonds. That is, by the manufacturing method of the polyarylene sulfide-based resin film in the present invention, the desired surface state of the above-described polyarylene sulfide-based resin film can be efficiently obtained. In addition, while obtaining a strong bonding state due to the M-O-S bond in the metal laminate described later, it is possible to reduce the molecular chains that do not become functional groups strongly bonded to the metal in the vulnerable state where the molecular chains in the polyarylene sulfide-based resin film portion are cleaved. Hereinafter, the manufacturing method of the polyarylene sulfide-based resin film of the present invention will be specifically described.

[0042] A preferred embodiment of the method for producing a polyarylene sulfide resin film of the present invention is to perform plasma treatment on the polyarylene sulfide resin film under reduced pressure from the viewpoint of enabling stable and efficient treatment. The plasma treatment is performed in an atmosphere with a pressure of 0.1 Pa or more and 100 Pa or less, and 0.1 kW·min / m 2 or more and 50 kW·min / m 2 or less of the treatment power density. Preferably, the method includes a step of performing plasma treatment. When performing plasma treatment under reduced pressure, the pressure of the atmosphere is preferably 0.1 Pa or more and 100 Pa or less, more preferably 0.1 Pa or more and 20 Pa or less, and even more preferably 0.1 Pa or more and 15 Pa or less. By setting it to 0.1 Pa or more, plasma discharge can be stably maintained, and since active species having energy suitable for functional group generation are present at an appropriate density, modification can be performed efficiently. By setting it to 100 Pa or less, it is possible to suppress the reaction and deactivation of active species with each other, and to give a sufficient treatment effect to the object to be treated. From the same viewpoint, 20 Pa or less is more preferable, and 15 Pa or less is even more preferable.

[0043] In plasma treatment, in order to increase the treatment efficiency or introduce specific functional groups, the atmosphere during plasma treatment may be adjusted by introducing a gas into the discharge space. The gases used can be various gases such as argon, N2, He, Ne, O2, CO2, CO, air, water vapor, H2, NH3, C n H 2n+2 (where n is an integer from 1 to 4), etc., and can be used alone or in combination. The gas to be used can be selected according to the ease of plasma discharge, the energy of the resulting active species, and the type of functional group to be introduced. In the modification of the polyarylene sulfide resin film, it is preferable to contain argon or N2, which is easy to generate plasma discharge and has relatively high energy of active species, and O2, CO2, or CO in order to facilitate the introduction of oxygen. Among them, a mixed gas of argon and O2 or argon and CO2 is more preferable, and a mixed gas of argon and O2 is even more preferable. Also, in order to suppress excessive surface treatment, the atmosphere is argon, He, Ne, O2, CO2, CO, water vapor, H2, C n H 2n+2It is preferably composed of at least one selected from the group consisting of hydrocarbons represented by (where n is an integer from 1 to 4). When it is a mixed gas, it is preferably a gas containing 50% or more oxygen atoms in terms of volume ratio so that a sufficient amount of oxygen can be introduced.

[0044] The shape of the high-voltage application electrode can be arbitrary, for example, a rod shape that can continuously process while transporting a film, a plate shape with a large area, etc. can be mentioned. Further, in order to increase the processing intensity or reduce the damage to the substrate, it can be a magnetron electrode or a dielectric-coated electrode. The counter electrode is not particularly limited as long as it can process while closely adhering to the film, but a drum-shaped electrode that can support film transportation is preferable. The number of high-voltage application electrodes and counter electrodes does not need to be the same. For example, if there are two or more high-voltage application electrodes for one counter electrode, the space can be saved and the processing efficiency can be increased. The distance between the electrodes can be appropriately set according to the gas pressure conditions and the processing intensity. From the viewpoint of suppressing damage to the film while improving the adhesion of the polyarylene sulfide-based film, it is preferably in the range of 0.05 cm or more and 30 cm or less.

[0045] The processing intensity is preferably 0.1 kW·min / m 2 or more and 50 kW·min / m 2 or less, and more preferably 0.3 kW·min / m 2 or more and 15 kW·min / m 2 or less. Here, the processing power density is the value obtained by dividing the product of the power input to the discharge and the time by the discharge area. In the case of processing a long film, it is the value obtained by dividing the input power by the width of the discharge part and the film processing speed. By setting the processing power density to 0.1 kW·min / m 2 or more, the energy required for modification can be given. From the same viewpoint, it is more preferably 0.3 kW·min / m 2 or more. By setting the processing power density to 50 kW·min / m 2By setting the following, it is possible to suppress damage to the film. From the same viewpoint, the treatment power density is 15 kW·min / m 2 It is more preferably the following. Regarding the conditions of plasma treatment, when the pressure is 0.1 Pa or more and less than 10 Pa, the treatment power density is 0.1 kW·min / m 2 or more and 50 kW·min / m 2 or less is preferable. When the pressure is 10 Pa or more and 100 Pa or less, 0.3 kW·min / m 2 or more and 15 kW·min / m 2 or less is more preferable.

[0046] In addition, from the viewpoint of suppressing embrittlement of the polyarylene sulfide-based resin film due to excessive surface treatment, the oxygen atoms detected by X-ray photoelectron spectroscopy (XPS) on at least one surface of the polyarylene sulfide-based resin film before plasma treatment are 17 atomic% or less, and the atomic ratio O / C of oxygen atoms to carbon atoms is preferably 0.25 or less. From the same viewpoint and the viewpoint of reducing the number of surface treatment times, it is more preferable that the oxygen atoms are 10 atomic% or less and O / C is 0.1 or less.

[0047] The metal laminate of the present invention has a metal layer in contact with the polyarylene sulfide-based resin film on the polyarylene sulfide-based resin film. The metal layer preferably has a thickness of 0.05 μm or more and 30 μm or less, and more preferably 0.1 μm or more and 20 μm or less. By having a thickness of 0.05 μm or more, oxidation of the metal can be suppressed. From the same viewpoint, it is preferably 0.1 μm or more. By having a thickness of 30 μm or less, the metal layer can be made flexible and cracking or warping of the laminate can be suppressed. From the same viewpoint, the thickness is more preferably 20 μm or less. The metal layer may be a single layer or two or more layers may be laminated.

[0048] In the present invention, the metal layer preferably has copper as the main component. The main component refers to the component whose constituent atoms account for 60 atomic% or more. The method of laminating the metal layer can be appropriately selected in consideration of productivity and the like. For example, a method of extruding or coating a polyarylene sulfide-based resin on a copper foil, a method of laminating a metal foil on a polyarylene sulfide-based resin film, and a method of forming a metal layer by a vapor deposition method typified by a vacuum evaporation method or a sputtering method can be mentioned. Among these, a preferred embodiment of the method for manufacturing the metal laminate of the present invention is from the viewpoint of maintaining a desirable surface state of the polyarylene sulfide-based resin film suitable for productivity and adhesion. Under an atmosphere of 0.1 Pa or more and 100 Pa or less of pressure on the polyarylene sulfide-based resin film, 0.1 kW·min / m 2 or more and 50 kW·min / m 2 After plasma treatment at the following treatment power density, it preferably includes a step of laminating a metal by a vapor deposition method or a method of bonding a metal foil. When bonding (laminating) a metal foil to a polyarylene sulfide-based resin film from the above viewpoint, it is more preferable to use a thermal lamination method for directly laminating the film and the metal foil. When the temperature of the thermal lamination is set to be Tm - 20°C or more and Tm + 50°C or less, where Tm is the melting point of the surface layer of the polyarylene sulfide-based resin film, it is more preferably Tm°C or more and Tm + 30°C or less. By setting the temperature of the thermal lamination to be Tm - 20°C or more, the resin on the film surface can be softened to obtain sufficient adhesion. From the same viewpoint, the temperature is preferably Tm°C or more. Also, by setting the temperature to be Tm + 50°C or less, a desirable surface state of the polyarylene sulfide-based resin film can be maintained, and it is possible to prevent the film from becoming brittle due to resin decomposition or crosslinking, resulting in a decrease in flexibility or being easily cohesively destroyed. It is also possible to suppress warping due to the difference in the thermal expansion coefficients of the resin and the metal foil. From the same viewpoint, the temperature is more preferably Tm + 30°C or less.

[0049] The pressure of the laminate is preferably 0.1 MPa or more and 10 MPa or less, more preferably 0.5 MPa or more and 8 MPa or less, and even more preferably 1.0 MPa or more and 5 MPa or less. By setting the pressure to 0.1 MPa or more, the metal and the film can be sufficiently brought into contact and bonded. From the same perspective, the pressure is more preferably 0.5 MPa or more, and even more preferably 1.0 MPa or more. Further, by setting the pressure to 10 MPa or less, deformation of the film can be suppressed, and problems such as resin flowing in the laminate can be avoided. From the same perspective, the pressure is more preferably 8 MPa or less, and even more preferably 5 MPa or less.

[0050] As a method for depositing a metal by a vapor deposition method, from the viewpoints of productivity and maintaining a desirable surface state of a polyarylene sulfide-based resin film suitable for adhesion, a vacuum evaporation method or a sputtering method can be preferably used. Since the surface roughness of the vapor deposition method is determined following the surface of the substrate to be deposited, it is preferable to use a smooth film so that the metal layer can be made smooth. In the case of the vacuum evaporation method, the methods include an induction heating evaporation method, a resistance heating evaporation method, a laser beam evaporation method, an electron beam evaporation method, etc. From the viewpoint of having a high film deposition rate, the electron beam evaporation method is preferably used. For the deposition on the film, roll-to-roll processing is preferably used from the viewpoint of productivity. However, since the film is exposed to heat during evaporation, it is preferable to evaporate while cooling with a cooling roll in contact with the back surface of the deposition surface of the film. Suppressing the deformation of the film due to the heat during evaporation and cooling can reduce the film stress of the metal layer, which is advantageous for suppressing the peeling of the metal layer and is also desirable from the viewpoint of maintaining a desirable surface state of the polyarylene sulfide-based resin film. From the same viewpoint, the maximum temperature of the polyarylene sulfide-based resin film during evaporation is preferably below the glass transition temperature of the film surface layer. When multiple glass transition temperatures of the film surface layer are observed, it is preferable to deposit the metal below the highest temperature. The glass transition temperature can be determined from a DSC chart obtained using a differential scanning calorimeter. Also in the case of the sputtering method, roll-to-roll processing is preferably used from the viewpoint of productivity. The sputtering method may use any power source of DC, AC, or pulse, and a magnet may be arranged in the apparatus to utilize a magnetic field or an ion beam may be utilized. For example, a magnetron sputtering method, a dual magnetron sputtering method, an ion beam sputtering method, etc. can be mentioned. From the viewpoints of productivity and maintaining a desirable surface state of a polyarylene sulfide-based resin film suitable for adhesion, it is preferable to perform sputtering with a power output of 5 kW or less.

[0051] In the present invention, two or more metal layers may be laminated. Particularly in the case of the vapor deposition method, a base metal layer can be laminated in order to improve the adhesion between the film and the metal layer or to suppress migration. When laminating the base metal layer, it is preferable to laminate the base metal on the polyarylene sulfide resin film and then laminate a layer mainly composed of copper in contact with the base metal layer. The base metal layer preferably contains at least one selected from the group consisting of copper, nickel, titanium, and alloys containing at least one of them. Among them, from the viewpoints of preventing oxidation of the metal layer and corrosion resistance, it preferably contains at least one selected from the group consisting of nickel, titanium, and alloys containing at least one of nickel or titanium. When the metal laminate of the present invention is used for a circuit board for high-speed signal transmission, since magnetic nickel attenuates the signal, the metal of the base metal layer is preferably titanium or an alloy containing titanium. The thickness of the base metal layer is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 50 nm or less. By setting the thickness of the base metal layer to 1 nm or more, it becomes easier to obtain a uniform effect in the plane, and by setting it to 100 nm or less, it is possible to suppress a decrease in wiring pattern processability due to the difference in etching rate between the copper layer and the base layer. Also, when the base metal is a magnetic material and its thickness is large, there may be a problem that the loss increases and the signal attenuates in high-speed signal transmission. As the film formation method of the base metal layer, a vapor deposition method typified by sputtering or vacuum evaporation is preferable from the viewpoints of the thickness accuracy of the thin film and productivity, and the sputtering method that reaches the film surface with stronger energy is more preferable in terms of improving adhesion. The method of forming the base metal layer and the layer laminated thereon may be the same or different. For example, both the base metal layer and the layer thereon may be formed by sputtering, or the base metal layer may be formed by sputtering and the layer thereon may be formed by vacuum evaporation. When both are formed by the vapor deposition method, they may be formed in two steps for each layer or continuously, but since the very thin base metal layer is easily oxidized, it is preferable to form the film continuously in order to reduce the influence of oxidation.Also, when forming a metal layer by a vapor deposition method, since it is often made into a thin film from the viewpoint of productivity, in order to obtain a sufficient metal thickness as a conductor with suitable resistance for a circuit, the layer obtained by the vapor deposition method can be used as a power supply layer, and a copper layer can be further laminated by electrolytic copper plating.

[0052] In the metal laminate of the present invention, the surface roughness Ra of the surface of the metal layer that is not in contact with the polyarylene sulfide-based resin film is preferably 0.01 μm or more and less than 0.20 μm, more preferably 0.01 μm or more and 0.15 μm or less, and even more preferably 0.01 μm or more and 0.10 μm or less. The surface roughness Ra is the arithmetic mean roughness defined in JIS B 0601-1994. Since the polyarylene sulfide-based resin film having good dielectric properties and the metal layer are in direct contact, when used as wiring for a circuit board, it is possible to suppress transmission loss of transmission signals due to the skin effect, particularly in the high-frequency band. A method of directly contacting the polyarylene sulfide-based resin film and the metal layer can be, in addition to laminating copper foil, vapor deposition by sputtering or evaporation. In the case of a vapor deposition method, particularly evaporation, since the metal layer tends to grow following the unevenness of the surface of the polyarylene sulfide-based resin film, the surface roughness of the surface of the metal layer that is not in contact with the polyarylene sulfide-based resin film is strongly affected by the surface roughness of the polyarylene sulfide-based resin film. Generally, when forming a laminate, the surface is roughened to enhance adhesion, but the present application is characterized in that, despite providing a metal layer on a smooth substrate, strong adhesion is achieved. When the surface roughness Ra of the surface of the metal layer that is not in contact with the polyarylene sulfide-based resin film is 0.01 μm or more and 0.20 μm or less, it is possible to suppress transmission loss due to the skin effect on the surface of the metal layer that is not in contact with the polyarylene sulfide-based resin film. Further, by adopting the above aspect, it can be used as wiring for a practical circuit board without a step of smoothing the metal layer surface again, and can contribute to the efficiency improvement and environmental load reduction in the wiring process of the circuit board.

[0053] In the case of a metal laminate using a conventional polyarylene sulfide resin film, there is room for improvement in adhesion to the metal layer, and a method for improving adhesion while maintaining smoothness was required. The present inventors considered performing various surface treatments on the polyarylene sulfide resin film and found a desirable state in the cross-sectional direction of the polyarylene sulfide resin film in the metal laminate. Since chemical bonding contributes to the adhesion between the polyarylene sulfide resin film and the metal layer while maintaining smoothness, it was found that the state at these interfaces, that is, the α-plane, greatly contributes to the adhesion. Therefore, the state will be described below.

[0054] Generally, polyarylene sulfide resin films have low polarity, making it difficult to form chemical bonds and leaving room for improvement in adhesion to metal layers. In order to improve the adhesive strength, it is necessary to increase the chemical bonding between the polyarylene sulfide resin film and the metal layer. However, the present inventors found that the state of the sulfur oxidation component (SO) and sulfide (S 2- ) present on the α-plane has a great influence on the adhesion. The mechanism by which these components improve the adhesive strength to the metal layer is considered to be due to the sulfur derived from the polyarylene sulfide resin film and the metal atom M of the metal laminate forming an M-O-S bond via the oxygen atom O. For example, in the case of an unmodified polyarylene sulfide resin film, SO is below the detection limit on its surface, and even after laminating the metal, SO is not detected when analyzing the α-plane, indicating that no bond is formed, so the adhesion is considered to be weak.

[0055] A preferred embodiment of the metal laminate of the present invention is a metal laminate having a metal layer in contact with the polyarylene sulfide resin film on the polyarylene sulfide resin film, and the metal atoms detected by XPS analysis of the surface (α-plane) of the metal layer that was in contact with the polyarylene sulfide resin film and peeled off from the polyarylene sulfide resin film under the following conditions are 10 atomic% or less.

[0056] Condition: Fix the polyarylene sulfide resin film side of a strip-shaped metal laminate with a metal layer thickness of 9 μm and a width of 10 mm to a flat plate, and in an environment of 23 °C and 50% humidity at room temperature, hold the metal layer and peel it at a peeling rate of 100 mm / min at an angle of 180°.

[0057] When the metal atoms detected by XPS analysis of the surface (α surface) in contact with the polyarylene sulfide resin film of the metal layer peeled from the metal laminate are 10 atomic% or less, it means that a large amount of the polyarylene sulfide resin film adheres to the peeled metal layer. When the metal atoms on the α surface are 10 atomic% or less, the adhesion of the metal layer can be made sufficient, and peeling during circuit formation can be suppressed. From the same viewpoint, it is more preferable that the metal atoms on the α surface are 5 atomic% or less. When two or more types of metal atoms are detected, the total is taken as the amount of metal atoms. The detected metal atoms depend on the configuration of the laminate. For example, when the metal layer is a single copper layer, the detected metal atoms are copper, but when a layer containing titanium is used as the underlying metal layer and a copper layer is laminated thereon, titanium and copper may be detected.

[0058] When the peak area attributed to S2p of sulfur atoms detected by XPS analysis of the α surface is taken as 100%, the peak area attributed to the oxidized component (SO) of sulfur is preferably 1% or more and 7% or less, and more preferably 2% or more and 5% or less. By setting the peak area attributed to the oxidized component (SO) of sulfur to 1% or more, the surface is sufficiently modified and the adhesion is improved. From the same viewpoint, 2% or more is more preferable. Also, when it is 7% or less, a decrease in adhesion due to deterioration of the polyarylene sulfide resin film can be reduced, and peeling during circuit formation can be suppressed. From the same viewpoint, 5% or less is more preferable.

[0059] When the peak area attributed to S2p of sulfur atoms detected by XPS analysis of the α surface is taken as 100%, sulfide (S 2- ) The peak area attributed to is preferably 5% or less, and more preferably 3% or less. Sulfide (S 2-) is considered to be what remains on the surface without becoming a functional group that strongly binds to the metal in a state where the molecular chains of the polyarylene sulfide-based resin film are cleaved. When the molecular chains are cleaved under conditions such as the presence of sufficient oxygen, it can become a functional group that contributes to adhesion. However, if the required amount of oxygen is not supplied or if it remains on the surface in a low molecular weight state, it remains on the surface without contributing to adhesion. The presence of these components that do not contribute to adhesion is thought to act as an adhesion inhibitor or weaken adhesion due to the alteration of the film or metal layer. Therefore, S 2- If the peak area attributed to is suppressed to 5% or less, excessive alteration of the polyarylene sulfide-based resin film as described above can be suppressed, and thus peeling during circuit formation can be reduced. From the same perspective, the peak area attributed to sulfide (S 2- ) is more preferably 3% or less. Also, the lower limit of the peak area attributed to S 2- is about 1% from the detection limit of the analysis.

[0060] In the production of the metal laminate, the film surface may be damaged or oxidized by heat, resulting in alteration of the surface layer and becoming fragile. When the metal layer is peeled from the polyarylene sulfide-based resin film, the polyarylene sulfide-based resin film has a peeling interface at a position where the strength is weak when viewed in the depth direction from the interface with the metal layer, and a part of the surface layer of the polyarylene sulfide-based resin film thinly adheres to the α-plane of the metal layer. When the polyarylene sulfide-based resin film is fragile, the peeling interface is at a position very close to the metal layer, and the polyarylene sulfide resin adhering to the metal layer is thin, and the elements of the metal layer can be detected by XPS analysis. On the other hand, when the vicinity of the metal layer of the polyarylene sulfide-based resin film is not damaged, the film adhering to the peeled metal layer becomes thick, and the detection amount of the elements of the metal layer decreases. Also, due to the alteration of the polyarylene sulfide-based resin, sulfur atoms may be desorbed. When the desorbed sulfur atoms exist as sulfide ions, they may become an adhesion inhibitor by forming a sulfide with the metal or the like.

[0061] The peeling of the metal layer can be carried out by the method described in the examples. The surface of the metal layer thus obtained that was in contact with the polyarylene sulfide resin film is defined as the α surface, and its surface is analyzed by XPS. The analysis of the α surface of the metal layer peeled from the polyarylene sulfide resin film is performed using monochromatic Al Kα 1,2 rays, with an X-ray diameter of 200 μm and a photoelectron detection angle of 45°. The obtained spectrum is smoothed by 9-point smoothing, and the horizontal axis is corrected with C1s (CH x , C-C) set at 284.6 eV, and the composition ratio is calculated from the peak area. For S2p, with the peak area of the spectrum from 174 to 160 eV taken as 100%, it is divided into Group 1 (C-S, S-S), Group 2 (SO), Group 3 (satellite peak SO x (2 ≤ x ≤ 4)), and Group 4 (S 2- ), and among these, the area ratios of Group 2 and Group 4 are calculated respectively and taken as the component ratios.

[0062] Note that the α surface is randomly measured 10 times, once each, and the component ratio is obtained by calculating for each measurement. When the calculated component ratio is at the detection limit, it is taken as 0%. The arithmetic mean of the component ratios for the 10 locations is taken as the XPS analysis result of the α surface.

[0063] The metal laminate of the present invention has good adhesion between the metal layer and the polyarylene sulfide resin film, and the surface of the metal layer is very smooth, so it can be suitably used for circuit material applications, touch panels, etc. For example, in the case of a circuit board, the metal layer is patterned to form a wiring circuit. The wiring circuit can be formed by known methods such as the subtractive method or the semi-additive method, but when the wiring width of the circuit is narrow, the semi-additive method with less reduction in wiring width by etching is more preferred.

Examples

[0064] The present invention will be described below based on examples. Note that the present invention is not limited to these examples, and these examples can be modified and changed based on the gist of the present invention, and they are not excluded from the scope of the invention.

[0065] [Evaluation Method] (1) Measurement of the melting point of the polyarylene sulfide-based resin film For any layer for which measurement is desired, sampling is performed by scraping off using a microplane. For the scraped sample, in accordance with JIS K7121-1987, as a differential scanning calorimeter, DSC (RDC220) manufactured by Seiko Instruments Inc. and as a data analysis device, Disk Station (SSC / 5200) manufactured by the same company are used. 5 mg of the above sample is placed on an aluminum pan and heated from room temperature to 350 °C at a heating rate of 20 °C / min (1st Run). After taking out the same sample and rapidly cooling it, it is heated from room temperature to 350 °C at a heating rate of 20 °C / min (2nd Run). The peak temperature of the endothermic peak of melting confirmed in the DSC chart of the obtained 2nd Run is defined as the melting point (Tm).

[0066] (2) Analysis of the polyarylene sulfide-based resin film surface by X-ray photoelectron spectroscopy (XPS) Analysis by the XPS method was measured and calculated under the following conditions also described in the text. Apparatus: ESCALAB220iXL Excitation X-ray: monochromatic Al Kα 1,2 Line (1486.6 eV) X-ray path: 1 mm Photoelectron escape angle: 90° (tilt of the detector with respect to the sample surface) Smoothing: 11-point smoothing Horizontal axis correction: C1s (CH x , C-C) was set to 284.6 eV. Measurement location and number of times: The surface of the polyarylene sulfide resin film was randomly measured 10 times at 10 locations, and the component ratio was determined by calculating for each measurement. When the calculated component ratio was below the detection limit, it was set to 0%. The arithmetic mean of the component ratios for the 10 locations was taken as the measurement result.

[0067] (3) Measurement of the surface roughness of the polyarylene sulfide resin film The surface roughness of the film refers to the arithmetic mean roughness defined in JIS B0601 - 1994 and was measured under the following conditions. Apparatus: Surfcorder ET4000A manufactured by Kosaka Laboratory Ltd. Stylus tip radius: 2 μm Measurement area: 500 μm × 500 μm Sample fixation: Kamaboko - shaped glass attached to the apparatus.

[0068] (4) Evaluation of the metal laminate (4 - 1) Measurement of the surface roughness of the metal layer The surface roughness Ra of the metal layer was measured in the same manner as the film in (3) above.

[0069] (4 - 2) Analysis of the metal layer (α - face) peeled from the metal laminate by XPS In this evaluation, the thickness of the metal layer was unified to 9 μm. When the thickness of the metal layer in the laminate was less than 9 μm, it was electroplated with electrolytic copper to reach 9 μm, and when it exceeded 9 μm, it was adjusted by polishing.

[0070] The metal layer was peeled at the interface between the polyarylene sulfide resin film and the metal layer of the metal laminate, and the peeled surface on the metal layer side was analyzed. The peeling of the metal layer was carried out by fixing a 10 - mm - wide strip - shaped laminate to a flat plate and peeling the metal layer at a peeling speed of 100 mm / min and an angle of 180° in an environment of room temperature 23°C and humidity 50%.

[0071] The analysis by the XPS method was measured and calculated under the following conditions also described in this text. Apparatus: Quantera SXM Excitation X - ray: monochromatic Al Kα1,2 Line (1486.6 eV) X-ray path: 200 μm Photoelectron emission angle: 45° (tilt of detector with respect to sample surface) Smoothing: 9-point smoothing Horizontal axis correction: Set C1s (CH x , C-C) to 284.6 eV. Measurement location and number of times: The α-plane was randomly measured at 10 locations, once each. The component ratio was calculated for each measurement, and when the calculated component ratio was below the detection limit, it was set to 0%. The arithmetic mean of the component ratios for the 10 locations was taken as the XPS analysis result of the α-plane.

[0072] (5) Measurement of adhesion of metal layer In the measurement of the adhesion of the metal layer, the thickness of the metal layer was unified to 12 μm. When the thickness of the metal layer of the metal laminate was less than 12 μm, electrolytic copper plating was performed, and when it exceeded 12 μm, the thickness was adjusted by etching or polishing.

[0073] The metal laminate was masked with a masking tape 5 mm wide and etched with ferric chloride to obtain a measurement sample 5 mm wide and 100 mm long. The sample was fixed to a SUS plate using an adhesive tape, and the adhesion was measured under the following conditions while gripping the metal layer. Apparatus: Adhesion / Film Peel Analysis Apparatus VPA-2 Sample width: 5 mm Sample length: 100 mm Peeling conditions: 90°, 100 mm / min Measurement distance: 75 mm.

[0074] Among the obtained measurement profiles, the average value of the adhesion between 4 mm and 50 mm of the peeling distance was taken as the adhesion of the metal layer. When the adhesion was 5 N / cm or more, it was rated as A; when it was 3 N / cm or more and less than 5 N / cm, it was rated as B; when it was 1.0 N / cm or more and less than 3 N / cm, it was rated as C; when it was 0.1 N / cm or more and less than 1.0 N / cm, it was rated as D; and when it was less than 0.1 N / cm, it was rated as E.

[0075] (6) Formation of wiring pattern A wiring pattern was processed using a metal laminate, and its processability was evaluated. Those that could be wired without any remaining copper were designated as A, those with remaining copper at the ends of the wiring pattern or between the wirings that could be processed were designated as B, those with remaining copper or rough straight lines at the wiring ends among those that could be processed were designated as C, and those that could not be wired were designated as D. The pattern processing method is as follows.

[0076] On the surface of the metal layer of the metal laminate, using "PMER (registered trademark)" P-LA900PM manufactured by Tokyo Ohka Kogyo Co., Ltd., a plating resist for a wiring pattern with a resist thickness of 20 μm and L / S = 10 / 10 μm was formed. Then, electrolytic copper plating was performed so that the metal layer thickness became 10 μm. For the electrolytic copper plating, a solution of 50 g / L of copper sulfate pentahydrate, 200 g / L of sulfuric acid, 50 ppm of chlorine, 2 ml / L of the additive "Cover Green (registered trademark)" ST-901A of Mertex Co., Ltd., and 20 ml / L of "Cover Green (registered trademark)" ST-901B was used, and the plating conditions were the jet method and a current density of 1.0 A / dm 2 After the electrolytic copper plating, the plating resist was removed with an alkaline stripping solution, and the metal layer for power supply between the wirings was removed using a hydrogen peroxide-sulfuric acid-based etching solution to form a wiring pattern. When the metal layer contains nickel or titanium as an underlying metal layer, since it is difficult to remove with a hydrogen peroxide-sulfuric acid-based etching solution, after etching the copper layer by the above method, the underlying metal was removed using "Mec Remover" manufactured by Mec Co., Ltd.

[0077] [Example 1] On one side of a biaxially stretched PPS film with a thickness of 100 μm ("Torelina" (registered trademark) film #100 - 3030 manufactured by Toray Industries, Inc., surface layer melting point 280°C), plasma treatment was performed in an argon atmosphere to obtain a polyarylene sulfide resin film. The treatment conditions were in an argon atmosphere, a pressure of 0.3 Pa, and a treatment power density of 0.8 kW·min / m 2 was used.

[0078] On the plasma-treated surface, a metal with a composition of Ni / Cr = 80 / 20 (molar ratio) was formed to a thickness of 25 nm as an underlayer metal layer by magnetron sputtering, and then copper was laminated to a thickness of 90 nm by magnetron sputtering to obtain a metal laminate. The sputtering conditions for both Ni / Cr and Cu were such that argon gas was introduced to achieve a vacuum degree of 0.2 Pa or less, and the output was 500 W using an RF power source.

[0079] [Example 2] A biaxially stretched PPS film with a thickness of 100 μm (Torelina (registered trademark) film manufactured by Toray Industries, Inc., three-layer structure, melting points of the layers on both sides of 255 °C, melting point of the central layer of 280 °C) was used, and a polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 1 except that the atmosphere for plasma treatment was set to argon / O2 = 50 / 50 (volume ratio).

[0080] [Example 3] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2 except that the underlayer metal layer was made of Ti.

[0081] [Example 4] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2 except that copper was directly sputtered onto the plasma-treated polyarylene sulfide resin film.

[0082] [Example 5] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2 except that Ni / Cr was formed as an underlayer metal layer on the plasma-treated polyarylene sulfide resin film, and then copper was laminated by vapor deposition. The copper vapor deposition was performed by vacuum vapor deposition using an electron beam to laminate a copper layer with a thickness of 0.5 μm.

[0083] [Example 6] A metal laminate was obtained by thermally laminating a copper foil on a polyarylene sulfide resin film obtained in the same manner as in Example 2. As the copper foil, electrolytic copper foil CF-T4X-SV, thickness 12 μm, manufactured by Fukuda Metal Co., Ltd. was used. The thermal lamination conditions were 260 °C, 4 MPa for 10 minutes using a vacuum press apparatus manufactured by Kitakawa Seiki Co., Ltd.

[0084] [Example 7] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2, except that the plasma treatment conditions were an argon atmosphere.

[0085] [Example 8] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2, except that the plasma treatment conditions were an O2 atmosphere.

[0086] [Example 9] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 8, except that the plasma treatment conditions were a treatment power density of 0.4 kW·min / m 2

[0087] [Example 10] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 1, except that the plasma treatment conditions were a treatment atmosphere of argon / O2 = 50 / 50 (volume ratio) and a treatment power density of 6.0 kW·min / m 2

[0088] [Example 11] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2, except that the plasma treatment conditions were a treatment power density of 3.5 kW·min / m 2

[0089] [Example 12] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 8, except that the plasma treatment conditions were a treatment power density of 15 kW·min / m 2

[0090] [Example 13] The plasma treatment conditions were the same as in Example 8 except that the treatment power density was 50 kW·min / m 2 A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 8 except for this.

[0091] [Example 14] The plasma treatment conditions were the same as in Example 8 except that the pressure was 0.1 Pa and the treatment power density was 7.0 kW·min / m 2 A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 8 except for this.

[0092] [Example 15] The plasma treatment conditions were the same as in Example 8 except that the pressure was 10 Pa, and a polyarylene sulfide resin film and a metal laminate were obtained.

[0093] [Example 16] The plasma treatment conditions were the same as in Example 8 except that the pressure was 15 Pa, and a polyarylene sulfide resin film and a metal laminate were obtained.

[0094] [Example 17] The plasma treatment conditions were set under a CO2 atmosphere, and the treatment power density was 1.2 kW·min / m 2 A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2 except for this.

[0095] [Example 18] The plasma treatment conditions were set under an N2 / CO2 = 90 / 10 (volume ratio) atmosphere, and a polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 17 except for this.

[0096] [Comparative Example 1] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 1 except that the plasma treatment was not performed and the metal was laminated.

[0097] [Comparative Example 2] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 6, except that the metal was laminated without plasma treatment.

[0098] [Comparative Example 3] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2, except that corona treatment was performed instead of plasma treatment. The corona treatment conditions were as follows: using a corona surface modification device manufactured by Kasuga Electric Co., Ltd., the treatment was performed 5 times at an electrode width of 25 mm, 100 W, and a speed of 0.3 m / min.

[0099] [Comparative Example 4] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2, except that blast treatment was performed instead of plasma treatment. For the blast treatment, silica sand with an average particle size of 200 μm was used as the abrasive, and the treatment was performed by the shot blast method of shooting at a film 1 m away, followed by washing with water.

[0100] [Comparative Example 5] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 2, except that the plasma treatment conditions were a treatment atmosphere of N2 / O2 = 50 / 50 (volume ratio) and a pressure of 0.02 Pa.

[0101] [Comparative Example 6] A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Comparative Example 5, except that the plasma treatment condition was a treatment power density of 15 kW·min / m 2 .

[0102] The evaluation results in each example and comparative example are shown in Tables 1 and 2.

[0103] When obtaining the polyarylene sulfide resin film of Example 1, plasma treatment was performed using a power supply with an AC power supply frequency of 13.56 MHz under the conditions of an output of 100 W and a conveyance speed of 0.5 m / min.

[0104] Also, when the biaxially stretched PPS film with a thickness of 100 μm used in Examples 1 and 2 was sliced with a single-edge blade to about half of its thickness and the cross-section was analyzed by the method of (2), the peak area ratio attributed to the sulfur oxidation component (SO) in any of the films was less than 1%, and the peak area ratio attributed to sulfide (S 2- ) was also less than 1%.

[0105] In Comparative Example 2, the peak area attributed to the sulfur oxidation component (SO) was relatively large due to oxidation during bonding at high temperature. In Comparative Example 4, the residue generated by the blasting treatment was detected in a state where the ends were oxidized, so it is considered that the peak area ratio attributed to the sulfur oxidation component (SO) is relatively high. Also, in Comparative Examples 1 and 2, the relatively high peak area ratio attributed to sulfide (S 2- ) is considered to be because the molecular chains were broken in an oxygen-deficient state during the formation of the base metal layer and remained as residues in a state where it was difficult to contribute to the bonding. Also, for Comparative Example 4, it is considered to be because the residue generated by the blasting treatment remained on the surface.

[0106]

Table 1

[0107]

Table 2

Explanation of Symbols

[0108] 1: Polyarylene sulfide resin film 2: Metal layer 3: Base metal layer 4: α-plane

Claims

1. A metal laminate having a metal layer in contact with a polyarylene sulfide resin film on the polyarylene sulfide resin film, wherein the metal atoms detected by XPS analysis of the surface (α surface) of the metal layer that was in contact with the polyarylene sulfide resin film peeled from the polyarylene sulfide resin film under the following conditions are 10 atomic% or less, and a metal laminate in which, when the peak area attributed to S2p of sulfur atoms detected by XPS analysis of the α surface is taken as 100%, the peak area attributed to the oxidized component (SO) of sulfur is 1% or more and 7% or less. Conditions: The polyarylene sulfide resin film side of a strip-shaped metal laminate with a metal layer thickness of 9 μm and a width of 10 mm is fixed to a flat plate, and in an environment of room temperature 23°C and humidity 50%, the metal layer is gripped and peeled at a peeling rate of 100 mm / min at an angle of 180°.

2. When the peak area attributed to S2p of sulfur atoms detected by XPS analysis of the α plane is taken as 100%, the metal laminate according to claim 1, wherein the peak area attributed to sulfide (S ２－ ) is 5% or less.

3. The metal laminate according to claim 1 or 2, wherein the polyarylene sulfide resin film is a laminate of two or more layers, and the melting point of the surface layer of the polyarylene sulfide resin film in contact with the metal layer is 275°C or lower.

4. The metal laminate according to any one of claims 1 to 3, wherein the main component of the metal layer is copper.

5. The metal laminate according to any one of claims 1 to 4, wherein the surface roughness Ra of the surface of the metal layer that is not in contact with the polyarylene sulfide resin film is 0.01 μm or more and 0.20 μm or less.

6. A method for manufacturing a metal laminate according to Claim 1, wherein the polyarylene sulfide resin film is subjected to plasma treatment at a treatment power density of 0.1 kW·min / m ２ or more and 50 kW·min / m ２ or less in an atmosphere of 0.1 Pa or more and 100 Pa or less, and then a step of laminating a metal by a vapor deposition method or a method of bonding a metal foil is included, and the metal laminate has a metal layer in contact with the polyarylene sulfide resin film on the polyarylene sulfide resin film.

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