JP5105217B2 - Metal laminate - Google Patents

Description

  The present invention relates to a metal laminate. More specifically, the present invention relates to a metal laminate comprising a base material, a barrier layer having a stress relaxation function, and two metal layers, having high bonding strength between the respective layers and excellent durability.

  A metal laminate comprising a base material and a metal layer has been widely used conventionally. For example, a metal laminate in which a conductive metal layer is formed on an insulating substrate is used for various electronic components such as wiring substrates, electromagnetic shielding materials, display shadow masks, semiconductor packages, photomasks, IC tags, connectors. It is used for sockets.

  As a technique for obtaining such a metal laminate as a hard mask for manufacturing a shadow mask, there is a technique described in JP-A-11-133588.

Japanese Patent Application Laid-Open No. 2004-255845 discloses a gas barrier polyimide film in which a metal layer is formed on one side of a polyimide film.
Japanese Patent Laid-Open No. 11-133588 JP 2004-255845 A

  For example, when the metal laminate is used stably for a long period of time in the above application, the bonding strength between the layers constituting the metal laminate is high, and even if it is exposed to a high temperature and high humidity atmosphere for a long time. There is no need for peeling or warping of each layer, no reduction in bonding strength, and the like, and prevention of deterioration of the substrate surface characteristics.

  And in the process of manufacturing the metal laminate and the process of processing the metal laminate according to each application, it is extremely important that the bonding strength of each layer is high and the impact resistance is excellent.

  In addition, resin materials are widely used for the base material layer of the metal laminate for reasons such as electrical insulation, processability, flexibility, economy, etc. Generally, the resin material layer and the metal layer are The thermal expansion characteristics or shrinkage characteristics are different, or the bonding strength between the two layers is often insufficient, and during the manufacturing process, processing process or use of the metal laminate, delamination or warpage occurs, The surface smoothness and the like sometimes deteriorated.

  When the metal layer of the metal laminate is formed by plating, or when the metal layer is patterned to form an electronic circuit or the like by patterning the metal layer, the metal laminate is sufficient for these treatments. Must be durable.

  However, as far as the present inventors know, conventional metal laminates are often insufficient in strength and durability, and are difficult to apply to a wide range of applications. Moreover, in order to give required strength etc., it was necessary to make the whole metal laminated body thick, and the use was also restricted from weight and economical efficiency.

  The present invention solves the above problem by disposing a specific barrier layer and two metal layers on at least one side of a substrate.

  Therefore, the metal laminate according to the present invention is characterized in that the base material and the barrier layer, the metal thin film layer, and the metal layer are arranged in this order on at least one surface of the base material. Is. In addition, this metal laminated body by this invention may be called "the 1st metal laminated body" in this specification.

  Another metal laminate according to the present invention is characterized in that a base material, a barrier layer formed on at least one surface of the base material, and a metal thin film layer are arranged in this order. It is what. In addition, this another metal laminated body by this invention may be called "the 2nd metal laminated body" in this specification.

  The “first metal laminate” and the “second metal laminate” according to the present invention include the following metal laminate as a preferred embodiment.

(1) A metal laminate in which the barrier layer is made of any one of an inorganic oxide, an inorganic nitride, an inorganic carbide, an inorganic oxide carbide, an inorganic oxynitride, an inorganic carbonitride, and an inorganic oxycarbonitride.

(2) The above barrier layer is an inorganic oxide or inorganic nitride of an inorganic element selected from the group consisting of silicon, aluminum, chromium, magnesium, calcium, titanium, niobium, molybdenum, tantalum, indium, tin and zirconium , An inorganic carbide, an inorganic oxide carbide, an inorganic oxynitride, an inorganic carbonitride, and an inorganic oxycarbonitride.

(3) The barrier layer is composed of silicon oxide, aluminum oxide, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, silicon nitride, aluminum oxynitride, aluminum nitride, chromium oxide, indium A metal genus laminate comprising one of oxide films.

(4) The metal laminate in which the barrier layer has a grain distance of 100 nm or less.

(5) A metal laminate in which the barrier layer has a relative density with respect to an ideal density of 70% or more.

(6) A metal in which the barrier layer is formed by a vapor deposition method, a sputtering method, a plasma CVD method, a hot wire CVD method, an ion plating method, or an ion plating method using a pressure gradient type plasma gun Laminated body.

(7) A metal laminate in which the metal layer has a grain distance of 100 nm or less.

(8) A metal laminate in which the base material has been subjected to a bonding strength improving treatment on the surface of the base material prior to the formation of the barrier layer.

(9) A metal laminate in which a stress relaxation layer is disposed between the barrier layer and the metal thin film layer.

(10) A metal laminate in which a stress relaxation layer is disposed on the opposite surface of the substrate on which the barrier layer and the metal thin film layer are formed.

(11) A metal laminate in which stress relaxation treatment is performed on the opposite surface of the base material on which the barrier layer and the metal thin film layer are formed.

(12) The base material is selected from polyimide, polyethylene terephthalate, polyethylene naphthalate, epoxy (meth) acrylate resin, urethane (meth) acrylate resin, (meth) acrylate resin, and polyorganosilsesquioxane-containing silicone resin. A metal laminate.

  The “first metal laminate” and the “second metal laminate” according to the present invention further include the following metal laminate as a preferred embodiment.

(13) A metal laminate in which the barrier layer has an oxygen barrier property with an oxygen permeability of ² cc / m ² / day · atm or less at a measurement condition of 23 ° C.

(14) A metal laminate in which the barrier layer has an oxygen barrier property with an oxygen transmission rate of ² cc / m ² / day or less at a measurement condition of 80 ° C.

(15) A metal laminate in which the barrier layer has a water vapor barrier property with a water vapor transmission rate of 2 g / m ² / day or less at a measurement condition of 40 ° C.

(16) A metal laminate in which the barrier layer has a water vapor barrier property with a water vapor transmission rate of 2 g / m ² / day or less at a measurement condition of 80 ° C.

(17) The metal laminate, wherein the total light transmittance in a non-arranged state of the metal layer and the metal thin film layer is 70% to 100%.

(18) The metal laminate according to any one of the metal laminates, wherein the total light transmittance in a non-arranged state of the metal layer and the metal thin film layer is 0% to 70%.

(19) A metal laminate in which the bonding strength improving process is a plasma discharge process.

(20) The metal laminate, wherein the bonding strength improving treatment is adhesion layer coating.

(21) A metal laminate in which the adhesion layer is an adhesive.

(22) A metal laminate in which the adhesion layer is an acrylic resin, an epoxy resin, a urethane resin, or a (meth) acrylate resin.

  In the metal laminate according to the present invention, the barrier layer, the metal thin film layer, and the metal layer are arranged in this order on the base material and at least one surface of the base material. The bonding strength is high and the durability is extremely high.

  Therefore, even when exposed to a high temperature and high humidity atmosphere for a long period of time, each layer is not peeled or warped, the bonding strength or the like is not lowered, and deterioration of the base material characteristics is prevented.

  In such a metal laminate according to the present invention, the metal laminate is subjected to stress applied from the outside and changes in conditions such as heat, humidity, and electric field at each stage of manufacturing, processing and use after processing. Since the stress generated inside the metal laminate that causes warpage and delamination in the laminate is relaxed, the metal laminate is effectively prevented from being deformed or damaged.

[Metal laminate]
A first metal laminate according to the present invention is characterized in that a barrier layer, a metal thin film layer, and a metal layer are arranged in this order on at least one surface of the substrate and the substrate. Is.

  Here, “the barrier layer, the metal thin film layer, and the metal layer are arranged in this order” means that the arrangement position of each layer of the barrier layer, the metal thin film layer, and the metal layer is the distance from the substrate surface. When it shows from the near side, it means that a barrier layer, a metal thin film layer, and a metal layer are arrange | positioned in this order.

  The metal laminate according to the present invention has the barrier layer, the metal thin film layer, the metal layer disposed over the entire region of at least one surface of the substrate, and the at least one surface of the substrate. The barrier layer, the metal thin film layer, and the metal layer partially disposed are included. For example, a metal thin film layer or a metal laminate in which a metal layer is partially disposed and applicable to a wiring board application is included in the metal laminate according to the present invention. In addition, the metal laminate according to the present invention includes at least one of the above-mentioned base material, barrier layer, metal thin film layer, and metal layer, which are essential constituent members, and another arbitrary layer material or material. Includes those arranged in any part of the metal laminate.

  The second metal laminate according to the present invention is characterized in that a base material and a barrier layer and a metal thin film layer are arranged in this order on at least one surface of the base material. is there. This 2nd metal laminated body can be set as said 1st metal laminated body by arrange | positioning a metal layer on the metal thin film layer. Such a second metal laminate can be regarded as a so-called semi-finished product of the first metal laminate.

[Metal laminate (specific example)]
Hereinafter, the metal laminate according to the present invention will be described in more detail with reference to the drawings.
1 and 2 show an outline of a particularly preferred embodiment of the metal laminate according to the present invention.
In the first metal laminate 1 according to the present invention shown in FIG. 1A, a barrier layer 3, a metal thin film layer 4, and a metal layer 5 are arranged in this order on one surface of a substrate 2. It will be. The metal laminate 1 including all of the substrate 2, the barrier layer 3, the metal thin film layer 4 and the metal layer 5 is the first metal laminate according to the present invention, and the substrate 2 shown in FIG. The metal laminate 11 including the barrier layer 3 and the metal thin film layer 4 is the second metal laminate according to the present invention.

<Base material>
The base material 2 of the metal laminate according to the present invention can be formed of various hard or soft inorganic materials and organic materials. In the present invention, (a) inorganic materials such as glass, silicon wafer, metal plate, fiber, nonwoven fabric, paper, and (b) resin material, preferably, for example, polyarylate resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate Resin, methacrylic resin, (meth) acrylic resin, (meth) acrylate resin, (meth) epoxy resin, polyethersulfone resin, polyetheretherketone resin, polyetherimide resin, polyimide resin, polyphenylene sulfide resin, polynorbornene resin and Resin materials such as a cyclic polyolefin resin, a urethane (meth) acrylate resin, and a cercisioxane-containing silicone resin, paper, and other organic materials can be used. Here, among the inorganic materials of (A), glass and metal are particularly preferable, and among (B) organic materials, particularly, polyethylene terephthalate resin, polyethylene naphthalate resin, polyimide resin, polynorbornene resin, cyclic Polyolefin, methacrylate resin, urethane (meth) acrylate resin, and polyorganosilsesquioxane-containing silicone resin are preferred. As the resin material, a resin material having a glass transition temperature (Tg) of 120 ° C. or higher is particularly suitable as a resin material in consideration of a sufficient temperature (100 ° C. or higher) at which the substrate can be dehydrated. Here, “(meth) acryl” means both acryl and methacryl, and “(meth) acrylate” means both acrylate and methacrylate.

  A base material exhibiting flexibility can be used for, for example, an FPC (Flexible Printed Circuit) application, and also reduces breakage due to stress.

  In many cases, the substrate 2 has a flat surface, but even if the substrate surface has an uneven shape, a substrate having holes or voids that penetrate or do not penetrate the substrate can be used. . For example, the base material 2 which consists of a woven fabric or a nonwoven fabric corresponds to this.

  In the present invention, prior to the formation of the barrier layer 3, the bonding strength improving treatment can be performed on the surface of the base material 2 as necessary. The base material that has been subjected to such a bonding strength improvement treatment has improved adhesion and bonding strength between the base material 2 and the barrier layer 3, and is a metal in the production, processing or use environment of the metal laminate. Deformation, delamination, and characteristic deterioration of the laminated body are further difficult.

  This bonding strength improving treatment can be performed on the entire region where the barrier layer 3 on the surface of the substrate 1 is bonded, or at least a partial region where the barrier layer 3 on the surface of the substrate 1 is bonded. In addition, the area | region where the barrier layer 3 is not joined on the base material 1 surface may or may not be subjected to the joining strength improving treatment.

  The bonding strength improving process can be performed by any method. Examples of preferable bonding strength improving treatment include physical treatment such as plasma discharge treatment and chemical treatment such as oxidation treatment. Another method is a method of providing an adhesion layer on the surface of the substrate (that is, an adhesion layer coating method). As this adhesion layer, it is preferable to use an acrylic resin, an epoxy resin, a urethane resin, or a (meth) acrylate resin. The adhesive layer may use an adhesive.

  The thickness of the base material 2 can be appropriately determined in consideration of the specific application, required performance, material, etc. of the metal laminate. 0.2 to 1.1 mm for display substrate applications, 0.4 to 10 mm for mask substrate applications, 0.2 to 1 mm for device elements such as semiconductors, 25 to 100 μm for FPC substrate applications, electromagnetic shielding material substrate For applications, 50 to 100 μm, for IC tags, 200 μm to 3 mm, etc. are preferably used. In general, 0.2 to 10 mm is preferable for inorganic substrates, and 50 to 400 μm is preferable for organic substrates.

<Barrier layer>
The barrier layer 3 of the metal laminate according to the present invention is disposed at a position closest to the surface of the substrate 2 in the metal thin film layer 4 and the metal layer 5.

  This barrier layer 3 mainly functions as a gas barrier layer that shields gas, and functions as a metal barrier layer for preventing migration from the metal thin film layer 4 or the metal layer 5 to the substrate 2 side. At the same time, it functions as a stress relaxation layer. Thereby, in each of the manufacturing stage, the processing stage, and the use stage of the metal laminate, the base material 2, the metal thin film layer 4 or the metal layer 5 deteriorates due to the influence of gas or metal diffusion, or is damaged by stress. It is prevented.

  In the film for exhibiting such a barrier function, the distance between grains of the barrier layer is preferably 100 nm or less, particularly preferably 80 nm or less. When the distance between grains is small, the permeation and diffusion of gas and metal can be prevented, and a laminate having excellent adhesion and durability can be obtained.

  Furthermore, it is preferable that the film for expressing the barrier function has a denseness in which the density of the barrier layer 3 is 60% or more of the ideal density obtained from the element composition. The more dense the film and the fewer the defects, the more the gas and metal can be prevented from permeating and diffusing, and a laminate having excellent adhesion and durability can be obtained.

The barrier layer 3 preferably has an oxygen permeability of ² cc / m ² / day · atm or less and a water vapor permeability of 2 g / m ² / day or less. When the oxygen permeability exceeds the above value, the metal layer is significantly oxidized by the oxygen gas that has permeated from the substrate side, and the metal film is deteriorated or peeled off due to the oxidation. Further, when the water vapor transmission rate exceeds the above value, corrosion of the metal film due to moisture becomes remarkable, and in any case, the film quality of the metal film is deteriorated or the metal film is peeled off.

  In the metal laminate according to the present invention, a gas (for example, an oxidizing gas such as oxygen or carbon dioxide, a reducing gas such as hydrogen or ammonia, or water vapor), a metal thin film layer 4 or a metal layer 5 is formed by the barrier layer 3. Since the permeation and diffusion of the contained metal are blocked, the characteristic deterioration of the base material 2, the metal thin film layer 4, the metal layer 5 and the metal laminate as a whole is prevented, and a remarkable improvement in durability is recognized. In particular, water vapor promotes ionization of the metal in the same manner as ionization promoting substances such as sodium, potassium, chlorine, etc., so when the metal laminate is placed in an electric field, it may cause the occurrence of migration, In the metal laminate according to the present invention, the barrier layer 3 blocks oxygen gas, water vapor, metal, and the like as described above, thereby preventing migration.

  Moreover, the barrier property of the barrier layer 3 needs to have a barrier property not only in the 23 ° C. to 40 ° C. region near room temperature but also at 80 ° C. which is a processing process and a storage environment.

  The barrier layer 3 functions as a stress relaxation layer as described above.

  In the metal laminate according to the present invention, the barrier layer 3 is disposed so as to be interposed between the base material 2, the metal thin film layer 4, and the metal layer 5. Since stress applied from outside in each stage of the later use stage, and stress generated inside the metal laminate that causes warpage to the metal laminate due to changes in conditions such as heat and humidity, are relaxed, The metal laminate is effectively prevented from being deformed or damaged.

  Here, as shown in FIG. 3, “stress” means “force to stretch (tensile stress)” and “force to compress (compressive stress)” of each base material generated between the thin film to be formed and the substrate. This is the vector quantity expressed as the difference between the two. When the film surface is concave as shown in FIG. 3A and the film is pulled from the substrate, tensile stress is applied. Conversely, as shown in FIG. 3B, the film surface becomes convex and the film is pushed from the substrate. Called compressive stress. When such stress is strong, the substrate deforms (curls), the thin film or the substrate cracks, the thin film peels off, and the physical properties of the thin film, such as electrical characteristics and optical characteristics It affects etc.

The following three factors can be considered as the cause of the stress.
(1) During film formation, the substrate temperature rises due to heat radiation from the evaporation source or heating the substrate itself. When the substrate temperature is lowered to room temperature after film formation, the substrate is deformed and stress is generated by a so-called bimetal effect due to a difference in thermal expansion coefficient between the thin film and the substrate. Stress caused by such heat effects is called thermal stress,
σ = Ef (αf−αs) ΔT Equation 1
Given in. Here, αf and αs are the thermal expansion coefficients of the film and the substrate material, Ef is the Young's modulus of the thin film, and ΔT is the temperature rise.

  Stress obtained by subtracting such thermal stress is called true stress. The causes of the true stress are roughly classified into those caused by volume changes and those caused by surface or interface effects.

  (2) Due to volume change, volume change due to phase transition (amorphous → crystal, liquid phase → solid phase, etc.) during thin film growth, or vacancies and voids existing in the film diffuse to the surface by annealing In addition, volume changes such as volume shrinkage due to disappearance can be given. When the volume contracts, tensile stress is generated, and when it expands, compressive stress is generated.

  (3) As the effect of the surface and interface, the generation of stress corresponding to each stage of the thin film formation process can be considered. In the island-like film at the initial stage of growth, the movement of the island is restricted by the substrate due to the adhesion force, and the surface is compressed by the surface tension, so that a compressive stress is generated. As islands grow and come close to each other, attractive forces act between the islands, creating tensile stress. The islands stick together to form a crystal grain boundary, but the crystal grain boundary disappears with growth, and the volume shrinks along with it, and tension is generated.

  It is known that the change in internal stress greatly depends on the vacuum conditions during film growth. This is particularly noticeable in changes after deposition. This may be due to the fact that compressive stress is generated by the residual gas being taken into the thin film as impurities, the compressive stress is generated by grain boundary diffusion even at a low temperature, or a mechanism in which a thin oxide film is formed on the surface.

  As a method for measuring stress, there are a method for measuring a deformation amount of a substrate, a method for measuring a change in a lattice constant and a surface interval, and a method for measuring a change in a physical property value such as a phonon frequency.

The stress is represented by a force σ per unit area acting on a cross section perpendicular to the substrate, and the unit is N / m ² or dyn / cm ² . In actual measurement, force S (total stress) acting on the entire thin film is measured. If there is no distribution of stress in the film thickness direction, the stress is given by σ = S / d, where d is the film thickness.

As a method for obtaining the stress from the deformation amount of the substrate, when a thin film containing uniform stress is deposited on the disc-like substrate, the disc is curved. Stress can be obtained by measuring the curvature of the curvature with a Newton ring method, a stylus method, a laser displacement meter, or the like. If the radius of curvature is r, the stress is given by the following equation when the thickness of the disk is sufficiently smaller than r.
σ = Eb2 / (6 (1-ν) rd) Equation 2
Here, E is the Young's modulus of the substrate, b is the thickness of the substrate, ν is the Poisson's ratio of the substrate, and d is the thickness of the thin film.

When one of the strip-shaped thin substrates is fixed and a thin film is deposited, the free end is displaced (cantilever method). It is possible to evaluate the stress by measuring the amount of displacement with a cathemeter, an optical lever, an electric capacity, a laser displacement meter, or the like. Since this method can also be continuously measured during the vapor deposition process, it can be used to measure the Sd curve, and the thickness dependence of stress can be obtained from this gradient. When the thickness of the thin film is sufficiently smaller than the thickness of the substrate, the stress is given by
σ = Eb ² δ / 3 (1-ν) dl ² Formula 3
Here, l is the length of the substrate, and δ is the amount of displacement of the free end. If the displacement is measured by a system of the order of 1 μm, the total stress can be measured with an accuracy of 10 ¹ to 10 ² dyn / cm.

In addition, the lattice constant or the surface interval can be measured by the X-ray diffraction method, the strain can be obtained, and the stress can be estimated therefrom. Specifically, the deviation of the (h, k, l) plane spacing d _{hkl from} the normal value d _{0 hkl}
ε = (d _0hkl −d _hkl ) / d _hkl Equation 4
Is the strain in the <h, k, l> direction of the (h, k, l) plane, and the stress is
σ = (E / 2ν) _ε Equation 5
Given in.
As another method, there is a method of obtaining from Raman scattering.
Here, the stress that is actually required will be described using Equation (2). As an example, assuming a case where the amount of warpage is relatively large and considered to be a limit on the severe side, a case is considered where the amount of warpage of a resin substrate having a length of 100 mm and a thickness of 0.05 mm is suppressed to 8 mm or less. In this case, the curvature radius r of the curvature is 155 mm. In general, in the case of a resin substrate, although there are differences depending on the material of the substrate, Young's modulus E = 10000 to 20000 kgf / cm ² and Poisson's ratio ν = 0.4 to 0.5. In the above, when Young's modulus E = 15000 gf / cm ² , Poisson's ratio 0.5, 1 kgf≈10 ⁶ dyn / cm ² is used, the total stress calculated is σ · d (dyn / cm) = {15000 × 9.8 × 10 ⁵ × (5 × 10 ⁻³ ) ² } / {6 × (1-0.5) × 15.5}
= 7.9 × 10 ³ ≈8000
It turns out that it is. Therefore, the role of the stress relaxation layer must be provided so that the total stress of the entire substrate is 8000 dyn / cm or less. Specifically, it is preferable to adjust the film thickness and film quality so as to suppress the total stress within the above range.

  The barrier layer 3 can be formed of any material as long as both the above-described predetermined gas barrier function and stress relaxation function can be obtained. Also, the thickness of the barrier layer 3 can be determined as appropriate in consideration of the specifically adopted material, gas barrier function, and stress relaxation function.

  Furthermore, the performance required for the barrier layer 3 to satisfy the above performance is (b) in addition to the barrier property against gas / metal, (b) sufficient adhesion to the substrate, the metal thin film layer or the metal layer, (C) Flexibility is required to prevent damage from external forces and stress.

  From the above viewpoint, the barrier layer 3 preferably has an inter-grain distance in the inorganic film of 100 nm or less, particularly 80 nm or less. Here, the grain appears as an island when a cross section of an AFM image obtained by observing the surface of the deposited film with an atomic force microscope (AFM) is divided at a predetermined height and binarized. Say part. That is, unevenness is formed on the surface of the vapor deposition film 3, and observation and image processing are performed using an atomic force microscope in order to make the unevenness easy to understand. It is a part.

  Moreover, the distance L between grains means the distance from the peak of a grain (the vertex part of a convex part) to the peak of the grain adjacent to the said grain. From the distance L between the grains, it can be understood how much grains (convex portions) exist per unit length, and the density of the grains formed on the surface of the deposited film can also be understood.

  As shown in FIG. 4 (A) and FIG. 4 (B) which is a partial enlarged view of the main part Z, grains are formed on both surfaces or one surface of the base material and formed on the surface of the deposited film. It is characterized in that the distance L between 3a is 100 nm or less.

  The portion of the grain 3a is a portion having high crystallinity or denseness in the barrier film 3 and has a property that gas, water vapor, and metal are difficult to permeate. Therefore, by setting the distance L between the grains within the above range, the region (a portion other than the grains) through which the gas or the like can permeate in the deposited film is reduced, so that the barrier property can be improved. When the distance L between the grains is in the above range, that is, 5 to 100 nm, it can be a deposited film having a good barrier property, and a more preferable range of the distance L between grains is 5 to 80 nm. A range of 5 to 50 nm is more preferable.

  In order to measure the distance between grains in a film produced by the plasma CVD method, the surface of the film is exposed to a highly crystalline grain portion using an aqueous hydrofluoric acid solution or the like, and a surface shape measuring device such as an AFM is used. It is also possible to measure these distances.

Furthermore, the barrier layer 3 should have a denseness of 60% or more, preferably 70% or more of the ideal density obtained from the elemental composition ratio. Here, with regard to the ideal density, for example, in the case of a SiO ₂ film, quartz glass is known as the highest density material, and this density is known to be 2.65 g / cm ³ . By determining the constituent elements and the composition ratio in this way, the density of the densest film theoretically possible for the film is set as the ideal density. On the other hand, the actual film density is calculated. Specific methods include a method of measuring and calculating the mass and volume (attached area and film thickness) of the formed film, and a method of calculating using an X-ray reflectivity measuring apparatus. For example, when the density of this film is 2.12 g / cm ³ , the density ratio of this film can be obtained as 2.12 ÷ 2.65 × 100 = 80%. Similarly, in the case of the SiC film, the ideal density is 3.12. Therefore, even if the actual film density is 2.12 g / cm ³ as in the previous example, the density ratio is 2.12 ÷ 3.12 × Only 100 = 68%, the actual denseness is lower than the previous example, and the barrier performance is inferior. Further, the ideal density of a film made of a plurality of elements may be calculated and defined according to the actual atomic ratio. In the case of a silicon oxide carbide film, if the atomic ratio of Si: C: O forming the film is 100: 50: 50 as a result of the composition analysis by ESCA, it is intermediate between the SiO ₂ film and the SiC film. And (2.65 + 3.12) ÷ 2 = 2.89 g / cm ³ in calculation. The ideal density of other materials is, for example, magnesium oxide (MgO) 3.62 g / cm ³ , aluminum oxide (Al ₂ O ₃ ) 4.075 g / cm ³ , tin oxide (SnO ₂ ) 6.915 g / cm ^3. As described above, it is clear that the relative density with respect to the ideal density reflects the denseness of the film.

The barrier layer 3 in the present invention is preferably composed of any one of (a) an inorganic oxide, an inorganic nitride, an inorganic carbide, an inorganic oxide carbide, an inorganic oxynitride, and an inorganic oxycarbonitride. Preferably, (b) oxides, nitrides, carbides of inorganic elements selected from the group consisting of silicon, aluminum, chromium, indium, magnesium, calcium, titanium, niobium, molybdenum, tantalum, indium, tin and zirconium, It is made of oxycarbide, oxynitride, carbonitride, or oxycarbonitride, and particularly preferably (c) silicon oxide (specifically, SiO _x (X = 0 to 2), aluminum oxide) , Silicon oxycarbide (specifically, for example, SiOC), silicon oxynitride (specifically, for example, SiON), silicon oxycarbonitride (material) Thereof include, for example SiONC), it is made of either.

  As a film having higher adhesion to the base material 2 and the metal thin film 4 and having flexibility, it is preferable that carbon, nitrogen, and oxygen are appropriately contained in the film. Accordingly, the silicon oxide is preferably Si: O = 100: 100 to 200 (atomic ratio). As the aluminum oxide, any of α-alumina, β-alumina, γ-alumina and ζ-alumina can be used, and the barrier layer 3 is particularly preferably Al: O = 100: 80 to 150.

  The silicon oxide carbide is preferably Si: O: C = 100: 40 to 190: 20 to 120 (atomic ratio). According to such silicon oxycarbide, not only the film becomes dense, but also an excellent film in terms of adhesion and flexibility.

  The silicon oxynitride is preferably Si: O: N = 100: 50 to 150: 30 to 120 (atomic ratio). According to such silicon oxynitride, not only the film becomes dense but also an excellent film in terms of adhesion and flexibility.

  As silicon oxycarbonitride, Si: O: C: N = 100: 80 to 180: 80 to 180: 30 to 120 (atomic ratio) is preferable. According to such silicon oxycarbonitride, not only the film becomes dense but also an excellent film in terms of adhesion and flexibility.

  The thickness of the barrier layer 3 can be appropriately determined in consideration of the specific application, required performance, material, etc. of the metal laminate. When the thickness of the barrier layer 3 is shown about the metal laminated body especially suitable for a FPC board use, generally 5 nm-1000 nm, especially 10 nm-300 nm are preferable.

  And when the metal laminated body by this invention is attached | subjected to an etching process, the barrier layer 3 has a preferable water repellency. In particular, those having water repellency with a contact angle of water at 23 ° C. of 60 degrees or more are preferable. When such a water-repellent barrier layer 3 is exposed by the etching process, the etching solution is repelled and spreads on the barrier layer 3, and the surrounding walls (the cross section of the metal thin film layer 4, the metal layer 5, etc.) are effective. Therefore, a portion where etching progresses slowly is not generated.

  The barrier layer made of silicon oxide, silicon carbide, silicon oxycarbide, silicon oxynitride, and silicon oxycarbonitride is usually preferable from the viewpoint of water repellency because it has the above water repellency. is there.

When the barrier layer 3 does not have the above water repellency, or when the water repellency is further improved, by introducing fluorine or methyl group on the surface of the barrier layer, the water repellency is positively imparted or enhanced. Can be As such treatment, a method of using a gas such as CF ₄ or SiF ₆ by a plasma CVD method (CVD: Chemical Vapor Deposition) or the like is preferable.

  The barrier layer can be formed by stacking two or more layers. In that case, the material constituting each layer and the method of forming each layer may be the same or different from each other.

Formation of Barrier Layer In the production of the metal laminate according to the present invention, the barrier layer 3 is preferably formed by a vapor deposition method, a sputtering method, a plasma CVD method, a hot wire CVD method, an ion plating method, a pressure gradient type. Examples thereof include an ion plating method using a plasma gun, a surface wave plasma CVD method, and an atmospheric pressure plasma CVD method. Among these, a vacuum film forming method, particularly ion plating using a plasma CVD method or a pressure gradient type plasma gun is more preferable.

  The barrier layer 3 can be formed not only by the film forming method described above but also by a sol-gel method, a spray pyrolysis method, or a chemical solution lamination method.

  Here, the sol-gel method is a method in which an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer and one or more kinds of metal alkoxides and / or hydrolysates thereof is applied and then dried by heating. As the water-soluble polymer, for example, polyvinyl alcohol can be used, and as the metal alkoxide, for example, tetraethoxysilane, triisopropoxyaluminum, titanium tetraisopropoxide, or a mixture thereof can be used.

The spray pyrolysis method is a method for obtaining a metal oxide film by spraying a solution containing the metal salt constituting the metal oxide film onto a high-temperature substrate, and evaporating the solvent to be supplied by heating the substrate. In this method, the metal oxide film is obtained by evaporation and thermal decomposition reaction of the metal source. Specifically, as disclosed in, for example, JP-A-2002-145615, a raw material solution is prepared by adding hydrogen peroxide or aluminum acetylacetonate to a solution containing a TiO ₂ precursor, and the substrate is kept at a high temperature. A method of thermally decomposing the TiO ₂ precursor into TiO ₂ by intermittently spraying the above raw material solution to obtain a TiO ₂ film on the substrate can be used.

Further, the chemical solution liquid phase method is based on bringing a metal oxide film forming solution in which a metal salt or a metal complex is dissolved as a metal source into contact with a substrate heated to a temperature equal to or higher than the metal oxide film forming temperature. This is a method for obtaining a metal oxide film on a material. The metal oxide forming solution may contain at least one of an oxidizing agent and a reducing agent, ceramic fine particles, an auxiliary ion source, a surfactant, and the like as additives. Specifically, when forming a cerium oxide film (CeO ₂ ), cerium nitrate (Ce (NO ₃ ) ₃ ) as a metal source, borane-dimethylamine complex (also known as dimethylamine borane, DMAB) as a reducing agent, and solvent In this method, water is prepared and supplied onto a substrate heated to a temperature of about 150 to 600 ° C. or higher by spraying, dipping, roll coating, or the like to form a film.

<Metal thin film layer>
The metal thin film layer 4 of the metal laminate according to the present invention is disposed on the base material side of the metal layer 5 in contact with the metal layer 5. In the present invention, since the metal thin film layer 4 is formed as a so-called underlayer of the metal layer 5, the metal layer 5 can be easily formed by a method such as electroplating and bonded. The metal layer 5 having high strength can be formed. From this, a metal laminate excellent in durability can be obtained easily.

  The metal thin film layer 4 in the present invention is made of, for example, gold, silver, iron, copper, nickel, chromium or alloys thereof, tin oxide, ITO, ATO, for example, vapor deposition, ion plating, sputtering, electroless plating It can be easily formed by other methods.

  The inter-grain distance of the metal laminate is preferably 100 nm or less, preferably 80 nm or less, and more preferably 5 to 50 nm, like the barrier layer. By setting the distance between the grains of the metal thin film layer and the metal layer in this way, the permeation of gas such as oxygen and water vapor and the diffusion of the metal element itself can be suppressed from the side of these layers, and the adhesion to the base material It is possible to provide a high-quality laminate without causing deterioration of the metal film.

  When the inter-grain distance of the metal thin film layer is set in the above range, when the metal layer is further formed thereon, the inter-grain distance is also in the same range.

  The thickness of the metal thin film layer 4 can be appropriately determined in consideration of the specific use, required performance, material, etc. of the metal laminate, but is preferably 10 nm to 5 μm, particularly preferably 10 nm to 1 μm.

  The metal thin film layer can be formed by stacking two or more layers. In this case, the material constituting each layer and the method of forming each layer may be the same or different from each other.

<Metal layer>
The metal layer 5 of the metal laminate according to the present invention is disposed on the metal thin film layer 4. In the metal laminated body by this invention, since the metal thin film layer 4 is arrange | positioned, the metal layer 5 with high joint strength can be formed. Therefore, according to this invention, the metal laminated body excellent in durability can be obtained.

  The metal layer 5 is made of, for example, copper, chromium, nickel, or an alloy thereof, for example, an electroplating method, an electroless plating method, a vacuum film forming method (for example, vapor deposition method, sputtering method, plasma CVD method, hot wire). CVD, surface wave plasma CVD, ion plating, ion plating using a pressure gradient plasma gun, etc.) and atmospheric pressure plasma, and other methods. An electroplating method is particularly preferable.

  The metal forming the metal layer 5 may be the same as or different from the metal thin film layer 4 described above, but is preferably used in a combination that further increases the bonding strength between the two layers. In addition, the metal layer 5 can be formed by stacking two or more layers. In this case, the material constituting each layer and the method for forming each layer may be the same or different from each other.

  The metal layer 5 can function as a conductive layer. That is, when the metal laminate according to the present invention is used for, for example, a wiring board, the metal layer 5 can be processed so as to obtain a desired wiring pattern therefor and function as wiring of the wiring board. When the metal laminate according to the present invention is used, for example, as an electromagnetic shielding material, the metal layer 5 can be processed into a mesh shape to function as an electromagnetic shielding layer.

  As a method of processing the metal layer into, for example, a wiring pattern or mesh, a method comprising removing at least a part of the metal layer formed as a continuous layer is suitable. As such a method, a photoresist layer is applied to the surface of the metal layer 5, a resist pattern is formed by pattern exposure and development, etching is performed using the formed resist pattern, and metal in unnecessary portions is formed. Examples thereof include a method of removing a part of the surface side of the layer, the whole metal layer in the thickness direction, or the metal layer and the metal thin film layer.

  The inter-grain distance of the metal laminate is preferably 100 nm or less, preferably 80 nm or less, and more preferably 5 to 50 nm, like the barrier layer. By setting the distance between the grains of the metal thin film layer and the metal layer in this way, the permeation of gas such as oxygen and water vapor and the diffusion of the metal element itself can be suppressed from the side of these layers, and the adhesion to the base material It is possible to provide a high-quality laminate without causing deterioration of the metal film.

  The thickness of the metal layer 5 can be appropriately determined in consideration of the specific application, required performance, material, etc. of the metal laminate. When the thickness of the metal layer 5 is shown about the metal laminated body especially suitable for a FPC board use, generally 0.1 micrometer-100 micrometers, especially 0.1 micrometer-30 micrometers are preferable.

  Two or more metal layers can be formed to overlap each other. In that case, the material constituting each layer and the method of forming each layer may be the same or different from each other.

  The metal laminate preferably has a sheet resistance of 10Ω / □ or less.

[Metal laminates (other examples)]
The metal laminate according to the present invention has the above-described base material 2, barrier layer 3, metal thin film layer 4, and metal layer 5 as essential constituent members, and at least one layer of each other, and another arbitrary layer material. Or as above-mentioned that a material includes what was arrange | positioned in the arbitrary places of a metal laminated body.

  Preferable specific examples of the metal laminate according to the present invention in which such other layers or materials are arranged include those described in FIGS. 2 (A) to 2 (E), for example.

  In the metal laminate 12 according to the present invention shown in FIG. 2 (A), the barrier layer 3 of the substrate 2 of the first metal laminate 1 according to the present invention shown in FIG. 1 (A) is arranged. A barrier layer 31 is further arranged on the surface opposite to the surface. As the barrier layer 31, those described above as the barrier layer 3 can be preferably used, but may be different from the barrier layer 3.

  The metal laminate 13 according to the present invention shown in FIG. 2 (B) has a stress between the barrier layer 3 and the metal thin film layer 4 of the first metal laminate 1 according to the present invention shown in FIG. A relaxation layer 6 is further arranged. Examples of the resin forming the stress relaxation layer 6 include polyimide, polyamide, polyamideimide, epoxy, phenol, silicone, other elastomers, and plastomers. The thickness of the stress relaxation layer 6 is preferably 10 to 200 μm, more preferably 35 to 150 μm.

  The metal laminate 14 according to the present invention shown in FIG. 2 (C) has a stress relaxation between the substrate 2 and the barrier layer 3 of the first metal laminate 1 according to the present invention shown in FIG. 1 (A). The layer 61 is further arranged. As the stress relaxation layer 61, the above-described stress relaxation layer 6 can be preferably used, but it may be different from the stress relaxation layer 6.

  A metal laminate 15 according to the present invention shown in FIG. 2 (D) is similar to the first metal laminate 1 according to the present invention shown in FIG. 1 (A), with a barrier layer 31, a metal thin film layer 41, and a metal. The layers 51 are further arranged in this order. As the metal thin film layer 41, those described above as the metal thin film layer 4 can be preferably used, but they may be different. As the metal layer 51, the above-described metal layer 5 can be preferably used, but it may be different.

  The metal laminate 16 according to the present invention shown in FIG. 2 (E) is such that the metal layer 5 of the first metal laminate 1 according to the present invention shown in FIG. 1 (A) forms a wiring pattern. is there. The wiring pattern can be similarly formed on the metal layer 5 shown in FIGS. 1B and 2A to 2D.

  The metal laminate according to the present invention has, for example, a heat resistance of 200 ° C./10 minutes in the initial stage and has sufficient durability that can be continuously used even after being exposed to wet heat conditions of a temperature of 80 ° C./humidity of 90% / 1000 hours. It has the nature.

[Usage form of metal laminate]
The metal laminate according to the present invention can produce products suitable for various applications.
For example, by selecting the material that constitutes the metal layer and the pattern at the time of etching, in addition to printed circuit board materials, electronic circuit substrate materials such as semiconductor packages, IC tags, photomasks, connectors, sockets, etc., electromagnetic waves The present invention can be widely used for manufacturing a suspension for supporting a chip-shaped magnetic head such as a metal mesh for shielding and a hard disk.

  The metal laminate according to the present invention is one in which each layer is not peeled off or warped even when exposed to a high temperature and high humidity atmosphere for a long period of time, and the bonding strength and the like are prevented from being deteriorated. Stress applied from the outside in each stage of the metal laminate manufacturing process, processing stage, and utilization stage after processing, or stress generated inside the metal laminate that causes warpage or delamination in the metal laminate It has been relaxed. Therefore, it can be used under conditions that are harsher than in the past, and the thickness of the metal laminate can be reduced, so it can be applied to new applications.

Next, an Example is shown and this invention is demonstrated further in detail.
<Example 1>
(Preparation of substrate with barrier layer)
A roll-shaped biaxially stretched polyester film (manufactured by Toyobo Co., Ltd., A4300, thickness 50 μm, width 600 mm, length 5000 m) is prepared as a base material, and this is taken up by winding-type plasma CVD as shown in FIG. It was installed in the vacuum chamber 102 of the apparatus 101. Next, the inside of the vacuum chamber of the plasma CVD apparatus was depressurized to an ultimate vacuum of 4.0 × 10 ⁻³ Pa by a vacuum pump (oil rotary pump and oil diffusion pump).

  Further, tetraethoxysilane (TEOS) (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04) and oxygen gas (manufactured by Taiyo Nippon Sanso Corporation, purity 99.9999% or more) were prepared as raw material gases.

  Next, one electrode plate 113 is disposed in the vicinity of the coating drum 105 so as to face the coating drum, and a high frequency voltage of 40 kHz is applied between the coating drum and the electrode plate (input power 2.5 kW). ). A raw material supply nozzle 109 is provided near the electrode plate in the chamber, TEOS is introduced at a flow rate of 0.2 slm, oxygen gas is introduced at a flow rate of 4 slm, and the degree of opening and closing of a valve between the vacuum pump and the chamber is controlled. Thus, a thin film of silicon oxide was formed on the substrate 2 while maintaining the pressure in the vacuum chamber at the time of film formation at 6.7 Pa. The running speed of the substrate was set to 8 m / min so that the thickness of the silicon oxide thin film was 500 angstroms. Moreover, the film thickness of the formed thin film was calculated | required by performing a cross-sectional measurement using the scanning electron microscope (SEM; Hitachi Ltd. make, S-5000H).

(Evaluation of substrate with barrier layer)
The produced base material with a barrier layer was evaluated as follows.

(Evaluation 1: Grain distance)
In order to facilitate the measurement of the inter-grain distance of the barrier film 3 as a pretreatment, an etching process of the base material with a chemical solution was performed for the purpose of removing a low-density region. The film was dipped in 0.5% by mass hydrofluoric acid (23 ° C.) used as a chemical etching solution for 10 seconds, washed with water, and dried to dissolve and remove the low-density region of the film.

  The surface of the substrate subjected to the pretreatment was measured with an atomic force microscope (AFM, Nano Scope III manufactured by Digital Instruments), and the uneven surface was measured in an area of 500 nm × 500 nm in tapping mode. After image processing, a uniform cross section was displayed, and the average distance between grains, that is, the distance between peaks was measured to obtain the distance between grains.

(Evaluation 2: relative density)
In order to measure the film density, elemental analysis was first conducted by ESCA to determine the composition ratio of each element. Based on this composition ratio analysis result, the relative density was calculated from the measured density ratio with respect to the theoretical density by calculating with an X-ray reflectivity measuring device (manufactured by Rigaku Corporation, ATX-E) and attached software.

(Evaluation 3: Barrier property measurement)
Gas barrier properties include oxygen permeability measuring device (MOCON, OX-TRAN 2/20 type, measurement conditions: temperature 23 ° C., humidity 90% Rh, with independent measurement) and water vapor permeability measuring device (MOCON, PERMATRAN W3 / 31 type, measurement conditions: temperature 40 ° C., humidity 90% Rh). This obtained the transparent barrier film (sample 1) of this invention.

(Formation of metal thin film layer)
A Cu film was formed as a metal thin film layer with a film thickness of 300 nm on the barrier layer-side substrate produced by the above method by sputtering on the barrier layer side.
(Formation of metal layer)
A copper layer (metal layer) having a thickness of 10 μm was formed by an electrolytic plating method on the metal thin film layer and the metal thin film layer side of the base material with the barrier layer produced by the above method.
(Evaluation of base material with metal layer, metal thin film layer and barrier layer)
The produced base material with a barrier layer was evaluated as follows.

(Evaluation 4: Measurement of substrate warpage)
The adhesion evaluation of the metal layer, the metal thin film layer, and the substrate with a barrier layer was performed as follows. The processed substrate was cut into a size of 20 mm × 20 mm and placed in a heat-circulating heating furnace using hot air. The processing substrate installation method in the heating furnace is set on a flat glass stage through spacers for supporting the corners (four corners) of the processing substrate sample, and the processing substrate is metalized with polyimide tape at the corners. It was fixed to the spacer with the layer side facing down. From the glass stage, the heating furnace was heated to 80 ° C. with the initial position of the substrate as the origin, and the amount of warpage was measured using a semiconductor laser having a wavelength of 670 nm as the maximum displacement caused by the substrate warpage. With the metal layer side (lower side) of the substrate as the-side and the opposite side (upper side) as the + side, the maximum warp height at the measurement temperature was taken as the amount of warpage.

(Evaluation 5: Adhesion evaluation)
The adhesion evaluation of the metal layer, the metal thin film layer, and the substrate with a barrier layer was performed as follows. (B) Accelerated test in a dry oven at 80 ° C. for 1000 hours, (b) Accelerated test performed in an environment of 60 ° C. and humidity of 95%, tape peel test from the metal layer side, and evaluation of film peeling did.

(Evaluation 6: Migration resistance evaluation)
The adhesion evaluation of the metal layer, the metal thin film layer, and the substrate with a barrier layer was performed as follows. First, comb electrodes having a pitch of 40 μm were formed on the metal layer and the metal thin film layer by photolithography. A voltage (DC60V) is applied to this electrode, placed in a high-temperature and high-humidity tank with 80 ° C and humidity of 85%, and the insulation resistance value is measured and recorded every 5 minutes with the voltage loaded. The resistance value between lines is 100MΩ or less. The time to reach this was measured and used as a migration evaluation.
The above evaluation results are summarized in Table 1.

<Example 2>
A roll-shaped biaxially stretched polyethylene terephthalate film (A4300, thickness 50 μm, width 600 mm, length 5000 m) is prepared as a base material, and this is provided with a return electrode as shown in FIG. This was mounted in a vacuum chamber 102 of a take-off type hollow cathode (pressure gradient) type ion plating apparatus 101. Next, the inside of the vacuum chamber was depressurized to an ultimate vacuum of 1 × 10 ⁻⁴ Pa by a vacuum pump (oil rotary pump and oil diffusion pump).

  Further, silicon dioxide (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.97%, particle size 2 to 5 mm) was prepared as an evaporation source and placed on the anode 106.

Next, oxygen gas is introduced near the coating drum 104 of the chamber at a flow rate of 5 sccm, and the opening / closing degree of the valve between the vacuum pump and the chamber is controlled, so that the pressure in the chamber during film formation is 8 ×. The pressure was kept at 10 ⁻² Pa. Then, using a hollow cathode type plasma gun 107 into which argon gas has been introduced, the evaporation source on the anode (hearth) is focused and irradiated to evaporate, and the evaporated molecules are ionized by the high-density plasma, and the substrate is ionized. A thin film of silicon oxide (SiO _y (y = 1.5)) was formed on the material 2. The running speed of the substrate was set at 80 m / min so that the thickness of the silicon oxide thin film was 500 angstroms. Moreover, the film thickness of the formed thin film was calculated | required by performing a cross-sectional measurement using the scanning electron microscope (SEM; Hitachi Ltd. make, S-5000H).

(Evaluation of substrate with barrier layer)
The produced base material with a barrier layer was evaluated as follows.
(Evaluation 1: Grain distance)
Measurement was performed in the same manner as in Example 1 except that no pretreatment was performed.
(Evaluation 2: relative density) Measurement was performed in the same manner as in Example 1.
(Evaluation 3: Barrier property measurement) Measurement was carried out in the same manner as in Example 1.
(Formation of metal thin film layer and metal layer)
A metal thin film layer and a metal layer were formed in the same manner as in Example 1 on the base material with a barrier layer produced by the above method.
(Evaluation of base material with metal layer, metal thin film layer and barrier layer)
The produced metal layer, metal thin film layer, and substrate with a barrier layer were evaluated in the same manner as in Example 1 as follows.

The evaluation results are summarized in Table 1.
(Evaluation 4: Warpage measurement)
(Evaluation 5: Adhesion evaluation)
(Evaluation 6: Migration resistance evaluation)

<Example 3>
A roll-shaped biaxially stretched polyethylene terephthalate film (PET film A4300 manufactured by Toyobo Co., Ltd., thickness 50 μm, width 300 mm, length 1000 m) having a width of 30 cm as a base material was prepared, and the winding having the configuration as shown in FIG. It was installed in the vacuum chamber 102 of the take-off type dual cathode type sputtering apparatus 101. The sputtering apparatus 101 includes a vacuum chamber 102, a base material unwinding roll 103 a, a winding roll 103 b, a coating drum 104, and partition plates 109 and 109 that are disposed in the vacuum chamber 102. The film forming chamber 105, the target mounting bases 106 a and 106 b disposed in the film forming chamber 105, the power source 107 for applying a voltage to the target, the plasma emission monitor 108, and the valve 111. Are connected to the vacuum pump 110, a gas flow rate control device 112 for controlling the flow rate of nitrogen gas, and valves 113 and 114 for adjusting the supply amounts of oxygen gas and argon gas.

  Next, silicon (single crystal, electric resistivity 0.02 Ωcm) was mounted on the target mounting table 106 in the film forming chamber 105 as a target material. The distance (TS distance) between this target and the substrate film was set to 10 cm. Next, oxygen gas (manufactured by Taiyo Nippon Sanso Corporation (purity 99.9995% or more)), nitrogen gas (manufactured by Taiyo Nippon Sanso Corporation (purity 99.9999% or more)) as an additive gas during film formation ) And argon gas (manufactured by Taiyo Nippon Sanso Corporation (purity 99.9999% or more)).

Next, the inside of the vacuum chamber 102 and the film forming chamber 105 was depressurized by the vacuum exhaust pump 110 to the ultimate vacuum of 2.0 × 10 ⁻³ Pa. Next, oxygen gas was introduced into the film formation chamber 105 at a flow rate of 0.5 sccm, and argon gas was introduced at a flow rate of 150 sccm. Nitrogen gas was simultaneously supplied. The nitrogen gas flow rate to be supplied was supplied at an optimum flow rate while controlling the Si emission intensity during plasma discharge to be constant using a plasma emission monitor (PEM-05, manufactured by Von Ardenne). Further, by controlling the degree of opening and closing of the valve 111 between the vacuum exhaust pump 110 and the film forming chamber 105, the pressure of the film forming chamber 105 is maintained at 0.1 Pa, the substrate is run, and the dual magnetron sputtering method is used. A barrier layer made of a silicon oxynitride film was formed on the substrate with an input power of 3 kW. The substrate was run at 0.1 m / min so that the thickness of the formed thin film was 50 nm. The film thickness was determined by performing cross-sectional measurement using a scanning electron microscope (SEM; manufactured by Hitachi, Ltd., S-5000H).

(Evaluation of substrate with barrier layer)
The produced base material with a barrier layer was evaluated as follows.
(Evaluation 1: distance between grains) Measurement was performed in the same manner as in Example 1 except that no pretreatment was performed.
(Evaluation 2: relative density) Measurement was performed in the same manner as in Example 1.
(Evaluation 3: Barrier property measurement) Measurement was carried out in the same manner as in Example 1.
(Formation of metal thin film layer and metal layer)
A metal thin film layer and a metal layer were formed in the same manner as in Example 1 on the base material with a barrier layer produced by the above method.
(Evaluation of base material with metal layer, metal thin film layer and barrier layer)
The produced metal layer, metal thin film layer, and substrate with a barrier layer were evaluated in the same manner as in Example 1 as follows. The evaluation results are summarized in Table 1.
(Evaluation 4: Warpage measurement)
(Evaluation 5: Adhesion evaluation)
(Evaluation 6: Migration resistance evaluation)

<Example 4>
In Example 1,
The source gas was changed from tetraethoxysilane (TEOS) to hexamethyldisiloxane (HMDSO).

The flow rate of oxygen gas used for film formation was 0.6 slm.

The substrate film running speed was 10 m / min.

Further, in the pretreatment conditions for measuring the distance between grains of the substrate with a barrier layer, the chemical etching solution treatment conditions were dip-treated for 10 seconds in 25% hydrofluoric acid (23 ° C.).
Other than the above, production and evaluation were performed in the same manner as in Example 1.

<Example 5>
In Example 1,
The source gas was changed from tetraethoxysilane (TEOS) to hexamethyldisilazane.

Nitrogen gas was changed to 2 slm instead of oxygen gas used for film formation.

The substrate film running speed was 10 m / min.
Other than the above, production and evaluation were performed in the same manner as in Example 1.

<Examples 6 to 10>
In Examples 1-5, except that the base film was changed from a biaxially stretched polyester film to a polyimide film (manufactured by Toray DuPont Co., Ltd., Kapton, EN, thickness 25 μm), it was produced in exactly the same manner as in Examples 1-5. went.
Moreover, about evaluation, a part measurement condition was changed as follows, and evaluation was performed similarly to Example 1 except these.
(Evaluation 3: Barrier property measurement)
The oxygen barrier property evaluation was performed by modifying the measuring cell of MOCON's oxygen permeability measuring device (OX-TRAN 2/20 type) to a specification that can be heated at a high temperature, and measuring conditions: temperature 80 ° C., humidity 90% Rh, individual Measured with measurement.
The water vapor barrier property was measured at a measurement condition of a temperature of 80 ° C. and a humidity of 90% Rh by remodeling a measurement cell of a water vapor permeability measuring apparatus (PERMATRAN W3 / 31 type) manufactured by MOCON to a specification capable of high temperature setting.
(Evaluation 4: Measurement of substrate warpage)
The measurement was performed in the same manner as in Example 1 except that the amount of warpage was measured with the heating temperature in the heating furnace being 200 ° C.

<Comparative Example 1>
In Example 1, production and evaluation were performed in the same manner as in Example 1 except that the barrier layer 3 was not formed.

<Comparative example 2>
In Example 6, production and evaluation were performed in the same manner as in Example 6 except that the barrier layer 3 was not formed.

<Summary>
As can be seen from the examples and comparative examples, it can be seen that in the practice according to the present invention, there is no base material warpage, adhesion is good, and the base material is excellent in migration resistance.

FIG. 1A and FIG. 1B are cross-sectional views showing an outline of a preferred metal laminate according to the present invention. FIG. 2 (A) to FIG. 2 (E) are cross-sectional views showing an outline of another preferred metal laminate according to the present invention. Explanatory drawing of the effect | action of the stress which acts on the board | substrate with which the thin film was formed. 4A and 4B are explanatory diagrams showing the grain and the inter-grain distance for the substrate on which the thin film is formed. The figure which shows the outline | summary of a winding type plasma CVD apparatus. The figure which shows the outline | summary of a winding type | formula hollow cathode type ion plating apparatus. The figure which shows the outline | summary of a winding type dual cathode type | mold sputtering apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,11 Metal laminated body 2 Base material 3 Barrier layer 4 Metal thin film layer 5 Metal layer 12, 13, 14, 15, 16 Metal laminated body 31 Barrier layer 41 Metal thin film layer 51 Metal layer 6, 61 Stress relaxation layer

Claims (7)

From a base material selected from polyimide and polyethylene terephthalate, a barrier layer selected from silicon oxide, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride on at least one surface of the base material, and copper A metal laminate in which a metal thin film layer and a metal layer made of copper are arranged in this order, wherein the barrier layer has a grain distance of 80 nm or less and a relative density with respect to an ideal density. There is of 60% or more, and the metal laminate is characterized by having a耐Ma Lee gray Deployment of more than 800 hours, the metal laminate (where耐Ma Lee gray Deployment of more than 800 hours a, to form a comb-shaped electrodes of 40μm pitch by photolithography to the metal layer and the metal thin film layer of the metal laminate, applying a voltage (DC 60V) to the electrode, 8 ℃ When the left insulation resistance value of the voltage load conditions placed in a humidity of 85% high-temperature and high-humidity vessel were measured, the time which the resistance value between lines reaches below 100MΩ means that at least 800 hours). Wherein the barrier layer is a vapor deposition method, a sputtering method, a plasma CVD method, hot wire CVD method, and is formed by ion plating method using an ion plating method or a pressure gradient type plasma gun, to claim 1 The metal laminate according to the description. The metal laminate according to claim 1 or 2 , wherein the metal layer has a grain distance of 100 nm or less. The metal laminate according to any one of claims 1 to 3 , wherein the base material is obtained by performing a bonding strength improving process on the surface of the base material prior to the formation of the barrier layer. . The metal laminate according to any one of claims 1 to 4 , wherein a stress relaxation layer is disposed between the barrier layer and the metal thin film layer. The metal laminate according to any one of claims 1 to 5 , wherein a stress relaxation layer is disposed on an opposite surface of the base material on which the barrier layer and the metal thin film layer are formed. The metal laminate according to any one of claims 1 to 6 , wherein a stress relaxation treatment is applied to an opposite surface of the base material on which the barrier layer and the metal thin film layer are formed.

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