JP7298218B2 - LAMINATED BOARD AND CIRCUIT BOARD USING THE SAME - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate having excellent high-frequency transmission characteristics, bending resistance, and circuit workability, and a circuit board using the laminate.

In the field of electrical and electronic components, materials with low transmission loss are in demand due to the trend toward higher speed and larger capacity. Conventionally, circuit boards (wiring boards) used as parts of electric and electronic devices include substrates obtained by impregnating glass cloth with epoxy resin (hereinafter abbreviated as glass epoxy substrates), polyimide films, fluorine-based films, and glass cloths. A base material impregnated with a fluorine-based resin is used. However, these substrates each have the following problems. Glass-epoxy substrates are inferior in high-frequency characteristics and have problems with hygroscopic characteristics, so there is a problem that the transmission characteristics deteriorate further at higher frequencies. be. Polyimide films are excellent in heat resistance, but are inferior in high-frequency characteristics. In addition, substrates obtained by impregnating a fluorine-based film or a glass cloth with a fluorine resin have the problem that printing during circuit formation, metal foil lamination processing, and paste and plating during through-hole processing are difficult to adhere.

Therefore, in recent years, a circuit board using a liquid crystal polymer film as a low transmission loss material has been known (Patent Document 1). However, when a liquid crystal polymer is used, it has a structure in which the molecular chains are extremely oriented and its elongation is low. be.

Polyarylene sulfide films typified by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) are being applied to electrical insulating materials, taking advantage of their high transmission loss and low hygroscopicity. For example, a technique for improving the dimensional stability of a PPS film for use as a circuit board has been disclosed (Patent Document 2). There was no problem. Also disclosed is a technique relating to a metal base circuit board laminated on a metal layer via a layer comprising a copolymerized polyphenylene sulfide resin composition containing at least one or more copolymerized units other than p-phenylene sulfide units. However, there has been a problem that metal is used as a support layer and the flex resistance is not sufficient as a laminate (Patent Document 3).

JP 2011-60449 A JP-A-2002-47360 JP-A-6-91812

An object of the present invention is to solve the above problems. That is, the object is to provide a laminate having excellent high-frequency transmission characteristics, bending resistance, and circuit workability, and a circuit board using the same.

In order to solve the above problems, the laminate of the present invention has the following configuration. That is, a laminate comprising at least one layer (A layer) containing a polyarylene sulfide resin as a main component and a layer (M layer) containing a metal as a main component, and wherein the A layer and the M layer are in contact with each other. It is a laminate having a folding endurance of 100 times or more in a folding endurance test.

Since the laminate of the present invention is excellent in high-frequency transmission characteristics, bending resistance, and circuit workability, it can be suitably used as various electric/electronic circuits, particularly as a circuit material for high frequencies.

It is a schematic diagram of a pattern when evaluating a bending endurance test of a laminate.

The laminate of the present invention will be described in detail below with reference to specific examples.
The laminate of the present invention includes at least one layer (A layer) containing a polyarylene sulfide resin as a main component and a layer (M layer) containing a metal as a main component, and the A layer and the M layer are in contact with each other. characterized by becoming Here, the term "main component" means that it accounts for 80% by mass or more of the raw material that constitutes the layer. With the above configuration, the M layer, which is a conductor, and the A layer, which is an insulating layer, are in contact, and the A layer is in contact with the conductor surface, which is a transmission path, so that the transmission loss is small and the change over time due to temperature and humidity is small. It is possible to develop characteristics excellent in maintaining transmission characteristics.

As the laminated structure of the laminate of the present invention, when the composition of the M layer is m and the composition of the A layer is a, two layers of m / a, m / a / m, a / m / a, m / a /m/a, m/a/m/a/m, a/m/a/m/a, etc. multilayer structures include, but are not limited to. In addition, when c is a resin with a composition different from that of the A layer, the configuration is such as m / a / c, m / a / c / a / m, m / a / c / m / a / c , it is also possible to express different characteristics.

It is important that the laminate of the present invention has a folding endurance of 100 times or more in a folding endurance test. By setting the folding endurance of the laminate within the above range, it is possible to suppress disconnection of the conductor when it is cut or bent when incorporating it into a device as a circuit board, and reliability is improved when used in the repeatedly bent part of the hinge part. can get. If the folding endurance is less than 100 times, disconnection may occur when inserted into a circuit, resulting in poor conduction.

Here, the number of folding endurance is a value obtained by measuring the number of times of continuity of the laminate when performing a folding endurance test according to JIS C6471 using an MIT bending tester. The conditions for measuring the number of folding endurances in the present invention are as follows. The continuity of the sample shall be measured in minutes. In addition, the measurement is performed 5 times, and the average value of these measurements is adopted as the number of folding resistance of the film.

From the standpoint of bending resistance and reliability, the laminate of the present invention has a folding endurance of preferably 200 times or more, more preferably 300 times or more. In the present invention, the number of folding endurances can be controlled within the above range by controlling the resin composition and resin lamination among the film-forming conditions described later.

The polyarylene sulfide resin used for layer A of the laminate of the present invention is a copolymer having repeating units of --(Ar--S)--. Examples of Ar include units represented by the following formulas (1) to (11).

(R1 and R2 are substituents selected from hydrogen, 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-based resin used in the laminate of the present invention, the p-arylene sulfide unit represented by the above formula (1) is preferable. , polyphenylene sulfide ketone, etc. Particularly preferred p-arylene sulfide units include p-phenylene sulfide units from the viewpoint of film properties and economy.

In the polyarylene sulfide resin used for the A layer of the laminate of the present invention, the p-phenylene sulfide unit represented by the following structural formula is 75 to 100 mol%, more preferably 75 to 98 mol%, more preferably 75 to 98 mol% of the total repeating units. preferably accounts for 85 to 98 mol %. If the main component is less than 75 mol %, the durability may be lowered.

In the laminate of the present invention, the orientation parameter I _A of the A layer obtained by laser Raman spectroscopy in the cross-sectional direction is preferably less than 6 in both the longitudinal direction and the width direction of the A layer, and more preferably. is 3 or more and less than 6, more preferably 4 or more and 5.5 or less, and still more preferably 4.5 or more and 5 or less. By setting the content in the above range, it is possible to show that the orientation of the A layer is relaxed, and to improve the adhesion with the M layer and to achieve both circuit workability. If the orientation parameter _IA exceeds the above range, the shrinkage of the A layer increases during circuit processing due to residual orientation stress, and peeling may occur due to the difference in shrinkage between the M layer and the A layer. On the other hand, if the orientation parameter I _A is less than the above range, it indicates that the orientation relaxation of the A layer progresses and becomes amorphous, and the A layer may become brittle and the bending resistance may decrease. The orientation parameter I _A of the A layer in the present invention can be obtained by changing the resin composition in the manufacturing method described later.

The orientation parameter I in the present invention is calculated by the following formula (i). In the present invention, in the case of a roll-shaped laminate, the longitudinal direction of the laminate corresponds to the winding direction of the roll as the longitudinal direction and the width direction of the roll as the width direction. On the other hand, when the laminate is in the form of a cut sheet, the long side direction of the laminate is regarded as the longitudinal direction for calculation. When the laminate has a substantially square shape, any one of the directions parallel to each side is regarded as the longitudinal direction and the width direction for calculation.
(i) Orientation parameter I=I ₁₀₈₀ /I ₇₄₀
I ₁₀₈₀ : Intensity of 1080 cm ^-1 Raman band with polarized light arranged parallel to the film plane I ₇₄₀ : Intensity of 745 cm ^-1 Raman band with polarized light arranged parallel to the film plane Although the measurement method by the above laser Raman spectroscopy is not particularly limited. , For example, using a laser Raman device (PDP320 (manufactured by Photon Design Co., Ltd.)), a microprobe objective lens of 100 times, the objective lens has transparency in the near infrared region (1064 to 1300 nm), NA 0.95, A chromatic aberration corrected one can be used. Cross slit 1 mm, spot diameter 1 μm, light source Nd-YAG (wavelength 1064 nm, output: 1 W), diffraction grating Spectrograph 300 g/mm, slit: 100 μm, detector InGaAs (Roper Scientific 512) are preferably used. The laminate used for measurement was sampled, embedded in epoxy resin, and then cross-sectioned with a microtome. Five samples were measured using the center point of each sample as the measurement point, and the average value was calculated. Measurements were detected through a polarizer placed with the polarization direction parallel to the polarization direction of the incident light, the sample was rotated and the spectrum was obtained with the polarization direction parallel to the film plane with respect to the polarization direction of the laser light.

In addition, from the viewpoint of workability, the melting point of the polyarylene sulfide resin constituting the layer A is preferably 275 ° C. or less, more preferably 220 ° C. or higher and 275 ° C. or lower, further preferably 245 ° C. or higher and 265 ° C. or lower. is. By setting the melting point to the above range, when used as a laminate, the adhesiveness to the M layer is increased, and the circuit workability can be improved. If the melting point exceeds the above range, the adhesion of the laminate may be lowered, and the M layer and the A layer may separate during circuit processing. When the melting point is lower than the above melting point, it is shown that the amorphousness increases, and the hygroscopicity increases, which may deteriorate the high-frequency transmission characteristics. The melting point of the polyarylene sulfide-based resin that constitutes the A layer can be obtained by the method described below. Moreover, the melting point of the resin constituting the A layer can be confirmed by the method described later.

The polyarylene sulfide resin used in the A layer of the laminate of the present invention is 2 to 25 mol%, preferably 2 to 15 mol% of the repeating unit of the above polyarylene sulfide resin. is preferably obtained by If the content of such copolymerized units is less than 2 mol %, the melting point of the polyarylene sulfide -based resin cannot be within the range described above, and processability may be lowered. On the other hand, when the copolymerization unit exceeds 25 mol %, the degree of polymerization of the polyarylene sulfide -based resin becomes low, making it difficult to increase the molecular weight of the polyarylene sulfide-based resin.

Preferred copolymer units are

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

(Here, R represents an alkyl, nitro, phenylene, or alkoxy group), and particularly preferred copolymer units are m-phenylene sulfide units.

The mode of copolymerization with the copolymerization component is not particularly limited, but a random copolymer is preferred. The melting point of the polyphenylene sulfide resin can be confirmed by using the technique described below.

Various additives such as antioxidants, heat stabilizers, antistatic agents and antiblocking agents are added to the composition of the polyarylene sulfide resin constituting the laminate of the present invention as long as the effects of the present invention are not impaired. may be included.

The laminate of the present invention may contain layers made of other resins in addition to the A layer and the M layer. Examples of resins constituting the laminate include polyimide resin, polyamide resin, polyetheretherketone, polyetherimide, polyamideimide resin, polyolefin resin such as polyethylene and polypropylene, polystyrene, polycarbonate, acrylic resin, urethane resin, and fluorine resin. , polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyketones, and epoxy resins, but are not limited thereto. Two or more selected from the above and polyarylene sulfides can also be blended and used.

The metal used for the M layer of the laminate of the present invention is not particularly limited as long as it has conductivity, and metals such as gold, silver, copper, stainless steel, nickel, and aluminum, or alloys of two or more thereof can be mentioned. be able to. Further, the M layer of the present invention may be formed by laminating two or more layers of the above metals. A metal that is preferably used includes copper. As copper, for example, a method of forming directly on the A layer by vapor deposition or plating, or a method of laminating a copper foil produced by a rolling method or an electrolysis method on the A layer can be used.

The thickness of the M layer of the laminate of the present invention is preferably 0.3 to 150 μm. It is more preferably in the range of 1 to 80 μm, still more preferably in the range of 5 to 50 μm. Flexibility can be expressed by setting it within the above range. Moreover, when the thickness of the M layer exceeds 150 μm, the rigidity of the metal layer increases and the bending resistance may decrease. If the thickness of the M layer is less than 0.3 μm, there may be a defect in conduction failure.

When a polyarylene sulfide film is used as the material for the laminate of the present invention, the polyarylene sulfide film may contain at least a layer A and a layer B containing a polyarylene sulfide-based resin as a main component and having a higher orientation parameter than the layer A. preferable. By forming two or more layers with different orientation parameters, it is possible to have multiple properties such as bending resistance and circuit workability. As the laminated structure, when the composition of the layers is A and B, the two layers of A/B, the multilayer structure of A/B/A, A/B/A/B, A/B/A/B/A, etc. include, but are not limited to. Further, a layer structure in which a layer having a composition different from that of the A layer and the B layer is further added can be used.

The orientation parameter I _B of the layer B of the laminate of the present invention is preferably 6 or more and 12 or less, more preferably 7 or more and 12 or less in both the longitudinal direction and the width direction of the B layer. By setting it within the above range, the orientation of the B layer can be controlled and the bending resistance can be improved. When the orientation parameter _IB of the B layer is less than 6, there is no difference in orientation from the A layer, and the rigidity is lowered, which may lead to a decrease in flex resistance. When the orientation parameter _IB of the B layer is 12 or more, the orientation is high, and the shrinkage stress increases, which may cause shrinkage and peeling due to heat applied during circuit processing. In the present invention, the orientation parameter _IB of layer B can be controlled by the molding conditions described later. The orientation parameter of the B layer can be evaluated by the method described above.

The layer B of the laminate of the present invention is preferably composed of layer B (I) or layer B (II), which will be described later.

The B layer (I) of the laminate of the present invention preferably has pores. When the B layer (I) has pores, the density of the resin constituting the laminate is lowered, shrinkage stress can be reduced, and circuit workability can be improved. The porosity of layer B is preferably 20% or more and 70% or less, more preferably 30% or more and 60% or less. If the porosity exceeds 70%, the mechanical properties may deteriorate and breakage may occur during circuit processing. As a method for forming pores, a dry method (a method in which a resin is melted and extruded into a sheet shape and then made porous by stretching) can be used because the process can be simplified and productivity is excellent. In addition, among the dry methods, in consideration of retention stability and productivity, a method in which inorganic particles are added to the layer to be made porous and stretched to form voids around the particles to make the layer porous is preferably used. .

The particle concentration used in the B layer (I) of the laminate of the present invention is preferably 5% by mass or more when the raw material composition of the layer composed of the constituent resin and other additives is 100% by mass. , more preferably 5 to 60% by mass, more preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass. By setting the particle concentration within the above range, the pores can be efficiently formed, and the falling off of the particles from the outermost layer can be suppressed. If the particle concentration is less than 5% by mass, the particle concentration is low during film production, which will be described later, so that voids are less likely to be formed, and electrical properties may deteriorate when the thermoplastic resin film is used as a constituent member of a laminate. be. On the other hand, if the particle concentration exceeds 50% by mass, stretching becomes difficult during the production of the thermoplastic resin film, and productivity may decrease.

Particles used in layer B (I) of the laminate of the present invention include oxide ceramics such as alumina, silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide and iron oxide, silicon nitride, titanium nitride and boron nitride. Nitride ceramics, silicon carbide, calcium carbonate, aluminum sulfate, barium sulfate, potassium titanate, talc, kaolin clay, kaolinite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite, asbestos , ceramics such as zeolite, calcium silicate, magnesium silicate, diatomaceous earth and silica sand, and inorganic compounds such as glass fiber. A single type of particles may be used, or a mixture of a plurality of types may be used. Among these, calcium carbonate, barium sulfate, zinc oxide, and silica are preferred from the viewpoint of dispersibility, and calcium carbonate is most preferred from the viewpoint of low cost.

The volume-average particle size of the particles used in layer B (I) of the laminate of the present invention is preferably 0.5 to 10 μm, more preferably 1 to 5 μm. By using particles with the above volume average particle diameter, aggregation of particles that tends to occur when particles are blended at a high concentration is suppressed, and stress is concentrated around the particles when stretched, so layer B Voids can be efficiently formed inside. If the volume average particle diameter of the particles is less than 0.5 μm, it becomes difficult to form pores during stretching, the porosity decreases due to the decrease in the size of the pores, or the surface area of the particles increases due to aggregation. may cause Further, if the volume average particle diameter is larger than 10 μm, the size of the pores becomes large, which may cause variations in transmission characteristics.

Layer B (II) of the laminate of the present invention preferably contains a polyarylene sulfide-based resin as a main component and contains a thermoplastic resin (α) different from the polyarylene sulfide-based resin and having any of the following chemical formulas. Layer B (II) contains a thermoplastic resin (α) having any one of the following chemical formulas, whereby the amorphous chains of the polyarylene sulfide- based resin are constrained by the interaction of the molecular chains to suppress thermal deterioration, resulting in a laminate It is possible to improve the bending durability in the case of. More preferably, it contains chemical formulas (L), (M), (N) and (O), and more preferably contains chemical formulas (L) and (O). If the thermoplastic resin (α) does not contain the structure of the following chemical formula, not only will it not be possible to obtain sufficient durability, but there will be no interaction with the polyarylene sulfide resin, and durability may be reduced. .

(where R ₁ to R ₆ in the formula are each H, OH, methoxy group, ethoxy group, trifluoromethyl group, aliphatic group having 1 to 13 carbon atoms, or aromatic group having 6 to 10 carbon atoms is.)
Examples of the thermoplastic resin (α) include various polymers such as polyamide, polyetherimide, polyethersulfone, polyphenylsulfone, polysulfone, polyphenylene ether, polyester, polyarylate, polyamideimide, polycarbonate, polyetheretherketone, and the like. Blends containing at least one of these polymers can be used. From the viewpoint of bending durability, the thermoplastic resin (α) is more preferably a resin selected from polyphenylsulfone, polyethersulfone and polyetherimide, and more preferably polyphenylsulfone.

The thermoplastic resin (α) used in layer B (II) of the laminate of the present invention preferably has a sulfonyl group. Having a sulfonyl group enhances the interaction of the polyarylene sulfide -based resin, restrains the amorphous chains, suppresses thermal deterioration, and can improve the bending durability in the case of forming a laminate.

In the present invention, the method of mixing the polyarylene sulfide resin and the thermoplastic resin (α) is not particularly limited, but the mixture of the polyarylene sulfide resin and the thermoplastic resin is preliminarily melt-kneaded (pelletized) before melt extrusion. There is a method of making master pellets by pressing, and a method of mixing and melt kneading during melt extrusion. Among them, a method of master pelletizing using an apparatus such as a twin-screw extruder that is subjected to shear stress is preferable. In this case, in the kneading unit, kneading is preferably carried out so that the resin temperature ranges from the melting point of the polyarylene sulfide resin +5°C to 80°C, more preferably from the melting point of the polyarylene sulfide resin +10°C to 80°C. More preferably, the temperature range is 15° C. to 70° C. or lower than the melting point of the polyarylene sulfide resin.

The concentration of the thermoplastic resin (α) used in the B layer (II) of the laminate of the present invention is 0.1% by mass or more and 30% by mass or less when the raw material composition of the layer is 100% by mass. is preferred. More preferably, it is 0.5% by mass or more and 15% by mass or less. By setting the concentration of the thermoplastic resin (α) within the above range, the interaction of the molecular chains acts efficiently, and the bending durability of the laminate can be improved. If the content of the thermoplastic resin (α) exceeds 30% by mass, the thermoplastic resin (α) becomes dominant and the bending durability is lowered, or frequent tears occur during stretching, making it impossible to form a film stably. There is In addition, when the content of the thermoplastic resin (α) is less than 0.1% by weight, the amorphous restraint effect is reduced and the bending durability may be reduced. , preferably a layer in which a thermoplastic resin (α) exists as a dispersed phase in a polyarylene sulfide-based resin. The dispersed phase as used herein refers to an island component of a sea-island structure composed of a polyarylene sulfide-based resin and a thermoplastic resin (α). The shape of the thermoplastic resin (α) means that the thermoplastic resin (α) is present in the polyarylene sulfide film of the present invention in a circular, elliptical, spindle-shaped, irregular shape, or the like. The morphology can be confirmed by (TEM) observation, scanning electron microscope (SEM) observation, or the like.

In the layer B (II) of the laminate of the present invention, the thermoplastic resin (α) present as a dispersed phase in the polyarylene sulfide resin has a dispersed diameter ratio of the major axis to the minor axis of 1.20 or more. is preferred. More preferably, it is 2.00 or more, still more preferably 3.50 or more, and most preferably 4.00 or more. When the ratio of the major axis to the minor axis is less than 1.20, peeling occurs at the interface between the polyarylene sulfide resin and the thermoplastic resin (α) during film stretching, and amorphous restraint due to interaction does not occur, and bending durability is improved. It may not improve. It is believed that the larger the ratio of the major axis to the minor axis, the stronger the interaction between the polyarylene sulfide resin and the thermoplastic resin (α), which contributes to the improvement of the heat-resistant bending resistance. Therefore, although no particular upper limit is set, it is estimated that the ratio of the major axis to the minor axis is about 20.00 as the practical upper limit, based on the draw ratio.

The A layer that constitutes the laminate of the present invention can be formed by extruding onto the M layer when forming the laminate, or by dissolving the resin in a solvent that dissolves the resin and coating it on the M layer. Alternatively, a film containing at least one layer of the layer A separately prepared as the outermost layer can be used to laminate the layer M by thermal lamination. It is also preferable to form the M layer directly on the A layer by a vapor deposition method or a plating method. Among the above, it is preferable from the viewpoint of productivity to bond the substrates by heat lamination using a film. Although the method of laminating by the heat lamination method is not particularly limited, a hot roll press method, a hot plate press method, and a vacuum hot plate press method are usually used.

In the present invention, from the viewpoint of improving the adhesion between the M layer and the A layer, the A layer may be subjected to corona treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, or embossing.
In the present invention, the heat lamination temperature is preferably Tm _A −20° C. or more and Tm _A +50° C. or less, where Tm _A is the melting point of the A layer. By heat laminating in the above temperature range, the adhesiveness with the M layer is increased, so that the flexibility of the laminate is improved. If the heat lamination temperature is lower than Tm _A , the adhesion may be lowered, and the M layer may be peeled off during circuit processing, resulting in a decrease in workability. Further, if the heat lamination temperature exceeds Tm _A +50° C., the resin may be decomposed or crosslinked depending on the temperature, so that the layer A may become brittle and the flexibility may decrease. The thermal lamination temperature is more preferably Tm _A or higher and Tm _A +30° C. or lower, and still more preferably Tm _A +5° C. or higher and Tm _A +20° C. or lower.

In the present invention, the heat lamination pressure is preferably 0.1 MPa or more and 10 MPa or less. By thermally laminating in the above pressure range, the A layer slips into the fine irregularities on the surface of the M layer, and the adhesion is enhanced by the anchor effect, so that the flex resistance of the laminate is improved. If the heat lamination pressure is less than 0.1 MPa, the resin may not flow to the irregularities on the surface of the M layer, resulting in a decrease in adhesion. Further, if the heat lamination pressure exceeds 10 MPa, the resin may flow and deform, which may cause process contamination due to extrusion or the like, and the resin layer may become thin, resulting in a decrease in flex resistance. The heat lamination pressure is more preferably 0.5 MPa or more and 8 MPa or less, and still more preferably 1 MPa or more and 5 MPa or less.

The thickness of the laminate of the present invention is preferably 10-300 μm, more preferably 40-200 μm. By setting it as said thickness, the high frequency transmission characteristic and flexibility can be compatible. When the thickness of the laminate is 10 μm or less, the laminate has no stiffness when folded, and may be bent or damaged. On the other hand, when the thickness is 300 μm or more, the rigidity may be high and the flexibility may be lowered. The thickness of the laminate can be confirmed by a method of cutting or polishing the laminate and calculating from a cross-sectional image obtained by a polarizing microscope from the cross-sectional direction, or by a method of calculating from the cross-sectional direction using a scanning electron microscope, but is not particularly limited. . The thickness of the laminate can be adjusted by adjusting the molding conditions, or by adjusting the thickness of the film or metal foil when using a film or metal foil.
The laminate of the present invention is particularly suitable as a base material for circuit boards. The circuit board of the present invention is obtained by forming an electric circuit on at least one side of the laminate by subjecting the laminate to circuit processing. An electric circuit is an electric path formed by patterning a conductor, and as the conductor, a metal such as copper, aluminum, iron, copper or silver, or a conductive paint containing carbon or the like is usually used. Also, an electric component or an electronic component may be mounted on the electric circuit. Also, the circuit board may be laminated in two or more layers. Holes can be easily formed in such circuit boards by a drill, laser, fusion penetration method, or the like. The circuit is formed by applying a photosensitive resin to the laminate, baking the circuit shape with light, then removing the resin from the unexposed areas, and etching with an aqueous solution of ferric chloride in the case of copper foil. It is mentioned as.

The method for producing the laminate of the present invention will be described using a polyarylene sulfide film and copper foil as materials, but the present invention is not limited to this example.

Sodium sulfide and p-dichlorobenzene and m-dichlorobenzene are blended in the ratio of the present invention, and in the presence of a polymerization aid in an amide-based polar solvent such as N-methyl-2-pyrrolidone (NMP), under high temperature and high pressure. react with If necessary, a copolymer component such as trihalobenzene can also be included. As polymerization degree modifiers, caustic potash, carboxylic acid alkali metal salts, etc. are added, and the polymerization reaction is carried out at a temperature of 200 to 290°C. After the polymerization, the polymer is cooled, and the polymer is made into an aqueous slurry and filtered through a filter to obtain a granular polymer. After washing with high-temperature water of 30 to 100°C, it is washed with an acetic acid aqueous solution or an acetate aqueous solution (for example, sodium acetate or calcium acetate) two or more times, more preferably three or more times, and then washed at 30 to 80°C. of deionized water and dried to obtain a granular polymer of copolymerized polyphenylene sulfide (hereinafter referred to as copolymerized PPS).

Alternatively, sodium sulfide and p-dichlorobenzene alone are reacted in an amide-based polar solvent such as N-methyl-2-pyrrolidone (NMP) in the presence of a polymerization aid at high temperature and high pressure. If necessary, a copolymer component such as trihalobenzene can also be included. As polymerization degree modifiers, caustic potash, carboxylic acid alkali metal salts, etc. are added, and the polymerization reaction is carried out at a temperature of 200 to 290°C. After the polymerization, the polymer is cooled, and the polymer is made into an aqueous slurry and filtered through a filter to obtain a granular polymer. After washing with high-temperature water of 30 to 100°C, it is washed with an acetic acid aqueous solution or an acetate aqueous solution (for example, sodium acetate or calcium acetate) two or more times, more preferably three or more times, and then washed at 30 to 80°C. of deionized water and dried to obtain a polyphenylene sulfide (PPS) granular polymer.

The above-obtained copolymerized PPS granular polymer and PPS granular polymer alone, or the granular polymer and inorganic particles, additives, etc., mixed in arbitrary proportions, and extruders with vents separately heated to 300 to 330. , melt extruded into strands, cooled with water at a temperature of 25° C., and then cut into chips.

In the present invention, it is preferable to blend 0 to 15% by mass of PPS chips with the copolymerized PPS chips obtained above as the resin constituting layer A. By setting the above range, the orientation parameter I _A of the A layer can be set within a predetermined range. More preferably 1 to 12% by mass, still more preferably 5 to 10% by mass.

The resin chips constituting layer A and the resin chips constituting layer B are separately dried under reduced pressure at 180°C for 3 hours, and then separately supplied to two extruders heated to 300 to 320°C. In the molten state, three layers (Lamination structure: A layer / B layer / A layer, lamination ratio: A layer: B layer = 1 to 5: 1 to 5) This sheet material is brought into close contact with a cooling drum having a surface temperature of 20 to 70° C. and solidified by cooling to obtain a substantially non-oriented unstretched film.

Next, in the case of biaxial stretching, the unstretched film obtained above is successively biaxially stretched or simultaneously biaxially stretched in the range from the glass transition point of the copolymerized PPS resin to the cold crystallization temperature of the PPS. After being biaxially stretched by a machine, a single-stage or multi-stage heat treatment is performed at a temperature in the range of 150 to 280° C. to obtain a biaxially oriented PPS film. Thereafter, after cooling to a temperature of preferably 35° C. or less, more preferably 25° C. or less, the film edges are removed and wound onto a core. Here, a relaxation annealing treatment may be applied to remove distortion of the molecular structure and reduce wrinkles and undulations during thermal lamination. The obtained PPS film and copper foil were laminated with the copper foil at a pressure of 0.2 MPa to 10 MPa using a roll group controlled to a temperature of Tm _A −20° C. or more and Tm _A +50° C. or less of the melting point of layer A. obtain.

An electric circuit is formed in the laminate thus obtained. An electric circuit can be formed by a known method, for example, circuit pattern etching. For etching, a ferric chloride aqueous solution or the like is usually used. Furthermore, the circuit board is obtained by forming through holes by a drill, laser, fusion penetration method, or the like.

The laminate of the present invention is useful as a high-frequency antenna substrate, a high-speed transmission cable, etc., because it is excellent in high-frequency characteristics, bending resistance, and workability.

[Method for measuring characteristics]
(1) Laminate folding endurance test A circuit pattern (Fig. 1) is formed on the laminate. At this time, if the M layer is present only on one side of the outermost layer, the pattern is formed on that layer. When both sides of the outermost layer are M layers, a pattern is formed on one side, and the M layer is removed from the entire surface of the other outermost layer by etching. Subsequently, using an MIT bending endurance tester, the conductivity of the sample was measured according to JIS C6471 with a radius of curvature of 0.38 mm, a load of 4.9 N, a bending angle of 135°, and a bending frequency of 175 times/min. In addition, each sample is measured five times, and the average value of these measurements is adopted as the number of folding resistance of the film.

(2) Laminate thickness and thickness of each layer When measuring the overall thickness of the laminate, use a dial gauge to measure the thickness of five arbitrary locations on the sample cut from the laminate, and obtain the average value. rice field. In addition, when measuring the thickness of each layer, the cross section of the laminate is cut out with a microtome, and the cross section of the film is photographed at a magnification of 100 using a metallurgical microscope Leica DMLM manufactured by Leica Microsystems. Then, the layer thickness of each layer of the laminated film was measured at arbitrary five points for each layer, and the average value was taken as the layer thickness of each layer.

(3) Presence or absence of voids The cross-sectional sample prepared in (2) was observed with a scanning electron microscope at a magnification of 5000, and the presence or absence of voids was confirmed from the observed image and evaluated according to the following criteria.
A: With voids B: Without voids (4) Confirmation of dispersed phase A film was cut in a direction parallel to the longitudinal direction and perpendicular to the film, and a cross-sectional sample was prepared by a frozen ultrathin section method. If the longitudinal direction cannot be determined, one of the directions is set to 0 °, and the direction is changed every 10 ° from -90 ° C to 90 ° C in the film plane, and the direction with the highest Young's modulus is the longitudinal direction. and In order to clarify the contrast of the dispersed phase, it may be stained with osmic acid, ruthenic acid, phosphotungstic acid, or the like. Using a transmission electron microscope (HT7700 manufactured by Hitachi), the cut surface was observed under the condition of an acceleration voltage of 100 kV, and a photograph was taken at a magnification of 2000 to confirm the shape of the dispersed phase. The obtained photograph is captured as an image in an image analyzer (Leica Application Suite LAS ver4.6 manufactured by Leica MICROSYSTEMS), 20 arbitrary dispersed phases are selected, the circumscribed circle of each dispersed phase is taken, and the average value of the diameter is calculated. and the size of the dispersed phase. Also, the major axis and minor axis of the dispersed phase were read and their ratio was calculated.

(5) Using a microplane, any layer to be measured is scraped and sampled within a range not exceeding the thickness confirmed in (2) from the layered body having the melting point of the resin constituting the layered body. When sampling, the M layer may be removed by etching if necessary. For the scraped sample, according to JIS K7121-1987, a DSC (RDC220) manufactured by Seiko Instruments Inc. as a differential scanning calorimeter and a disk station (SSC/5200) manufactured by Seiko Instruments Inc. as a data analysis device, 5 mg of the above sample was placed on an aluminum pan. , from room temperature to 350° C. at a rate of 20° C./min (1st Run). After the same sample is taken out and rapidly cooled, the temperature is raised from room temperature to 350° C. at a heating rate of 20° C./min (2nd Run).

The melting point (Tm) of the resin is defined as the peak temperature of the endothermic peak of melting confirmed on the DSC chart in the 2nd run.

(6) Orientation Parameter of Resin Constituting Laminate After the laminate was embedded in an epoxy resin, a cross section of the laminate was produced with a microtome. In the cross section of the produced laminate, the orientation parameter was obtained under the following conditions using a laser Raman device (PDP320 (manufactured by Photon Design)).
Microprobe Objective lens: 100x Cross slit: 1mm
Spot diameter: 1 μm
Light source: Nd-YAG (wavelength 1064 nm, output: 1 W)
Diffraction grating: Spectrograph 300g/mm
Slit: 100 μm
Detector: InGaAs (Roper Scientific 512)
Measurements were detected through a polarizer placed with the polarization direction parallel to the polarization direction of the incident light, the sample was rotated and the spectrum was obtained with the polarization direction parallel to the film plane with respect to the polarization direction of the laser light. Five samples were measured with the central point of each sample as the measuring point, and the average value was calculated according to the following formula (i) for the obtained spectrum.
(i) Orientation parameter I=I ₁₀₈₀ /I ₇₄₀
I ₁₀₈₀ : Intensity of 1080 cm ⁻¹ Raman band with polarization parallel to the film plane I ₇₄₀ : Intensity of 745 cm ⁻¹ Raman band with polarization parallel to the film plane (7) High-frequency transmission loss retention of laminate In order to evaluate the transmission characteristics of the laminate, a circuit having a line length of 100 mm and a characteristic impedance of 50Ω was formed with a microstrip structure. The formed circuit was treated for 2000 hours at a temperature of 85° C. and a humidity of 80%. Retention rate was calculated. Evaluation B is unacceptable.
Assuming that the transmission loss before the treatment is E0 and the transmission loss after the heat and humidity resistance test is E1, the retention rate of the transmission characteristics is calculated by the following formula. The retention rate of transmission loss was judged according to the following criteria.
Adhesive strength retention = E1/E0 x 100
A: Transmission loss retention rate is 80% or more.
B: Transmission loss retention rate is less than 80%.

(8) Laminate circuit workability (I)
In order to modelally evaluate the circuit processability of the laminate, a UV-YAG laser (ESI MODEL5335) was used to form through holes at a laser wavelength of 355 nm. The laminate is cut so as to pass through the center of the formed through-hole, observed with an electron microscope, and evaluated according to the following criteria. Evaluation C is unacceptable.
A: No burrs and M layer interfacial peeling.
B: Can be used without M layer interfacial peeling although there is burr.
C: Burrs occurred and delamination occurred at the interface of the M layer, resulting in poor conduction and unusable (9) Circuit workability of laminate (II)
A sample of 150 mm × 150 mm is cut out from the laminate and a dry film (Hitachi Chemical Co., Ltd. Phototech RD-2015) is laminated on the surface at a temperature of 105 ° C., exposed through a patterned mask, and a developer (sodium carbonate aqueous solution ) was developed. This was etched with a ferric chloride solution to form 10 patterns with a width of 0.2 mm and a length of 100 mm. If there is an M layer on one side of the outermost layer, a pattern is formed on that layer. When both sides of the outermost layer are M layers, one side is patterned and the other outermost layer is etched to remove the M layer. The state of circuit formation is evaluated according to the following criteria. Evaluation C is unacceptable.
AA: No peeling or curling.
A: There is no peeling of the pattern, and the laminate is slightly curled, but can be used.
B: The pattern is partially peeled and/or the laminate is curled, but it is conductive and can be used.
C: Peeling of the pattern and/or curling of the laminate to a large degree, and poor electrical connection, so that it cannot be used.

(10) Bending workability In order to model the insertion into equipment by bending and folding as a circuit board, a tensile tester was used, and after pulling the laminate with a certain amount of elongation, the differential interference microscope was measured. Observe the surface condition. The conditions are as follows.
(Tensile tester)
・Measuring device: Film strength and elongation automatic measuring device “Tensilon AMF / RTA-100” manufactured by Orientec Co., Ltd.
・Sample size: 5 mm in the width direction of the support × 100 mm in the longitudinal direction of the support,
・Tensile speed: 10%/min ・Tensile elongation: Measured at 10 points in increments of 0.5% in the range of 0.5% to 5% ・Measurement environment: Temperature 23°C, humidity 65% RH
(differential interference microscope)
・Measuring device: Leica DMLB HC, manufactured by Leica Microsystems Co., Ltd. ・Observation magnification: 1,000 times Ten samples were prepared by stretching at each elongation, and 10 fields of view were randomly observed for each sample. If a total of 8 or more places are observed, it is determined that cracks are present. Then, the flexibility is evaluated according to the following criteria. Reject C.
AA: When no cracks occur on the surface of the M layer with an elongation of 3% A: When cracks occur on the surface of the M layer with an elongation of 2% or more and less than 3% B: When the elongation is 1% or more and less than 2%, the surface of the M layer C: When cracking occurs on the surface of the M layer with an elongation of less than 1% (11) Bending durability In an oven (DRV420DA) manufactured by ADVANTEK set at 200 ° C., the folding endurance test described above The layered product with the circuit pattern (FIG. 1) formed thereon was left to stand for 1000 hours, and the heat-treated layered product was measured in the same manner as in (1). From the number of folding endurances before the endurance test and the number of endurance foldings after the endurance test, the retention rate was calculated by the following formula, and the value was defined as the bending durability. The bending durability was judged according to the following criteria.
Folding endurance retention rate = Folding endurance after endurance test/Folding endurance after endurance test × 100
AA: Folding number retention rate is 80% or more A: Folding number retention rate is 70% or more and less than 80% B: Folding number retention rate is less than 60%

In the following, Examples 2 and 5 shall be read as Reference Examples 2 and 5.
(Reference Example 1) Production method of copolymerized PPS resin 100 mol of sodium sulfide nonahydrate, 45 mol of sodium acetate and 25 liters of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were placed in an autoclave. was charged, the temperature was gradually raised to 220° C. while stirring, and the contained water was removed by distillation. 90 mol of p-dichlorobenzene as a main component monomer and 10 mol of m-dichlorobenzene as an auxiliary component monomer were added to the dehydrated system together with 5 liters of NMP. After pressure encapsulation in ^{step 2} , the temperature was raised and polymerization was carried out at a temperature of 260° C. for 4 hours. After the polymerization was completed, the mixture was cooled, the polymer was precipitated in distilled water, and a small mass of polymer was collected using a wire mesh having 150 mesh openings. The nodular polymer thus obtained was washed twice with distilled water at 90°C, then washed three times with an aqueous sodium acetate solution, then once with distilled water, and dried at a temperature of 120°C under reduced pressure. Granules of a copolymerized PPS resin having a melting point of 255° C. were obtained. The obtained granules were put into a vented co-rotating twin-screw kneading extruder (manufactured by Nippon Steel Works, screw diameter 30 mm, screw length/screw diameter = 45.5) heated to 300°C, and the residence time was 90. The mixture was melt-extruded at a screw speed of 150 rpm and extruded into strands, cooled with water at a temperature of 25° C., and immediately cut to prepare chips of copolymerized PPS (I).

(Reference Example 2) Production method of PPS resin (granules) 100 mol of sodium sulfide nonahydrate, 45 mol of sodium acetate and 25 liters of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) are placed in an autoclave. ) was charged, the temperature was gradually raised to 220° C. while stirring, and the contained water was removed by distillation. After dehydration, 100 mol of p-dichlorobenzene was added as a main component monomer together with ⁵ liters of NMP. C. for 4 hours. After the polymerization was completed, the mixture was cooled, the polymer was precipitated in distilled water, and a small mass of polymer was collected using a wire mesh having 150 mesh openings. The nodular polymer thus obtained was washed twice with distilled water at 90°C, then washed three times with an aqueous sodium acetate solution, then once with distilled water, and dried at a temperature of 120°C under reduced pressure. to obtain PPS resin granules having a melting point of 280°C.

(Reference example 3)
The granules of the PPS resin obtained in Reference Example 2 were heated to 330°C in a vented co-rotating twin-screw kneading extruder (manufactured by Nippon Steel Works, screw diameter 30 mm, screw length/screw diameter = 45.5). The mixture was melt-extruded at a residence time of 90 seconds and a screw rotation speed of 150 rpm, extruded into strands, cooled with water at a temperature of 25° C., and immediately cut to prepare chips of PPS (I).

(Reference example 4)
90% by mass of the copolymer PPS resin (I) chips obtained in Reference Example 1 and 10% by mass of the PPS resin (I) chips obtained in Reference Example 3 were blended for 15 minutes in a blender (manufactured by Kawada Seisakusho Co., Ltd.). After stirring, the mixture was taken out and used as chips of copolymerized PPS (II).

(Reference example 5)
80% by mass of the PPS resin granules obtained in Reference Example 2 and 20% by mass of calcium carbonate (CS-3NA (average particle size 1.5 μm, manufactured by Ube Material Industries, Ltd.)) were heated to 320 ° C. in a vent. It is put into a co-rotating twin-screw kneading extruder (manufactured by Japan Steel Works, screw diameter 30 mm, screw length / screw diameter = 45.5), and melt extrusion is performed at a residence time of 90 seconds and a screw rotation speed of 150 rpm. After cooling with water at a temperature of 25° C., the mixture was immediately cut into chips to prepare chips of PPS (II).

(Reference example 6)
95% by mass of the PPS resin granules obtained in Reference Example 2 and 5% by mass of polyphenylsulfone resin (PPSU: Solvay Advanced Polymers Co., Ltd., Radel R5800-NT)) were heated to 320° C. in a vented co-rotating It is put into a twin-screw kneading extruder (manufactured by Japan Steel Works, screw diameter 30 mm, screw length/screw diameter = 45.5), and melt extruded at a residence time of 90 seconds and a screw rotation speed of 150 rpm to form a strand. After discharging and cooling with water at a temperature of 25° C., the mixture was immediately cut into chips to obtain chips of PPS (III).

(Reference example 7)
95% by mass of the PPS resin granules obtained in Reference Example 2 and 5% by mass of polyethersulfone resin (PES: Veradel A201, Solvay Advanced Polymers Co., Ltd.) were heated to 320° C. in a vented co-rotating biaxial It is put into a kneading extruder (manufactured by Japan Steel Works, screw diameter 30 mm, screw length / screw diameter = 45.5), and is melt-extruded at a residence time of 90 seconds and a screw rotation speed of 150 revolutions / minute, and discharged into a strand. After cooling with water at a temperature of 25° C., it was immediately cut into chips to obtain PPS (IV) chips.

(Reference example 8)
95% by mass of the PPS resin granules obtained in Reference Example 2 and 5% by mass of polyetherimide resin (PEI: Ultem 1010 manufactured by SABIC Innovative Plastics Co., Ltd.) were heated to 320° C. and co-rotating twin-screw kneading with a vent. It is put into an extruder (manufactured by Japan Steel Works, screw diameter 30 mm, screw length / screw diameter = 45.5), a residence time of 90 seconds, a screw rotation speed of 150 rotations / minute, melt extruded and extruded into strands, and the temperature After cooling with water at 25° C., it was immediately cut into chips to obtain PPS (V) chips.

(Example 1)
Chips of copolymerized PPS (I) prepared in Reference Example 1 were dried under reduced pressure at 180°C for 3 hours, and then supplied to extruder 1 (layer A) whose melting section was heated to 300°C. Also, the chips of PPS (I) produced in Reference Example 3 were dried under reduced pressure at 180°C for 3 hours, and then supplied to extruder 2 (B layer) whose melting section was heated to 320°C.
The polymer melted in these two extruders was then passed through a fiber-sintered stainless steel metal filter (14 μm cut), followed by three-layer lamination (A/ B/A). The flow rate of the polymer passing through the confluence block was determined by adjusting the thickness of each layer so that the lamination ratio was A:B:A = 1:4.25:1 and adjusting the rotation speed of the gear pump installed on each line. adjusted by controlling In this way, the molten polymer is made into a three-layered state, melted and extruded from the mouthpiece of a T-die set at a temperature of 310 ° C., and then solidified by contact cooling while applying an electrostatic charge to a cast drum with a surface temperature of 25 ° C. to a thickness of 700 μm. An unstretched film was obtained. Next, after preheating the obtained unstretched film with a plurality of heating rolls heated to a surface temperature of 90° C., the heating roll heated to a surface temperature of 95° C. and the peripheral speed of the heating roll provided next to the heating roll It was stretched 3.5 times in the longitudinal direction (MD direction) between different cooling rolls at 30°C. The uniaxially stretched sheet thus obtained was stretched 3.5 times in the direction perpendicular to the longitudinal direction (TD direction) at 100°C using a tenter, and then heat-treated at 240°C. Subsequently, the film was subjected to a 5% relaxation treatment in the transverse direction (TD direction) for 4 seconds in a relaxation treatment zone at 240° C., cooled to room temperature, and then removed from the film edges to obtain a biaxially stretched PPS film having a thickness of 50 μm. .

Next, an electrolytic copper foil FLEQ HD2 (manufactured by Fukuda Metal Foil & Powder Co., Ltd., 12 μm) is laminated as a copper foil. The structure shown in Table 1 is superimposed. At this time, a vacuum press (manufactured by Mikado Technos Co., Ltd.) is used in a state in which the roughened matte surface of the electrolytic copper foil and the PPS film are overlapped. , in a vacuum degassed state, the laminate was laminated and joined at a temperature of 260° C., a pressure of 1 MPa, and a time of 5 minutes to obtain a laminate.

(Example 2)
The chips of the copolymerized PPS (I) prepared in Reference Example 1 were dried under reduced pressure at 180°C for 3 hours, then supplied to an extruder heated to 300°C, and heated to 300°C in a molten state to form fiber sintered stainless steel. After passing through a metal filter (14 μm cut), it is melt-extruded from the mouthpiece of a T-die set at a temperature of 300° C., and solidified by contact cooling while applying an electrostatic charge to a cast drum with a surface temperature of 25° C., resulting in an unstretched thickness of 700 μm. got the film. Then, the film was biaxially stretched in the same manner as in Example 1 to obtain a 50 μm-thick copolymerized PPS film composed only of the copolymerized PPS (I). Next, it was laminated with a copper foil in the same manner as in Example 1 to obtain a laminate composed of the copper foil and the copolymerized PPS.

(Example 3)
A laminate was obtained in the same manner as in Example 1, except that the copolymer PPS (II) chips prepared in Reference Example 4 were used for the A layer.

(Example 4)
A laminate was obtained in the same manner as in Example 3, except that the PPS (II) chip produced in Reference Example 5 was used for the B layer.

(Example 5)
The chips of PPS (I) prepared in Reference Example 3 were dried under reduced pressure at 180°C for 3 hours, supplied to an extruder heated to 330°C, and heated to a temperature of 330°C in a molten state to form a sintered fiber stainless metal filter. (14 μm cut), melt extruded from the mouthpiece of a T-die set at a temperature of 330 ° C., and solidified by contact cooling while applying an electrostatic charge to a cast drum with a surface temperature of 25 ° C. to form an unstretched film with a thickness of 700 µm. Obtained. Then, it was biaxially stretched in the same manner as in Example 1 to obtain a 50 μm biaxially stretched PPS film composed only of PPS (I). Next, it was laminated with a copper foil in the same manner as in Example 1 except that the temperature was changed to 290° C. to obtain a laminate composed of the copper foil and PPS.

(Example 6)
A laminate was produced in the same manner as in Example 3, except that the PPS (III) chip produced in Reference Example 6 was used for layer B, and the stretching ratio in the MD direction was set to 3.0 times from the viewpoint of film formation stability. Obtained.

(Example 7)
A laminate was obtained in the same manner as in Example 6, except that the PPS (IV) chip produced in Reference Example 7 was used for the B layer.

(Example 8)
A laminate was obtained in the same manner as in Example 6 except that the PPS (V) chip produced in Reference Example 8 was used for the B layer. (Comparative example 1)
A biaxially stretched PPS film was obtained in the same manner as in Example 5. An epoxy adhesive "Kemit TE 2301" (manufactured by Toray Fine Chemicals) was applied to both sides of the obtained PPS film with a thickness of 5 µm using a gravure roll, and dried at 100°C for 3 minutes. A PPS film with an adhesive layer was prepared. The obtained PPS film with adhesive and the copper foil were superimposed in the configuration shown in Table 1 and laminated at a temperature of 120° C. and 1 MPa for 5 minutes. A laminate consisting of foil, adhesive and PPS was obtained.

(Comparative example 2)
The chips of PPS (I) obtained in Reference Example 3 were dried under reduced pressure at 180°C for 3 hours, fed to an extruder heated to 330°C, and heated to a temperature of 330°C in a molten state to form a sintered fiber stainless metal filter. (14 μm cut), melted and extruded from the mouthpiece of a T-die set at a temperature of 330° C., adhered and cooled while applying static charge to a cast drum with a surface temperature of 25° C., and solidified, unstretched PPS film with a thickness of 50 μm. got The obtained unstretched PPS film was laminated with a copper foil in the same manner as in Example 1 except that the temperature was changed to 290° C. to obtain a laminate composed of the copper foil and PPS.

(Comparative Example 3)
Using a liquid crystal polymer (LCP) film VecstarCT-Z (manufactured by Kuraray Co., Ltd., 50 μm) as a film constituting the resin layer, superimposed in the configuration shown in Table 1, using a vacuum press at a temperature of 340 ° C. and a pressure of 1 MPa. , to obtain a laminate in which the resin layer was composed of LCP by laminating and bonding in 5 minutes.

Table 1 shows the evaluation results of the characteristics of the laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 3.

The laminate of the present invention and the circuit board using it are excellent in high-frequency transmission characteristics, bending resistance, and circuit processability, and are therefore suitably used as high-frequency antenna substrates and high-speed transmission cables used in electrical and electronic equipment. be able to.

1 circuit pattern (L/S=1mm/1mm)

Claims (8)

A laminate comprising at least one layer (A layer) containing a polyarylene sulfide resin as a main component and at least one layer (M layer) containing a metal as a main component, and wherein the A layer and the M layer are in contact with each other, , the number of times of folding is 100 or more in a bending resistance test, the laminate includes at least a layer B having a higher orientation parameter than the layer A, and the orientation obtained by laser Raman spectroscopy from the cross-sectional direction of the layer B A laminate having a parameter _IB of 8 or more and 8.5 or less , wherein the B layer contains a polyarylene sulfide resin as a main component . 2. The laminate according to claim 1, wherein the orientation parameter _IA obtained by laser Raman spectroscopy from the cross-sectional direction of the layer A is less than 6. 3. The laminate according to claim 1, wherein the layer B comprises layer B (I) having pores. The layer B comprises a layer (II) having a thermoplastic resin (α) different from the polyarylene sulfide resin, and the thermoplastic resin (α) having any of the following skeletons. 4. The laminate according to any one of 3.

(where R ₁ to R ₆ in the formula are each H, OH, methoxy group, ethoxy group, trifluoromethyl group, aliphatic group having 1 to 13 carbon atoms, or aromatic group having 6 to 10 carbon atoms is.) 5. The laminate according to claim 4, wherein the ratio of the major axis to the minor axis of dispersed diameters of the thermoplastic resin is 2.0 or more. 6. The laminate according to any one of claims 1 to 5, wherein said layer A has a melting point of 275°C or less. A circuit board using the laminate according to any one of claims 1 to 6. A circuit board comprising at least one layer (A layer) containing a polyarylene sulfide resin as a main component and at least one circuit containing a metal as a main component, wherein the A layer and the circuit are in contact with each other. , the number of times of folding is 100 or more in a bending resistance test, the circuit board includes at least a layer B having a higher orientation parameter than the layer A, and the orientation obtained by laser Raman spectroscopy from the cross-sectional direction of the layer B A circuit board having a parameter _IB of 8 or more and 8.5 or less , wherein the B layer contains a polyarylene sulfide resin as a main component .

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