WO2021020289A1

WO2021020289A1 - Polyarylene sulfide resin film, metal layered product, production method for polyarylene sulfide resin film, and production method for metal layered product

Info

Publication number: WO2021020289A1
Application number: PCT/JP2020/028494
Authority: WO
Inventors: 山田絵美; 佐藤誠
Original assignee: 東レ株式会社
Priority date: 2019-07-30
Filing date: 2020-07-22
Publication date: 2021-02-04
Also published as: TW202112913A; CN114245810A; KR20220042307A; JPWO2021020289A1

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

A method for producing a polyarylene sulfide-based resin film, a metal laminate, a polyarylene sulfide-based resin film, and a method for producing a metal laminate.

The present invention relates to a method for producing a polyarylene sulfide resin film, a metal laminate, a polyarylene sulfide resin film, and a method for producing a metal laminate, which can be suitably used for wiring board applications, circuit material applications, and the like.

With the development of communication technology and information processing technology, the speed and capacity of electrical signals handled in the information and communication field have been increasing in recent years. Electric signals are becoming higher in frequency in order to achieve higher communication speeds and larger capacities, but high-frequency electrical signals tend to have large transmission losses, so circuit boards that support high-frequency electrical signals are required. ing. The transmission loss can be separated into a conductor loss and a dielectric loss, and it is necessary to reduce each loss.

The dielectric loss is derived from the insulator layer of the circuit board, and it is known that the smaller the dielectric constant and the dielectric loss tangent of the insulator layer, the smaller the dielectric loss. Moreover, since it is proportional to the frequency, the higher the frequency, the more easily it is affected. Therefore, a resin having a small dielectric constant and a small dielectric loss tangent has been attracting attention as a material suitable for a high-frequency compatible circuit board, and a circuit board using a film having a small dielectric constant and a small dielectric loss tangent such as a fluorine film or LCP has been developed (Patent Documents). 1).

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

Typical methods for wiring processing include the subtractive method and the semi-additive method. The subtractive method is a method in which the entire surface of a thin metal layer is thickened by electrolytic copper plating, and then resist is applied only to the pattern to be wired so that the metal layer remains, and an unnecessary region is etched with a chemical solution. In the semi-additive method, the metal part of the wiring pattern to be processed is exposed on a thin metal layer, the other area is covered with a resist, and the wiring pattern part is electrolytically plated to form a thick conductor layer, and then the resist. This is a method of removing a thin metal layer in a region other than the wiring covered with by soft etching. Etching is indispensable for wiring formation in either method, and if it is attempted to accurately form a fine pattern by these methods, etching variation in the wiring portion becomes an issue, so that the surface of the conductor layer is required to be smooth. ..

Japanese Unexamined Patent Publication No. 2004-6668 Japanese Patent No. 4646580

Conventionally, a polyimide film has been used for a circuit board due to its high heat resistance, but there is concern that polyimide has poor dielectric properties for use in the high frequency band and that the dielectric properties change due to moisture absorption. .. Recently, as a circuit board compatible with high frequencies, a fluorine film having good dielectric properties has been attracting attention, but the fluorine film has a property of high releasability due to its composition and poor adhesion to a conductor. Therefore, in Patent Document 1, in order to directly bond the fluororesin electrical insulating layer and the conductive metal foil with sufficient adhesion, fine protrusions are formed on the surface of the fluororesin electrical insulating layer to form one surface of the conductive metal foil. The surface is roughened to produce a laminated body. However, as described above, since surface smoothness is required to accurately form a fine pattern, it has been difficult to obtain sufficient performance. In addition, when a circuit is formed by the semi-additive method, it is often etched in a short time because only a thin metal layer is etched, and if the smoothness is poor, copper residue is generated depending on the variation in roughness. there were. Furthermore, it is known that the current flowing through the conductor has a skin effect that is transmitted only on the surface layer. When the surface roughness of the conductor is large, the transmission length becomes large, which becomes a resistance and the transmission loss becomes large. Are known. Therefore, if the interface between the film and copper is roughened in order to improve the adhesion, there is a problem that the transmission loss increases and the performance deteriorates.

Therefore, as a material having good dielectric properties, we focused on a polyphenylene sulfide resin film represented by polyphenylene sulfide (hereinafter, may be abbreviated as PPS). However, the polyarylene sulfide resin also has few functional groups on the surface, and there is room for improvement in adhesion to the metal layer, and a method for improving adhesion while maintaining smoothness is required.

A preferred embodiment of the polyarylene sulfide resin film of the present invention is that the oxygen atom detected by the analysis by X-ray photoelectron spectroscopy (XPS) on at least one surface is 10 atomic% or more and 17 atomic% or less, and the oxygen atom and carbon A polyarylene sulfide resin film having an atomic number ratio O / C of 0.10 or more and 0.25 or less.

A preferred embodiment of the metal laminate of the present invention is a metal laminate having a metal layer on a polyarylene sulfide resin film in contact with the polyarylene sulfide resin film, and the polyarylene sulfide is provided under the following conditions. It is a metal laminate in which the metal atom detected by XPS analysis of the surface (α surface) of the metal layer peeled off from the based resin film in contact with the polyarylene sulfide resin film is 10 atomic% or less.

Conditions: The polyarylene sulfide resin film side of a strip-shaped metal laminate having a thickness of 9 μm and a width of 10 mm is fixed to a flat plate, and the metal layer is gripped and peeled at a room temperature of 23 ° C. and a humidity of 50%. Peel at an angle of 100 mm / min and 180 °.

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

A preferred embodiment of the method for producing a metal laminate of the present invention is 0.1 kW · min / m ² or more and 50 kW · min / m ² or less under an atmosphere of a pressure of 0.1 Pa or more and 100 Pa or less on a polyarylene sulfide resin film. This is a method for producing a metal laminate, which comprises a step of laminating metals by a vapor phase film forming method or a method of laminating metal foils after plasma treatment at a processing power density.

According to the present invention, it is possible to obtain a metal laminate having both smoothness and adhesion, and it is possible to obtain a circuit board having excellent performance.

It is sectional drawing which shows the structure of the metal laminate. It is the schematic which shows the α plane which peeled off the metal layer from a metal laminate.

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

The polyarylene sulfide-based resin film of the present invention is a film containing a polyarylene sulfide-based resin as a main component. The main component means that it occupies 80% by mass or more of the raw material 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 resin is a homopolymer or a copolymer having a repeating unit of-(Ar—S) −. Examples of Ar include units represented by the following equations (1) to (11) and the like.

(R ₁ and R ₂ are substituents selected from hydrogen, alkyl group, alkoxy group and halogen group, and R ₁ and R ₂ may be the same or different).
As the repeating unit of the polyarylene sulfide resin used in the present invention, the p-allylene sulfide unit represented by the above formula (1) is preferable, and typical examples thereof are polyphenylene sulfide, polyphenylene sulfide sulfone, and polyphenylene sulfide ketone. , These random copolymers, block copolymers and mixtures thereof and the like. As a particularly preferable p-ylene sulfide unit, a p-phenylene sulfide unit is preferably exemplified from the viewpoint of film physical characteristics and economy. In the present invention, from the viewpoint of durability, dimensional stability, etc., the p-phenylene sulfide unit represented by the structural formula (12) below is 75 mol% or more, more preferably 80 mol% or more of the total repeating unit. Above, it is more preferable to occupy 85 mol% or more.

The polyarylene sulfide-based resin film of the present invention preferably has a melting point of at least one surface layer of 275 ° C. or lower, more preferably 220 ° C. or higher and 275 ° C. or lower, and 245 ° C. or higher and 265 ° C. or lower. Is even more preferable. Here, the surface layer means a layer located at the outermost layer when the polyarylene sulfide-based 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.

When the melting point of the surface layer is 275 ° C. or lower, two or more layers may be laminated in order to maintain the heat resistance of the entire polyarylene sulfide resin film. By setting the melting point to 275 ° C. or lower, the adhesion to the metal layer can be improved, and the peeling of the metal layer in the circuit processing in the subsequent process can be reduced. From the same viewpoint, it is more preferable that the melting point is 265 ° C. or lower. Further, it can be processed at a low temperature in the laminating of the metal layer, and it is possible to suppress defects due to oxidation of the resin or metal, or to prevent the film from warping due to residual stress due to the difference in the coefficient of thermal expansion between 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 viewpoint, 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 melting endothermic peak of the DSC chart obtained by scraping the surface layer and sampling it according to JIS K7121-1987 using a differential scanning calorimeter. When a plurality of peak temperatures are observed, the peak temperature on the low temperature side is defined as the melting point.

The polyarylene sulfide resin for lowering the melting point of the surface layer to 275 ° C. or lower is 2 to 25 mol%, more preferably 2 to 15 mol%, in 100 mol% of the repeating unit of the above polyarylene sulfide resin. It is preferable that the copolymer is copolymerized with the copolymerization unit in the range. By having such a copolymerization unit in an amount of 2 mol% or more, the melting point of the polyarylene sulfide resin can be within the above-mentioned range, and the processability can be made sufficient. Further, when the copolymerization unit is 25 mol% or less, the degree of polymerization of the polyarylene sulfide resin can be sufficiently increased and the mechanical properties are improved.

Preferred copolymerization units are represented by the following formulas (13) to (17).

(Here, X indicates alkylene, CO, SO ₂ units.)

(Here, R represents an alkyl, nitro, phenylene, or alkoxy group.)
A particularly preferred copolymerization unit is the m-phenylene sulfide unit. The mode of copolymerization with the copolymerization component is not particularly limited, but a random copolymer is preferable. The composition of the polyarylene sulfide resin may contain various additives such as an antioxidant, a heat stabilizer, an antistatic agent and an antiblocking agent as long as the effects of the present invention are not impaired.

The polyarylene sulfide-based resin film of the present invention may contain a layer made of another resin. Examples of resins constituting the laminate include polyimide resins, polyamide resins, polyether ether ketones, polyetherimides, polyamideimide resins, polyolefin resins such as polyethylene and polypropylene, polystyrene, polycarbonate, acrylic resins, urethane resins, and fluororesins. , Polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyketone, epoxy resin and the like, but are not limited thereto. Further, two or more kinds selected from the above and polyarylene sulfide-based resins can be blended and used.

The thickness of the polyarylene sulfide-based resin film of the present invention is not particularly limited, but is preferably 2 μm or more and 300 μm or less, more preferably 5 μm or more and 180 μm or less, and further 25 μm or more and 150 μm or less from the viewpoint of film forming property and processability. preferable.

The surface roughness Ra of at least one surface of the polyarylene sulfide-based 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, it is possible to prevent the film from slipping appropriately when rolled into a roll and causing scratches and wrinkles. When it is 0.20 μm or less, it is possible to reduce the obscure pattern of the metal layer forming the circuit due to the surface roughness, suppress the generation of copper residue in the etching process, and transmit by the skin effect. It is possible to suppress a large loss.

Polyarylene sulfide resin has few functional groups on the surface and there is room for improvement in adhesion, so it is necessary to increase the interaction with the metal layer to be laminated. As a result of diligent studies, the inventors have found a state of surface functional groups capable of modifying the surface of a polyarylene sulfide-based resin film to improve adhesion. This will be described in detail below.

A preferred embodiment of the polyarylene sulfide resin film of the present invention is that the oxygen atom detected by the analysis by X-ray photoelectron spectroscopy (XPS) on at least one surface is 10 atomic% or more and 17 atomic% or less, and the oxygen atom and carbon The atomic number ratio O / C of the atom is 0.10 or more and 0.25 or less. XPS irradiates the sample surface with soft X-rays in an ultra-high vacuum, detects photoelectrons emitted from the surface with an analyzer, and obtains elemental information on the surface from the binding energy value of bound electrons in the substance, and each peak. It is an analytical method that can obtain information on the binding state from the energy shift of the above and further quantify it using the peak area ratio. Since XPS is an analysis of a depth region corresponding to the length (mean free path) at which photoelectrons can travel in a substance, surface information on the measurement surface can be obtained. The oxygen atom detected by the XPS analysis of the film surface is preferably 10 atomic% or more and 17 atomic% or less, and more preferably 11 atomic% or more and 15 atomic% or less. By setting the oxygen atom to 10 atomic% or more, it is possible to secure a functional group that contributes to adhesion and obtain an effect of improving adhesion with the metal layer. From the same viewpoint, the oxygen atom is more preferably 11 atomic% or more. Further, by setting the oxygen atom to 17 atomic% or less, it is possible to suppress deterioration of adhesion due to excessive oxidation of the resin and oxidation of the metal layer in direct contact with the resin. From the same viewpoint, the oxygen atom is more preferably 15 atomic% or less. The atomic number ratio O / C of the oxygen atom and the carbon atom on the film surface is preferably 0.10 or more and 0.25 or less, and more preferably 0.15 or more and 0.23 or less. By setting the atomic number ratio O / C to 0.10 or more, necessary functional groups can be introduced. From the same viewpoint, the atomic number ratio O / C is more preferably 0.15 or more. Further, by setting the atomic number ratio O / C to 0.25 or less, it is possible to suppress the surface layer weakening due to excessive oxidation and enhance the adhesion. From the same viewpoint, the atomic number ratio O / C is more preferably 0.23 or less.

The polyarylene sulfide resin film of the present invention has an atomic number ratio S / C of sulfur atom to carbon atom of 0.10 or more and 0.16 detected by analysis by X-ray photoelectron spectroscopy (XPS) on at least one surface. It is preferably 0.12 or more, and more preferably 0.16 or less. When an oxygen atom is introduced into a polyarylene sulfide-based resin film, it is considered that the sulfur atom is eliminated. Therefore, by setting the atomic number ratio S / C of sulfur atoms to carbon atoms to 0.10 or more, it is possible to prevent the surface layer from becoming fragile due to a large decrease in sulfur due to molecular chain breakage, and to reduce adhesion to the metal layer. It can be prevented, and by setting it to 0.16 or less, the number of functional groups becomes sufficient and the adhesion can be improved.

The polyarylene sulfide resin film of the present invention is a sulfur oxide when the peak area attributable to S2p of sulfur atoms detected by analysis by X-ray photoelectron spectroscopy (XPS) on at least one surface is 100%. The peak area attributed to is preferably 5% or more and 20% or less, and more preferably 5% or more and 15% or less. In the process of modifying a polyarylene sulfide resin film, surface oxidation often proceeds at the same time as the modification, and not only oxygen is introduced into the skeleton end of the polyarylene sulfide resin, but also it reacts relatively. Sulfur, which is an easy part, is also oxidized. However, since sulfur oxides do not always contribute to the adhesion of metals, if surface oxidation progresses more than necessary, the resin may deteriorate and the adhesion may be disadvantageous. When the peak area attributed to sulfur oxides is 5% or more, functional groups that contribute to adhesion can be secured, and when it is 20% or less, resin deterioration due to oxidation can be suppressed and adhesion with metals can be ensured. ..

The analysis of the polyarylene sulfide-based resin film by XPS uses monochromatic Al Kα _1.2 rays as excitation X-rays, and measures at 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 , CC) is corrected on the horizontal axis with 284.6 eV, and the composition ratio is calculated from the peak area. For sulfur oxides, group 1 (CS, SS), group 2 (SO), and group 3 (satellite peak, SO _x ), with the peak area in the range of 174 to 160 eV attributed to S2p as 100%. (2 ≦ x ≦ 4)) and group 4 (S ^2- ), and the ratio is calculated by using the total of group 2 and group 3 as sulfur oxides.

The method of modifying the surface of the polyarylene sulfide-based resin film to obtain the above-mentioned preferable surface state is preferably the method of plasma treatment because it is easy to treat the in-plane uniformly and the surface state can be easily adjusted depending on the conditions. be able to.

Plasma treatment is a method of modifying the surface by exposing a polyarylene sulfide resin film to be treated to a discharge obtained by applying a high voltage of direct current or alternating current between a high voltage application electrode and a counter electrode. is there. The polyarylene sulfide-based resin film has problems such as low polarity, the coating film repelling and the entire surface cannot be covered, and poor adhesion, and various surface treatments have been conventionally used. The aim of the conventional surface treatment is to increase the polarity of the film surface to improve the wettability, and the goal has been to add a large amount of oxygen atoms by corona treatment or ozone treatment in the atmosphere. However, when the metal is laminated to improve the adhesion, if the film surface is excessively oxidized, the metal may be oxidized from the interface and the performance may be deteriorated. Further, in order to increase the number of functional groups introduced into the film surface, it is effective to cut a part of the bonds of the polyarylene sulfide resin film to introduce oxygen, but the film surface layer was examined by the inventors. If the molecular chain is cut too much, a force is applied to the interface between the metal and the film, which have different physical properties, when the metal laminate is formed, and the fragile film is coagulated and broken, making it difficult to obtain sufficient adhesion. It turned out to be. That is, the inventors have clarified that there is a problem in adhesion to the metal layer because the surface state or the embrittled state is not sufficiently controlled by the conventional treatment methods. Therefore, as a result of diligent studies, the inventors have found a method for effectively obtaining a functional group that can easily bond with a metal by appropriately cutting the bond while suppressing the weakening of the polyarylene sulfide-based resin film. That is, according to the method for producing a polyarylene sulfide-based resin film in the present invention, the desired surface state of the polyarylene sulfide-based resin film described above can be efficiently obtained. In addition, while obtaining a strong bond state due to the MOS bond in the metal laminate described later, it becomes a functional group that strongly bonds to the metal in a fragile state in which the molecular chain is cut in the polyarylene sulfide resin film portion. It is possible to reduce the number of molecular chains that do not become. Hereinafter, the method for producing the polyarylene sulfide-based resin film of the present invention will be specifically described.

A preferred aspect 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 that stable and efficient treatment is possible. It is preferable to include a step of performing plasma treatment at a processing 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. The pressure of the atmosphere in the case of plasma treatment under reduced pressure 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 further preferably 0.1 Pa or more and 15 Pa or less. When the value is 0.1 Pa or more, plasma discharge can be stably maintained, and active species having energy suitable for functional group formation are present at an appropriate density, so that the plasma discharge can be efficiently modified. By setting the value to 100 Pa or less, it is possible to suppress the reaction between active species and inactivation, 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 further preferable.

In the plasma treatment, the atmosphere at the time of plasma treatment may be adjusted by introducing a gas into the discharge space for the purpose of increasing the treatment efficiency or introducing a specific functional group. The gas used is represented by argon, N ₂ , He, Ne, O ₂ , CO ₂ , CO, air, water vapor, H ₂ , NH ₃ , C _n H _{2n + 2} (where n = an integer of 1 to 4). Various gases such as hydrocarbons 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 active species to be obtained, and the type of functional group to be introduced. In the modification of polyarylene sulfide-based resin film, easy to plasma discharge, active species energy is relatively high argon or N _2, to contain O _2, CO 2, _CO in order to facilitate introduction of oxygen preferable. Of these, a mixed gas of argon and O ₂ or a mixed gas of argon and CO ₂ is more preferable, and a mixed gas of argon and O ₂ is even more preferable. Further, in order to suppress excessive surface treatment, the atmosphere is argon, He, Ne, O ₂ , CO ₂ , CO, steam, H ₂ , C _n H _{2n + 2} (where n = an integer of 1 to 4). It preferably consists of at least one selected from the group consisting of the represented hydrocarbons. When the mixed gas is used, it is preferable that the gas contains 50% or more of oxygen atoms in terms of volume ratio so that a sufficient amount of oxygen can be introduced.

Any shape of the high-voltage application electrode can be used, and examples thereof include a rod shape that can be continuously processed while transporting a film, and a plate shape having a large area. Further, in order to increase the processing strength and reduce the damage to the base material, a magnetron electrode or a dielectric coated electrode can be used. The counter electrode is not particularly limited as long as the film can be brought into close contact with the film, but a drum-shaped electrode capable of supporting the film transfer is preferable. The number of high-voltage application electrodes and counter electrodes need not be the same. For example, if two or more high-voltage application electrodes are used for one counter electrode, space saving and processing efficiency can be improved. The distance between the electrodes may be appropriately set according to the gas pressure condition and the processing strength, but it is 0 from the viewpoint of improving the adhesion of the polyarylene sulfide film and suppressing the film from being damaged and damaged. The range is preferably 0.05 cm or more and 30 cm or less.

Processing intensity that process is preferably 0.1kW · min / ^{m 2} or more 50kW · min / ^{m 2} or less at a power density is 0.3kW · min / ^{m 2} or more 15kW · min / ^{m 2} or less More preferred. Here, the processing power density is a value obtained by dividing the product of the power input to the discharge and the time by the discharge area, and in the case of processing a long film, the input power is divided by the width of the discharged portion and the processing speed of the film. The value. By setting the processing power density to 0.1 kW · min / m ² or more, the energy required for reforming can be provided. From the same viewpoint, the processing power density is more preferably 0.3 kW · min / m ² or more. By setting the processing power density to 50 kW · min / m ² or less, it is possible to prevent the film from being damaged and damaged. From the same viewpoint, the processing power density is more preferably 15 kW · min / m ² or less. Regarding the plasma treatment conditions, when the pressure is 0.1 Pa or more and less than 10 Pa, the processing power density is preferably 0.1 kW · min / m ² or more and 50 kW · min / m ² or less. If the pressure of 10Pa or more 100Pa or less, more preferably 0.3kW · min / ^{m 2} or more 15kW · min / ^{m 2} or less.

From the viewpoint of suppressing brittleness of the polyarylene sulfide resin film due to excessive surface treatment, analysis of at least one surface of the polyarylene sulfide resin film before plasma treatment by X-ray photoelectron spectroscopy (XPS) is performed. It is preferable that the oxygen atom detected in the above is 17 atomic% or less, and the atomic number ratio O / C of the oxygen atom and the carbon atom is 0.25 or less. From the same viewpoint and the viewpoint of reducing the number of surface treatments, it is more preferable that the oxygen atom is 10 atomic% or less and the O / C is 0.1 or less.

The metal laminate of the present invention has a metal layer on a polyarylene sulfide resin film in contact with the polyarylene sulfide resin film. The thickness of the metal layer is preferably 0.05 μm or more and 30 μm or less, and more preferably 0.1 μm or more and 20 μm or less. When the thickness is 0.05 μm or more, oxidation of the metal can be suppressed. From the same viewpoint, it is preferable that the thickness is 0.1 μm or more. When the thickness is 30 μm or less, the metal layer becomes flexible and cracks and warpage of the laminated body 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.

The metal layer in the present invention preferably contains copper as the main component. The principal component means that the constituent atoms are 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 applying a polyarylene sulfide resin onto a copper foil, or a method of applying a metal foil to a polyarylene sulfide resin film. Examples thereof include a laminating method and a method of forming a metal layer by a vapor deposition method typified by a vacuum vapor deposition method or a sputtering method. Among these, a preferable aspect of the method for producing a metal laminate of the present invention is to apply pressure to the polyarylene sulfide resin film from the viewpoint of maintaining a desirable surface state of the polyarylene sulfide resin film suitable for productivity and adhesion. After plasma treatment at a processing 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, a vapor deposition method or a method of laminating metal foil is used. It is preferable to include a step of laminating metals. From the above viewpoint, when the metal foil is laminated (laminated) on the polyarylene sulfide resin film, it is more preferable to use the thermal laminating method for directly laminating the film and the metal foil. The temperature of the thermal lamination is preferably Tm-20 ° C. or higher and Tm + 50 ° C. or lower, and more preferably Tm ° C. or higher and Tm + 30 ° C. or lower, when the melting point of the surface layer of the polyarylene sulfide resin film is Tm. By setting the temperature of the thermal lamination to Tm-20 ° C. or higher, the resin on the film surface can be softened and sufficient adhesion can be obtained. From the same viewpoint, the temperature is preferably Tm ° C. or higher. Further, by setting the temperature to Tm + 50 ° C. or lower, the desirable surface state of the polyarylene sulfide resin film is maintained, and the film becomes brittle due to decomposition or cross-linking of the resin, the flexibility is lowered, and the film is easily coagulated and broken. In addition to being able to prevent warping, it is also possible to suppress warpage due to the difference in thermal expansion coefficient between the resin and the metal foil. From the same viewpoint, the temperature is more preferably Tm + 30 ° C. or lower.

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 further 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 with each other and bonded together. From the same viewpoint, the pressure is more preferably 0.5 MPa or more, further preferably 1.0 MPa or more. Further, by setting the pressure to 10 MPa or less, it is possible to suppress the deformation of the film and avoid the problem that the resin flows during the laminating. From the same viewpoint, the pressure is more preferably 8 MPa or less, further preferably 5 MPa or less.

As a method of laminating metals by the vapor phase film forming method, a vacuum vapor deposition method or a sputtering method can be preferably used from the viewpoint of maintaining productivity and a desirable surface state of a polyarylene sulfide resin film suitable for adhesion. The vapor phase film forming method is preferable because the surface roughness is determined by following the surface of the substrate to be laminated, and the metal layer can be smoothed by using a smooth film. In the case of the vacuum vapor deposition method, there are an induction heating vapor deposition method, a resistance heating vapor deposition method, a laser beam vapor deposition method, an electron beam vapor deposition method, etc., but the electron beam vapor deposition method is preferably used from the viewpoint of having a high film deposition rate. Be done. For film deposition, roll-to-roll processing is preferably used from the viewpoint of productivity, but since the film is exposed to heat during vapor deposition, it is cooled by a cooling roll in contact with the back surface of the film deposition surface. Deposition is preferred. When the film is cooled and the deformation of the film due to heat during vapor deposition is suppressed, the film stress of the metal layer can be suppressed to a small value, which is advantageous in suppressing the peeling of the metal layer, and the viewpoint of maintaining the desirable surface state of the polyarylene sulfide resin film. It is also desirable from. From the same viewpoint, the maximum temperature of the polyarylene sulfide resin film at the time of vapor deposition is preferably equal to or lower than the glass transition temperature of the film surface layer. When a plurality of glass transition temperatures of the film surface layer are observed, it is preferable to deposit the metal at the highest temperature or lower. The glass transition temperature can be obtained from a DSC chart obtained by 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. In the sputtering method, any power source of DC, AC, or pulse may be used, and a magnet may be arranged in the apparatus to use a magnetic field or an ion beam may be used. For example, a magnetron sputtering method, a dual magnetron sputtering method, an ion beam sputtering method and the like can be mentioned. From the viewpoint of maintaining a desirable surface condition of the polyarylene sulfide resin film suitable for productivity and adhesion, it is preferable to perform sputtering at a power output of 5 kW or less.

In the present invention, two or more metal layers may be laminated. In particular, in the case of the vapor phase film forming method, the underlying metal layer can be laminated in order to improve the adhesion between the film and the metal layer and suppress migration. When laminating the base metal layer, it is preferable to laminate the base metal on the polyarylene sulfide-based resin film and then laminate the layer containing copper as the main component in contact with the base metal layer. The underlying 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 viewpoint of antioxidant and corrosion resistance of the metal layer, it is preferable to contain at least one selected from the group consisting of nickel, titanium, and an alloy containing at least one of nickel or titanium. When the metal laminate of the present invention is used for a circuit board application for high-speed signal transmission, the metal of the underlying metal layer must be titanium or an alloy containing titanium because nickel as a magnetic material attenuates signals. Is preferable. The thickness of the base metal layer is preferably 1 nm or more and 100 nm or less, and 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 easy to obtain a uniform effect in the plane, and by setting it to 100 nm or less, it is possible to suppress the deterioration of the wiring pattern workability due to the difference in the etching rate between the copper layer and the base layer. Can be done. Further, when the base metal is a magnetic material and its thickness is thick, there may be a problem that the loss becomes large and the signal is attenuated in high-speed signal transmission. From the viewpoint of thin film thickness accuracy and productivity, a vapor phase film forming method represented by a sputtering method or a vacuum vapor deposition method is preferable as a film forming method for the underlying metal layer, and a sputtering method that reaches the film surface with stronger energy. It is more preferable to have it in terms of improving adhesion. The method for forming the base metal layer and the layer laminated on the base metal layer may be the same or different. For example, both the base metal layer and the layer above it may be formed by a sputtering method, or the base metal layer may be formed by a sputtering method and then formed on the base metal layer by a vacuum vapor deposition method. When both are formed by the vapor phase film formation method, the film may be formed twice for each layer or continuously, but a very thin underlying metal layer is easily oxidized. Therefore, it is preferable to continuously form a film in order to reduce the influence of oxidation. Further, when a metal layer is formed by the vapor deposition method, it is often made into a thin film from the viewpoint of productivity. Therefore, in order to obtain a sufficient metal thickness as a conductor of resistance suitable for a circuit, the vapor deposition method is used. A copper layer can be further laminated by electrolytic copper plating using the layer obtained in (1) as a feeding layer.

In the metal layer of the metal laminate of the present invention, the surface roughness Ra of the surface not in contact with the polyarylene sulfide resin film is preferably 0.01 μm or more and 0.20 μm or less, and 0.01 μm or more and 0.15 μm or less. It is more preferable that it is 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 resin film having good dielectric properties and the metal layer are in direct contact with each other, it is possible to suppress the transmission loss of the transmitted signal due to the skin effect especially in the high frequency band when used as the wiring of the circuit board. The method of directly contacting the polyarylene sulfide-based resin film with the metal layer can be laminated by a vapor phase film forming method such as sputtering or thin film deposition, in addition to bonding copper foils. In the gas phase film formation method, especially in the case of vapor deposition, the metal layer tends to grow following the unevenness of the surface of the polyarylene sulfide resin film, so that the surface roughness of the surface not in contact with the polyarylene sulfide resin film is , It is strongly influenced by the surface roughness of the polyarylene sulfide resin film. Generally, when forming a laminate, the surface is roughened in order to strengthen the adhesion, but the present application is characterized in that a strong adhesion is achieved even though a metal layer is provided on a smooth base material. When the surface roughness Ra of the surface of the metal layer not in contact with the polyarylene sulfide resin film is 0.01 μm or more and 0.20 μm or less, the skin effect on the surface of the metal layer not in contact with the polyarylene sulfide resin film Transmission loss due to can be suppressed. Further, by adopting the above aspect, it can be used as a practical circuit board wiring without a step of smoothing the surface of the metal layer again, and it can contribute to efficiency improvement and reduction of environmental load in the circuit board wiring process.

The conventional metal laminate using a polyarylene sulfide resin film has room for improvement in adhesion to the metal layer, and a method for improving adhesion while maintaining smoothness was required. The present invention has studied various surface treatments on a polyarylene sulfide-based resin film, and has found a desirable state in the cross-sectional direction of the polyarylene sulfide-based resin film in a metal laminate. It was found that the state at these interfaces, that is, the α-plane, greatly contributes to the adhesion because the adhesion between the polyarylene sulfide-based resin film and the metal layer while maintaining the smoothness contributes to the chemical bond. Therefore, the state will be described below.

In general, a polyarylene sulfide-based resin film has a low polarity, so that it is difficult to form a chemical bond, and there is room for improvement in adhesion to a metal layer. In order to improve the adhesion, it is necessary to increase the chemical bond between the polyarylene sulfide-based resin film and the metal layer. However, the present inventions present the sulfur oxidizing component (SO) and sulfide (SO) present on the α-plane. It was found that the state of S ^2- ) greatly affects the adhesion. The mechanism by which these components improve the adhesion to the metal layer is that sulfur derived from the polyarylene sulfide resin film and the metal atom M of the metal laminate are M-OS bonded via the oxygen atom O. Think of it. For example, in the case of an unmodified polyarylene sulfide resin film, SO is below the detection limit on the surface, SO is not detected even if the α plane is analyzed after laminating the metal, and a bond is formed. Since it is not done, it is considered that the adhesion will be weakened.

Conditions: The polyarylene sulfide resin film side of a strip-shaped metal laminate having a thickness of 9 μm and a width of 10 mm is fixed to a flat plate, and the metal layer is gripped and peeled off in an environment of room temperature of 23 ° C. and humidity of 50%. Peel at an angle of 100 mm / min and 180 °.

The fact that the metal atom detected by XPS analysis of the surface (α surface) of the metal layer exfoliated from the metal laminate in contact with the polyarylene sulfide resin film means that the exfoliated metal layer is poly. It means that a large amount of allylene sulfide resin film is attached. When the metal atom on the α-plane is 10 atomic% or less, the adhesion of the metal layer can be made sufficient, and peeling at the time of circuit formation can be suppressed. From the same viewpoint, it is more preferable that the metal atom on the α-plane is 5 atomic% or less. If there are two or more types of metal atoms detected, the total is taken as the amount of metal atoms. The metal atoms detected depend on the composition of the laminate. For example, when the metal layer is a single copper layer, the detected metal atom is copper, but when a layer containing titanium is used as the base metal layer and a copper layer is laminated on top of it, titanium and copper are detected. May be done.

When the peak area attributed to S2p of the sulfur atom detected by the XPS analysis of the α plane is 100%, the peak area attributed to the sulfur oxidizing component (SO) is preferably 1% or more and 7% or less. More preferably, it is 2% or more and 5% or less. By setting the peak area attributable to the oxidizing 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. Further, when it is 7% or less, deterioration of adhesion due to deterioration of the polyarylene sulfide-based resin film can be reduced, and peeling at the time of circuit formation can be suppressed. From the same viewpoint, 5% or less is more preferable.

Is taken as 100% of the peak area attributed to S2p sulfur atom which is detected by the XPS analysis of the α surface, preferably the peak area attributed to sulfide (S ^2-) is 5% or less More preferably, it is 3% or less. It is considered that the sulfide (S ^2- ) remains on the surface of the polyarylene sulfide-based resin film in a state where the molecular chain is cut, without becoming a functional group that strongly bonds with the metal. If the molecular chain is cleaved under conditions such as the presence of sufficient oxygen, it can become a functional group that contributes to adhesion, but the required amount of oxygen is not supplied or remains on the surface with the molecular weight reduced. If it does, it remains on the surface without contributing to adhesion. It is considered that the presence of these components that do not contribute to adhesion may act as an adhesion inhibitor or weaken the adhesion due to deterioration of the film or metal layer. Therefore, Osaere peak areas attributable to S ^2- to 5% or less, it is possible to suppress excessive alteration of polyarylene sulfide-based resin film as described above, it can be reduced exfoliation during circuit formation. From the same viewpoint, the peak area attributed to sulfide ( ^S2- ) is more preferably 3% or less. The lower limit of the peak area attributed to S ^2- is about 1% from the detection limit of analysis.

In the manufacture of metal laminates, the film surface may be damaged or oxidized by heat, and the surface layer may deteriorate and become fragile. When the metal layer is peeled off from the polyarylene sulfide resin film, the polyarylene sulfide resin film becomes the peeling interface at the position where the strength is weak when viewed in the depth direction from the interface with the metal layer, and becomes the α surface of the metal layer. A part of the surface layer of the polyarylene sulfide resin film adheres thinly. When the polyarylene sulfide resin film is fragile, the peeling interface is very close to the metal layer, the polyarylene sulfide resin adhering to the metal layer is thin, and even the elements of the metal layer are detected by the XPS analysis. Will be. On the other hand, when the vicinity of the metal layer of the polyarylene sulfide resin film is not damaged, the film adhering to the peeled metal layer becomes thicker and the amount of detected elements in the metal layer decreases. In addition, sulfur atoms may be eliminated due to alteration of the polyarylene sulfide resin. When the desorbed sulfur atom exists as a sulfide ion, it may form an adhesion inhibitor by forming a sulfide with a metal.

The metal layer can be peeled off by the method described in Examples. The surface of the metal layer thus obtained in contact with the polyarylene sulfide resin film is defined as the α surface, and the surface thereof is analyzed by XPS. The α-plane of the metal layer peeled from the polyarylene sulfide-based resin film is analyzed by using monochromatic Al Kα ₁ and ₂ rays as excitation X-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, C1s (CH _x , CC) is corrected on the horizontal axis with 284.6 eV, and the composition ratio is calculated from the peak area. For S2p, group 1 (CS, SS), group 2 (SO), and group 3 (satellite peak SO _x (2 ≦ x ≦ 4)), where the peak area of the spectrum of 174 to 160 eV is 100%. , Group 4 (S ^2- ), of which the area ratios of group 2 and group 4 are calculated and used as the component ratio.

Note that the α-plane is randomly measured once for each of 10 locations, and the component ratio is calculated for each measurement. When the calculated component ratio is the detection limit, it is set to 0%. The arithmetic mean of each component ratio for 10 locations is used as the result of XPS analysis of the α plane.

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 that it can be suitably used for circuit material applications, touch panels, and the like. For example, in the case of a circuit board, a metal layer is patterned to form a wiring circuit. The wiring circuit can be formed by a known method such as a subtractive method or a semi-additive method, but when the wiring width of the circuit is narrow, the semi-additive method in which the decrease in the wiring width due to etching is small is more preferable.

Hereinafter, the present invention will be described based on examples. The present invention is not limited to these examples, and these examples can be modified or modified based on the gist of the present invention, and they are not excluded from the scope of the invention. Absent.

[Evaluation method]
(1) Measurement of Melting Point of Polyarylene Sulfide Resin Film Any layer to be measured is scraped off with a microplane and sampled. Regarding the scraped sample, according to JIS K7121-1987, a DSC (RDC220) manufactured by Seiko Instruments Co., Ltd. was used as a differential scanning calorimeter, and a disk station (SSC / 5200) manufactured by Seiko Instruments Co., Ltd. was used as a data analysis device. Above, the temperature is raised from room temperature to 350 ° C. at a heating rate of 20 ° C./min (1st Run). The sample is taken out and rapidly cooled, and then the temperature is raised 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 on the obtained 2nd Run DSC chart is defined as the melting point (Tm).

(2) Analysis of the surface of the polyarylene sulfide resin film by X-ray photoelectron spectroscopy (XPS) The analysis by the XPS method was measured and calculated under the following conditions described in the text.
Equipment: ESCALAB220iXL
Excited X-ray: monochromatic Al Kα _{1 and 2} lines (1486.6 eV)
X-ray diameter: 1 mm
Photoelectron escape angle: 90 ° (inclination of detector with respect to sample surface)
Smoothing: 11-point smoothing
Horizontal axis correction: C1s (CH _x , CC) was set to 284.6 eV.
Measurement points / number of times: The surface of the polyarylene sulfide-based resin film was randomly measured once at each of 10 points, and the component ratio was calculated for each measurement. When the calculated component ratio was the detection limit, it was set to 0%. The arithmetic mean of each component ratio for 10 locations was used as the measurement result.

(3) Measurement of Surface Roughness of Polyarylene Sulfide Resin Film The surface roughness of the film is the arithmetic mean roughness defined in JISB0601-1994, and was measured under the following conditions.
Equipment: Surfcorder ET4000A manufactured by Kosaka Laboratory Co., Ltd.
Needle tip R: 2 μm
Measurement area: 500 μm x 500 μm,
Sample fixing: Kamaboko-shaped glass attached to the device.

(4) Evaluation of Metal Laminated Body (4-1) Measurement of Surface Roughness of Metal Layer The surface roughness Ra of the metal layer was measured in the same manner as in the film of (3) above.

(4-2) Analysis of the metal layer (α-plane) 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 of the laminate was less than 9 μm, electrolytic copper plating was performed so that the thickness was 9 μm, and when it exceeded 9 μm, it was adjusted by polishing.

The metal layer was peeled off at the interface between the polyarylene sulfide resin film of the metal laminate and the metal layer, and the peeled surface on the metal layer side was analyzed. To peel off the metal layer, a strip-shaped laminate with a width of 10 mm is fixed to a flat plate, and the metal layer is gripped in an environment of room temperature of 23 ° C. and humidity of 50%, and the metal layer is peeled off at an angle of 100 mm / min and 180 °. did.

The analysis by the XPS method was measured and calculated under the following conditions described in the text.
Equipment: QuanteraSXM
Excited X-ray: monochromatic Al Kα _{1 and 2} lines (1486.6 eV)
X-ray diameter: 200 μm
Photoelectron escape angle: 45 ° (inclination of detector with respect to sample surface)
Smoothing: 9-point smoothing
Horizontal axis correction: C1s (CH _x , CC) was set to 284.6 eV.
Measurement points / number of times: The α-plane was randomly measured once at each of 10 points, and the component ratio was calculated for each measurement. When the calculated component ratio was the detection limit, it was set to 0%. The arithmetic mean of each component ratio for 10 locations was used as the result of XPS analysis of the α plane.

(5) Measurement of Adhesion Strength of Metal Layer In the adhesion strength measurement 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.

The metal laminate was masked with masking tape having a width of 5 mm and etched with ferric chloride to obtain a measurement sample having a width of 5 mm and a length of 100 mm. The sample was fixed to a SUS plate using an adhesive tape, the metal layer was gripped, and the adhesion was measured under the following conditions.
Equipment: Adhesive / film peeling analyzer VPA-2
Sample width: 5 mm
Sample length: 100 mm
Peeling conditions: 90 °, 100 mm / min
Measuring distance: 75 mm.

Of the obtained measurement profiles, the value obtained by averaging the adhesion between the peeling distances of 4 mm and 50 mm was defined as the adhesion of the metal layer. A when the adhesion is 5N / cm or more, B when the adhesion is 3N / cm or more and less than 5N / cm, C when the adhesion is 1.0N / cm or more and less than 3N / cm, 0.1N / cm or more and 1.0N / When it was less than cm, it was designated as D, and when it was less than 0.1 N / cm, it was designated as E.

(6) Formation of Wiring Pattern A wiring pattern was processed using a metal laminate, and its workability was evaluated. A for wiring that can be processed without copper residue, B if there is copper residue at the end of the wiring pattern or between wirings that can be processed, and C for those that can be processed but have copper residue or the straight line at the wiring end is rough. , The one that cannot be wired is designated as D. The pattern processing method is as follows.

A plating resist having a wiring pattern having a resist thickness of 20 μm and L / S = 10/10 μm was formed on the surface of the metal layer of the metal laminate using “PMER®” P-LA900PM manufactured by Tokyo Ohka Co., Ltd. Then, electrolytic copper plating was performed so that the thickness of the metal layer was 10 μm. Electrolytic copper plating includes copper sulfate pentahydrate 50 g / L, sulfuric acid 200 g / L, chlorine 50 ppm, Meltex Inc. additive "Kappa Gleam (registered trademark)" ST-901A 2 ml / L, "Capper Gleam (registered)". A liquid of 20 ml / L of "ST-901B" was used, and the plating conditions were a jet flow method and a current density of 1.0 A / dm ² . After electrolytic copper plating, the plating resist was removed with an alkaline stripping solution, and the metal layer for power feeding between the wirings was removed using a hydrogen peroxide-sulfuric acid-based etching solution to form a wiring pattern. If the metal layer contains nickel or titanium as the base metal layer, it is difficult to remove it with a hydrogen peroxide-sulfuric acid-based etching solution. Therefore, after etching the copper layer by the above method, MEC Co., Ltd.'s "Meckli Mover" Was used to remove the underlying metal.

[Example 1]
A polyarylene sulfide resin film obtained by plasma-treating one side of a 100 μm-thick biaxially stretched PPS film (“Trelina” (registered trademark) film # 100-3030 surface layer melting point 280 ° C. manufactured by Toray Industries, Inc.) under an argon atmosphere. Got The processing conditions were an argon atmosphere, a pressure of 0.3 Pa, and a processing power density of 0.8 kW · min / m ² .

A metal having a composition of Ni / Cr = 80/20 (molar ratio) was formed on the plasma-treated surface as a base metal layer by a magnetron sputtering method at 25 nm, and then copper was laminated by a magnetron sputtering method at 90 nm to laminate the metal. I got a body. For all the sputtering conditions of Ni / Cr and Cu, the degree of vacuum reached was 0.2 Pa or less by introducing argon gas, and the output was 500 W using an RF power supply.

[Example 2]
A biaxially stretched PPS film with a thickness of 100 μm (“Trelina” (registered trademark) film manufactured by Toray Industries, Inc., 3-layer structure, melting points of both layers 255 ° C., melting point of central layer 280 ° C.) is used to create an atmosphere of plasma treatment. A polyarylene sulfide resin film and a metal laminate were obtained in the same manner as in Example 1 except that argon / O ₂ = 50/50 (volume ratio).

[Example 3]
A polyarylene sulfide-based resin film and a metal laminate were obtained in the same manner as in Example 2 except that the base metal layer was Ti.

[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.

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

[Example 6]
A copper foil was heat-laminated on the polyarylene sulfide-based resin film obtained in the same manner as in Example 2 to obtain a metal laminate. As the copper foil, an electrolytic copper foil CF-T4X-SV manufactured by Fukuda Metal Co., Ltd. with a thickness of 12 μm was used. The thermal laminating conditions were set at 260 ° C. and 4 MPa for 10 minutes using a vacuum press device manufactured by Kitagawa Seiki Co., Ltd.

[Example 7]
A polyarylene sulfide-based 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.

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

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

[Example 10]
The plasma treatment conditions were the same as in Example 1 except that the treatment atmosphere was argon / O ₂ = 50/50 (volume ratio) and the treatment power density was 6.0 kW / min / m ^2, and the polyarylene sulfide resin film and metal were used. A laminate was obtained.

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

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

[Example 13]
A polyarylene sulfide-based resin film and a metal laminate were obtained in the same manner as in Example 8 except that the plasma treatment conditions were set to a treatment power density of 50 kW · min / m ² .

[Example 14]
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 pressure of 0.1 Pa and a treatment power density of 7.0 kW · min / m ² .

[Example 15]
A polyarylene sulfide-based resin film and a metal laminate were obtained in the same manner as in Example 8 except that the plasma treatment conditions were set to a pressure of 10 Pa.

[Example 16]
A polyarylene sulfide-based resin film and a metal laminate were obtained in the same manner as in Example 8 except that the plasma treatment conditions were set to a pressure of 15 Pa.

[Example 17]
A polyarylene sulfide-based resin film and a metal laminate were obtained in the same manner as in Example 2 except that the plasma treatment conditions were a CO ₂ atmosphere and the treatment power density was 1.2 kW · min / m ² .

[Example 18]
A polyarylene sulfide-based resin film and a metal laminate were obtained in the same manner as in Example 17 except that the plasma treatment conditions were N ₂ / CO ₂ = 90/10 (volume ratio) atmosphere.

[Comparative Example 1]
A polyarylene sulfide-based resin film and a metal laminate were obtained in the same manner as in Example 1 except that the metals were laminated without plasma treatment.

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

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

[Comparative Example 4]
A polyarylene sulfide-based resin film and a metal laminate were obtained in the same manner as in Example 2 except that the blast treatment was performed instead of the plasma treatment. In the blasting treatment, silica sand having an average particle size of 200 μm was used as an abrasive, and the film was shot by a shot blasting method at a distance of 1 m and then washed with water.

[Comparative Example 5]
A polyarylene sulfide-based 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 N ₂ / O ₂ = 50/50 (volume ratio) and a pressure of 0.02 Pa.

[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 conditions were set to a treatment power density of 15 kW · min / m ² .

Tables 1 and 2 show the evaluation results in each Example / Comparative Example.

When the polyarylene sulfide-based resin film of Example 1 was obtained, plasma treatment was performed using a power source having an AC power frequency of 13.56 MHz under the conditions of an output of 100 W and a transport speed of 0.5 m / min.

Further, when the biaxially stretched PPS film having a thickness of 100 μm used in Examples 1 and 2 was sliced with a single edge to about half the thickness and the cross section was analyzed by the method (2), all the films were oxidized by sulfur. The peak area ratio attributed to component (SO) was less than 1%, and the peak area ratio attributed to sulfide (S ^2- ) was also less than 1%.

In Comparative Example 2, the peak area attributed to the sulfur oxidizing component (SO) due to oxidation during bonding at a high temperature is relatively large, and in Comparative Example 4, the residue generated by the blasting treatment is detected in a state where the ends are oxidized. As a result, it is considered that the ratio of the peak area attributed to the oxidizing component (SO) of sulfur is relatively high. Further, in Comparative Examples 1 and 2, the ratio of the peak area attributed to sulfide ( ^S2- ) is relatively high because the molecular chain is cleaved in a state of oxygen deficiency when the base metal layer is formed, which contributes to the bond. This is probably because it was a residue in a difficult state. Further, in Comparative Example 4, it is considered that the residue generated by the blasting treatment remained on the surface.

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

Claims

The oxygen atom detected by the analysis by X-ray photoelectron spectroscopy (XPS) on at least one surface is 10 atomic% or more and 17 atomic% or less, and the atomic number ratio O / C of the oxygen atom and the carbon atom is 0.10 or more and 0. A polyarylene sulfide resin film of 25 or less.
The polyarylene sulfide-based resin film according to claim 1, wherein the atomic number ratio S / C of the sulfur atom and the carbon atom detected by the analysis by the X-ray photoelectron spectroscopy (XPS) is 0.10 or more and 0.16 or less. ..
When the peak area attributable to S2p of the sulfur atom detected by the analysis by the X-ray photoelectron spectroscopy (XPS) is 100%, the peak area attributed to sulfur oxide is 5% or more and 20% or less. The polyarylene sulfide-based resin film according to claim 1 or 2.
The polyarylene sulfide-based resin film according to any one of claims 1 to 3, wherein the surface roughness Ra of at least one surface is 0.01 μm or more and 0.20 μm or less.
The polyarylene sulfide resin film according to any one of claims 1 to 4, wherein the polyarylene sulfide resin film is a laminate of two or more layers, and the melting point of at least one of the surface layers is 275 ° C. or lower.
A metal laminate having a metal layer on a polyarylene sulfide resin film in contact with the polyarylene sulfide resin film, and the poly of the metal layer peeled from the polyarylene sulfide resin film under the following conditions. A metal laminate in which the metal atom detected by XPS analysis of the surface (α surface) in contact with the arylene sulfide resin film is 10 atomic% or less.
Conditions: The polyarylene sulfide resin film side of a strip-shaped metal laminate having a thickness of 9 μm and a width of 10 mm is fixed to a flat plate, and the metal layer is gripped and peeled at a room temperature of 23 ° C. and a humidity of 50%. Peel at an angle of 100 mm / min and 180 °.
When the peak area attributed to S2p of the sulfur atom detected by the XPS analysis of the α plane is 100%, the peak area attributed to the sulfur oxidizing component (SO) is 1% or more and 7% or less. The metal laminate according to claim 6.
Claim 6 that the peak area attributed to sulfide (S 2- ) is 5% or less when the peak area attributed to S2p of the sulfur atom detected by the XPS analysis of the α plane is 100%. Alternatively, the metal laminate according to 7.
The invention according to any one of claims 6 to 8, 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. Metal laminate.
The metal laminate according to any one of claims 6 to 9, wherein the main component of the metal layer is copper.
The metal laminate according to any one of claims 6 to 10, 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.
A method for producing a polyarylene sulfide-based resin film, which comprises a step of performing plasma treatment at a processing power density of 0.1 kW · min / m 2 or more and 50 kW · min / m 2 or less in an atmosphere of a pressure of 0.1 Pa or more and 100 Pa or less.
A vapor phase film formation method is performed after plasma treatment is performed on a polyarylene sulfide resin film under an atmosphere of a pressure of 0.1 Pa or more and 100 Pa or less at a processing power density of 0.1 kW · min / m 2 or more and 50 kW · min / m 2 or less. Alternatively, a method for manufacturing a metal laminate, which comprises a step of laminating metals by a method of laminating metal foils.
A method for producing a metal laminate in which a metal is laminated on the polyarylene sulfide-based resin film according to any one of claims 1 to 5.