WO2019176937A1 - Corps colaminé et son procédé de production - Google Patents

Corps colaminé et son procédé de production Download PDF

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Publication number
WO2019176937A1
WO2019176937A1 PCT/JP2019/010002 JP2019010002W WO2019176937A1 WO 2019176937 A1 WO2019176937 A1 WO 2019176937A1 JP 2019010002 W JP2019010002 W JP 2019010002W WO 2019176937 A1 WO2019176937 A1 WO 2019176937A1
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WIPO (PCT)
Prior art keywords
layer
joined body
metal layer
ultrathin
rolled joined
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PCT/JP2019/010002
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English (en)
Japanese (ja)
Inventor
橋本　裕介
Original Assignee
東洋鋼鈑株式会社
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Priority claimed from JP2018120889A external-priority patent/JP7085419B2/ja
Application filed by 東洋鋼鈑株式会社 filed Critical 東洋鋼鈑株式会社
Priority to KR1020207023866A priority Critical patent/KR102573723B1/ko
Priority to CN201980008337.8A priority patent/CN111727087B/zh
Priority to US16/977,672 priority patent/US11999131B2/en
Publication of WO2019176937A1 publication Critical patent/WO2019176937A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/04—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a rolling mill
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material

Definitions

  • the present invention relates to a rolled joined body and a manufacturing method thereof.
  • Metal materials are used in various fields, and are used as internal protection members such as shield covers for integrated circuits in electronic devices such as mobile electronic devices. These metal materials are required to have high strength and moldability. Stainless steel is widely used as such a metal material.
  • a rolled joined body metal laminate material, clad material
  • the rolled joint is a high-functional metal material having composite characteristics that cannot be obtained by a single material. For example, a rolled joint in which stainless steel and copper are laminated for the purpose of improving thermal conductivity has been studied. .
  • Patent Document 1 a first layer formed of austenitic stainless steel, a second layer formed of Cu or Cu alloy and laminated on the first layer, and formed of austenitic stainless steel, the second layer A chassis made of a clad material obtained by rolling and joining a third layer laminated on the opposite side of the first layer, the thickness of the second layer being 15% or more of the thickness of the clad material, and its manufacture A method is disclosed.
  • Patent Document 2 after the mating plate pressed against by performing Cu plate and brushed treated by overlapping joining faces rolling reduction 2-10% cold rolling stainless steel, 10-4 A method for producing a Cu-stainless steel clad plate characterized by heating to 500 to 1050 ° C. in a vacuum of less than Torr is disclosed.
  • the thickness of the copper layer (second layer) laminated on the stainless steel layer is at most several tens ⁇ m to several hundreds ⁇ m. For example, a thin metal layer of about several ⁇ m to 20 ⁇ m is bonded. Was difficult.
  • Patent Document 1 When manufacturing a rolled joined body of copper and stainless steel as in Patent Document 1, it is possible to reduce the thickness by repeating rolling and heat treatment. However, when a reduction ratio is increased, metal is used particularly when thin metal layers are joined. There was a problem that wrinkles and cracks occurred in the layer, and the flatness of the metal layer was impaired. This problem is particularly apparent when the product shape of the rolled joined body is wide and long. Further, when heat treatment is performed, a brittle intermetallic compound may be formed between the layers depending on the constituent material, for example, a rolled bonded body of copper and aluminum, and there is a possibility that the starting point may be peeled off.
  • a technique for laminating an extremely thin layer made of another metal on the metal layer a technique such as plating or sputter deposition is also known.
  • plating as in the case of copper plating on aluminum, direct plating cannot be applied depending on the structure of the metal, and the base layer for forming the copper plating layer may interfere with the intended function.
  • single-side masking it is necessary to remove the masking in a subsequent process. When the masking is peeled off, if the thickness of the base material is thin, the base material may be deformed and may be broken. Further, in the case of sputtering deposition, there are problems in terms of productivity and cost.
  • an object of the present invention is to provide a rolled joined body in which an extremely thin metal layer is laminated on another metal without causing wrinkles or cracks, and a method for manufacturing the same. .
  • the gist of the present invention is as follows.
  • a rolled joined body in which at least three layers are laminated A rolled joined body comprising a peelable carrier layer, an ultrathin metal layer, and a metal foil, wherein the ultrathin metal layer has a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less.
  • the rolled joined body according to the above (1) which has one or more intermediate layers containing metal between the ultrathin metal layer and the metal foil.
  • a rolled joined body in which at least four layers are laminated Including a peelable first carrier layer, a first ultrathin metal layer, a second ultrathin metal layer and a peelable second carrier layer, the ultrathin metal layer has a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less.
  • the ultrathin metal layer is made of a metal selected from the group consisting of copper, iron, nickel, zinc, tin, chromium, gold, silver, platinum, cobalt and titanium and alloys based on any of these.
  • the rolled joined body according to any one of the above (1) to (4), which is a layer.
  • the metal foil is a metal foil selected from the group consisting of aluminum, iron, copper, nickel, magnesium, silver, gold, platinum, and an alloy based on any of these.
  • a method for producing a rolled joined body in which at least three layers are laminated A step of preparing a peelable carrier layer and a laminate composed of an ultrathin metal layer having a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less, and a metal foil; Activating the surface of the ultrathin metal layer by sputter etching; Activating the surface of the metal foil by sputter etching; Rolling and joining the activated surfaces at a rolling reduction of 0 to 30%; A method of manufacturing a rolled joined body in which heat treatment is not performed after rolling joining, or heat treatment is performed at 350 ° C. or lower.
  • a method for producing a rolled joined body in which at least four layers are laminated A first laminate comprising a first carrier layer that can be peeled and a first ultrathin metal layer having a thickness of 0.5 ⁇ m to 20 ⁇ m, and a second carrier layer that can be peeled and a thickness of 0.5 ⁇ m or more Preparing a second laminate composed of a second ultrathin metal layer of 20 ⁇ m or less; Activating the surface of the ultrathin metal layer by sputter etching; Rolling and joining the activated surfaces at a rolling reduction of 0 to 30%; A method of manufacturing a rolled joined body in which heat treatment is not performed after rolling joining, or heat treatment is performed at 350 ° C. or lower.
  • the metal foil is a metal foil selected from the group consisting of aluminum, iron, copper, nickel, magnesium, silver, gold, platinum, and an alloy based on any of these.
  • At least two or more layers are laminated, including an ultrathin metal layer and a metal foil, wherein the thickness of the ultrathin metal layer is 0.5 ⁇ m or more and 20 ⁇ m or less,
  • the manufacturing method of a rolling joined body including the process of peeling the carrier layer in the rolled joined body as described in said (1).
  • a rolled joined body in which an ultrathin metal layer and a metal foil are laminated The ultrathin metal layer is a copper layer having a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less, and the metal foil is aluminum, iron, nickel, copper, magnesium, silver, gold, platinum, or an alloy based on any of these.
  • the carrier layer functions as a support and / or protective layer for the ultrathin metal layer, the handleability of the ultrathin metal layer before bonding is excellent.
  • the carrier layer functions as a support layer and / or a protective layer of the rolled joined body even after the rolled joined body is obtained, the handleability of the rolled joined body is excellent.
  • FIG. 1A is a schematic configuration in which a peelable carrier layer 10 composed of a carrier layer body 11 and a release layer 12, an ultrathin metal layer 20, and a metal foil 30 are laminated in this order. Is done.
  • the carrier layer body 11 has a sheet shape, and functions as a support material or a protective layer for preventing generation of wrinkles and creases in the rolled bonded body 1A and scratches on the ultrathin metal layer 20.
  • Examples of the carrier layer body 11 include a foil or a plate-like body made of copper, aluminum, nickel, and alloys thereof (stainless steel, brass, etc.), a resin whose surface is coated with a metal, or the like. Preferably, it is a copper foil.
  • the thickness of the carrier layer body 11 is not particularly limited, and is appropriately set according to desired characteristics such as flexibility. Specifically, it is preferably about 10 ⁇ m to 100 ⁇ m. If the thickness is too thin, the handleability of the laminate of the carrier layer 10 and the ultrathin metal layer 20 may be impaired, such being undesirable. That is, the ultrathin metal layer 20 may be wrinkled or cracked due to deformation during handling. On the other hand, if the carrier layer body 11 is too thick, it is not preferable because it has excessive rigidity as a support material and may be difficult to peel off from the ultrathin metal layer 20. Furthermore, the cost for producing a laminate comprising a carrier layer and an ultrathin metal layer also increases.
  • the release layer 12 reduces the peel strength of the carrier layer body 11 and further heats the carrier layer 10 and the ultrathin metal layer 20 when joining the metal foil 30. It also has a function of suppressing interdiffusion that may occur between the thin metal layers 20.
  • the release layer 12 may be either an organic release layer or an inorganic release layer. Examples of components used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. Examples of nitrogen-containing organic compounds include triazole compounds and imidazole compounds.
  • triazole compounds examples include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1,2,4-triazole and 3-amino- And 1H-1,2,4-triazole.
  • sulfur-containing organic compound examples include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol and the like.
  • carboxylic acid examples include monocarboxylic acid and dicarboxylic acid.
  • membrane etc. are mentioned, for example.
  • the release layer 12 can be formed by bringing the component-containing solution of the release layer 12 into contact with the surface of the carrier layer body 11 and fixing the release layer component to the surface of the carrier layer body 11.
  • this contact may be performed by immersion in the release layer component-containing solution, spraying of the release layer component-containing solution, flowing down of the release layer component-containing solution, and the like. Then, it can be fixed by drying or the like.
  • a method of forming a film of the component of the release layer 12 by a vapor phase method such as vapor deposition or sputtering can be employed.
  • the thickness of the release layer 12 is typically 1 nm or more and 1 ⁇ m or less, and preferably 5 nm or more and 500 nm or less, but is not limited thereto.
  • the thickness of the peeling layer 12 is too thin, there is a problem that separation from the ultrathin metal layer 20 cannot be performed sufficiently and peeling becomes poor. Further, if the thickness is too large, peeling is possible, but the manufacturing cost becomes high, so that the thickness is appropriately set in consideration of these balances.
  • the metal constituting the ultrathin metal layer 20 can be appropriately selected according to the application and intended characteristics of the rolled joined body. Specific examples include copper, iron, nickel, zinc, tin, chromium, gold, silver, platinum, cobalt, titanium, and alloys based on any of these. In particular, a metal layer selected from the group consisting of copper, nickel, and alloys based on any of these is preferable.
  • a metal layer selected from the group consisting of copper, nickel, and alloys based on any of these is preferable.
  • the thickness of the ultrathin metal layer 20 is not less than 0.5 ⁇ m and not more than 20 ⁇ m. Preferably, they are 1 micrometer or more and 12 micrometers or less, More preferably, they are 1 micrometer or more and 7 micrometers or less.
  • the thickness of the ultrathin metal layer 20 was obtained by obtaining an optical micrograph of the cross section of the rolled joined body 1A and measuring the thickness of the ultrathin metal layer 20 at any 10 points in the optical micrograph. The average value. In the production of the rolled joined body, since the ultrathin metal layer 20 and the metal foil 30 are joined at a predetermined reduction rate, the thickness of the ultrathin metal layer 20 in the rolled joined body 1A is thinner than that before joining. Become.
  • the standard deviation ⁇ of the thickness of the ultrathin metal layer 20 is preferably less than 1 ⁇ m.
  • the standard deviation ⁇ of the thickness of the ultrathin metal layer 20 is obtained by obtaining an optical micrograph of the cross section of the rolled joined body, and the thickness t 1 of the ultrathin metal layer 20 is obtained for the cross section having a width of 300 ⁇ m in the optical micrograph. This is the standard deviation obtained by measuring 10 points at equal intervals and obtaining the 10 measured values.
  • Such an ultrathin metal layer 20 may be formed on the release layer 12 by a wet film formation method such as an electroless plating method or an electrolytic plating method, a dry film formation method such as sputtering or chemical vapor deposition, or a combination thereof. it can.
  • the peel strength of the ultrathin metal layer 20 and the metal foil 30 is compared with the peel strength of the carrier layer 10 and the ultrathin metal layer 20 (referred to herein as “carrier peel strength”), It is preferable that the peel strength of the metal foil 30 is larger. Thereby, when peeling the carrier layer 10 from the ultrathin metal layer 20, it can peel without producing a wrinkle, a tear, etc. to the ultrathin metal layer 20. FIG. However, if the peel strength value of the ultrathin metal layer 20 and the metal foil 30 is too close to the carrier peel strength value, the interface between the ultrathin metal layer 20 and the metal foil 30 is not actually affected.
  • the difference between the peel strength of the ultrathin metal layer 20 and the metal foil 30 and the carrier peel strength is preferably 0.5 N / 20 mm or more. More preferably, it is 1.0 N / 20 mm or more, and most preferably 3.0 N / 20 mm or more.
  • the peel strength of the ultrathin metal layer 20 and the metal foil 30 is preferably 1 N / 20 mm or more.
  • the carrier peel strength of the carrier layer 10 and the ultrathin metal layer 20 may be larger than 0, and preferably less than 1 N / 20 mm.
  • the material to be peeled off (carrier)
  • the carrier peel strength is more preferably in the range of 0.1 N / 20 mm or more and less than 1 N / 20 mm.
  • the peel strength or carrier peel strength value is obtained by preparing a test piece having a width of 20 mm from the rolled joined body 1A and partially forming the ultrathin metal layer 20 and the metal foil 30, or the carrier layer 10 and the ultrathin metal layer 20. After peeling, the force required to peel off when the thick film layer side or the hard layer side is fixed and the other layer is pulled 180 ° opposite to the fixed side (unit: N / 20 mm).
  • any metal plate material or foil-like material can be applied, and it is appropriately selected according to the use of the rolled joined body.
  • a metal foil selected from the group consisting of aluminum, iron, copper, nickel, magnesium, silver, gold, platinum, and alloys based on any of these is preferably used.
  • SUS304, SUS316 are used. Examples thereof include stainless steels such as AZ31, AZ61, AZ91, and LZ91, and foils such as aluminum and aluminum alloys such as A1050, A1100, and 1N30.
  • the thickness of the metal foil 30 is usually applicable if it is 0.01 mm or more, and in the range of 0.01 mm or more and 1.8 mm or less from the viewpoint of mechanical strength and workability of the obtained rolled joined body. Is preferred. In consideration of handling properties, it is preferably 0.015 mm or more. Further, from the viewpoint of weight reduction and thinning of the rolled joined body, the thickness of the metal foil 30 before joining is more preferably 1.2 mm or less, further preferably 0.8 mm or less, and particularly preferably 0.5 mm or less. . However, since the thickness of the rolled joined body can be reduced by re-rolling after joining, the thickness of the metal foil before joining is not limited to the above range.
  • the thickness of the metal foil 30 before joining is measurable with a micrometer etc., and means the average value of the thickness measured in 10 points
  • the deviation from the average value of 10 measured values is within 10% in all measured values.
  • a thin foil having a thickness of less than 1 mm is used as the metal foil to be joined, there is a concern that if the deviation is large, performance such as heat dissipation may vary.
  • an intermediate layer 40 containing a metal can be provided between the ultrathin metal layer 20 and the metal foil 30.
  • the intermediate layer 40 may be a single layer, or two or more layers may be laminated.
  • Examples of the intermediate layer 40 containing metal include a metal layer formed on the ultrathin metal layer 20 or the metal foil 30 by vapor deposition, electroplating, or electroless plating.
  • the metal constituting the intermediate layer 40 is selected from the group consisting of a single metal species selected from copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver and gold, or an alloy containing these metal species. It is preferable that it is a metal.
  • a single metal species selected from copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver and gold, or an alloy containing these metal species. It is preferable that it is a metal.
  • the surface of the ultrathin metal layer 20 or the metal foil 30 can be protected, and the adhesion between the ultrathin metal layer 20 and the metal foil 30 can be improved.
  • 40 can be given a function (for example, a function as an etching stopper layer at the time of etching).
  • the thickness of the intermediate layer 40 is not particularly limited as long as it can exhibit a function such as improvement in adhesion. Specifically, the thickness is preferably 0.5 ⁇ m or more and 20 ⁇
  • the surface of the metal foil 30 on the opposite side to the side in contact with the ultrathin metal layer 20 or the intermediate layer 40 in the rolled joined bodies 1A and 1B may have thermal conductivity and heat dissipation as required.
  • a protective layer can be provided for the purpose of preventing corrosion, preventing oxidation, preventing discoloration, and the like to such an extent that the functions such as these are not hindered.
  • examples of the protective layer for the metal foil made of copper include a chemical conversion treatment layer and a Ni plating layer.
  • the chemical conversion treatment layers such as a phosphoric acid type, a chromate type, and an anodizing process, can be mentioned.
  • a rolled joined body 1A shown in FIG. 1 prepares a laminate comprising a peelable carrier layer 10 and an ultrathin metal layer 20 and a metal foil 30, and these are cold rolled joined, hot rolled joined, and surface active. It can be obtained by bonding together by various methods such as chemical bonding and bringing the layers into close contact.
  • joining and / or heat treatment under high pressure when producing a rolled joined body significantly changes the metal texture in each layer of the rolled joined body before and after joining and / or before and after the heat treatment, thereby impairing the properties of the rolled joined body. Therefore, it is preferable to select bonding / heat treatment conditions that can avoid such a structural change.
  • Hot rolling joining is a method of rolling joining while applying heat above the recrystallization temperature of the joined body, and can be joined with a lower force than cold rolling joining, but it generates an intermetallic compound at the joining interface. Easy to do. Therefore, attention should be paid to the selection of the heating temperature and heating time conditions so as not to generate intermetallic compounds.
  • the heating temperature is preferably as low as possible.
  • a preferred embodiment as a method for producing the rolled joined body 1A is as follows. First, as shown in FIG. 3, a laminate 2 composed of a peelable carrier layer 10 and an ultrathin metal layer 20 having a thickness of 0.5 ⁇ m to 20 ⁇ m and a metal foil 30 are prepared, and an ultrathin metal layer is prepared. The surface 20a of 20 is activated by sputter etching, the surface 30a of the metal foil 30 is activated by sputter etching, and the activated surfaces are rolled and joined to each other (FIG. 3A), thereby producing a rolled joined body 1A. (FIG. 3B). The rolling reduction during the rolling joining is preferably 0 to 30%. More preferably, it is 0 to 15%.
  • the above-described surface activated bonding method can reduce the rolling reduction, so that it can be bonded while maintaining the function of the release layer 12, and thickness accuracy can be achieved without causing wrinkles or cracks. Can be formed. Furthermore, since the waviness at the interface between the ultrathin metal layer 20 and the metal foil 30 can be reduced, when the ultrathin metal layer or the metal foil is used as a circuit electrode by performing pattern etching on the rolled joined body 1A, Excellent thickness accuracy is advantageous for precise circuit formation. In particular, when an ultrathin metal layer having a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less is formed on a thin metal foil 30 having a thickness of 0.8 mm or less or 0.5 mm or less, warpage is likely to occur in the conventional manufacturing method.
  • the occurrence of warpage can be suppressed, and the shape of the rolled bonded body is wide. ⁇ Even if it is long, it is effective.
  • the laminated body 2 or the metal foil 30 to be joined is prepared as a long coil having a width of 100 mm to 600 mm, and the joining surface of the laminated body 2 or the metal foil 30 is used as one electrode grounded to insulate.
  • An alternating current of 1 MHz to 50 MHz is applied to the supported other electrode to generate a glow discharge, and the area of the electrode exposed in the plasma generated by the glow discharge is set to 1 of the area of the other electrode. / 3 or less.
  • the grounded electrode is in the form of a cooling roll to prevent the temperature of the conveying material from rising.
  • the adhering material on the surface is completely removed by sputtering the surface to which the laminate 2 or the metal foil 30 is bonded with an inert gas under vacuum, and part or all of the oxide layer on the surface is removed. Remove.
  • the ultrathin metal layer 20 or the metal foil 30 is aluminum, magnesium, or an alloy based on these, the oxide layer does not necessarily need to be completely removed, and even if it remains partially, it is sufficient. Bonding force can be obtained.
  • the sputter etching processing time can be greatly reduced as compared with the case where the oxide layer is completely removed, and the productivity of the rolled joined body can be improved.
  • the copper oxide layer it is preferable to completely remove the copper oxide layer.
  • the inert gas argon, neon, xenon, krypton, or a mixed gas containing at least one of these can be used.
  • the adsorbate on the surface of the ultrathin metal layer 20 or the metal foil 30 can be completely removed with an etching amount of about 1 nm, and the copper oxide layer is usually 5 nm to 12 nm ( It can be removed in the order of SiO 2 .
  • the sputter etching processing conditions can be appropriately set according to the type of the ultrathin metal layer 20 or the metal foil 30. For example, it can be performed under vacuum at a plasma output of 100 W to 10 kW and a line speed of 0.5 m / min to 30 m / min.
  • the degree of vacuum at this time is preferably higher in order to prevent re-adsorption on the surface, but it may be, for example, 1 ⁇ 10 ⁇ 5 Pa to 10 Pa.
  • the surfaces of the ultrathin metal layer 20 and the metal foil 30 that have undergone the sputter etching can be pressed by roll pressing.
  • the rolling line load for roll pressure welding is not particularly limited, and can be set, for example, within a range of 0.1 tf / cm to 10 tf / cm.
  • the rolling line load of the roll pressure welding is more preferably 0.1 tf / cm to 3 tf / cm, and further preferably 0.3 tf / cm to 1.8 tf / cm. It is.
  • the rolling line load when the roll diameter is increased or when the thickness of the laminate 2 or the metal foil 30 is large before joining, it may be necessary to increase the rolling line load in order to ensure the pressure during joining. Yes, it is not limited to this numerical range.
  • the rolling line load if the rolling line load is too high, not only the surface layer of the ultrathin metal layer 20 or the metal foil 30 but also the joining interface is likely to be deformed, and therefore the thickness accuracy of each layer in the rolled joined body may be reduced. is there. Further, if the rolling line load is high, the processing strain applied during joining may increase.
  • the rolling reduction during pressing is preferably 30% or less, more preferably 8% or less, and even more preferably 6% or less.
  • the lower limit value of the rolling reduction is 0%.
  • Bonding by roll pressure welding is performed in a non-oxidizing atmosphere, for example, in vacuum or in order to prevent a decrease in bonding strength between the two due to re-adsorption of oxygen to the surface of the ultrathin metal layer 20 or the metal foil 30. It is preferable to carry out in an active gas atmosphere.
  • the rolled joined body obtained by pressure welding can be further heat-treated as necessary.
  • the processing strain of the ultrathin metal layer 20 or the metal foil 30 is removed, and the adhesion between the layers can be improved.
  • this heat treatment is performed at a high temperature for a long time, bulges are generated in the carrier layer 10 starting from the release layer 12, and the carrier layer 10 may be peeled off starting from the bulges.
  • the carrier layer 10 and the ultrathin metal layer Adhesiveness to 20 may be increased by mutual diffusion or the like, and the carrier layer 10 may be difficult to peel off.
  • the above heat treatment is performed at a temperature of 350 ° C. or lower. Preferably it is 300 degrees C or less. Especially preferably, it is 250 degrees C or less. Alternatively, it is preferable not to perform heat treatment after roll joining. In addition, if it is after peeling and removing the carrier layer 10 from the rolled joined body after joining, you may heat-process in the temperature range which does not produce
  • the rolling joined body manufactured by said surface activation joining can be further rolled (reroll) as needed.
  • a rolled joined body having a thin structure with high added value can be manufactured and the material can be tempered by temper rolling.
  • the rolling reduction is measured in the state after rerolling. That is, the ratio T / T 0 between the total thickness T 0 of the laminate 2 and the metal foil 30 before joining and the thickness T of the rolled joined body after rerolling is the reduction ratio.
  • the rolled joined body 1A can be obtained through the above steps.
  • the peelable carrier layer 10 and the surface A laminate comprising an ultrathin metal layer 20 having an intermediate layer on the surface and a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less, or a metal foil having an intermediate layer on the surface, and the surface of these intermediate layers sputter etched Is bonded to the other metal foil or ultrathin metal layer whose surface is activated by sputter etching.
  • the rolled joined body 1B can be obtained according to the above-described method for producing the rolled joined body 1A.
  • a rolled joined body 1C shown in FIG. 4 is a rolled joined body having a two-layer structure in which an ultrathin metal layer 20 and a metal foil 30 having a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less are laminated.
  • This rolled joined body 1C can be obtained from a rolled joined body 1A provided with a carrier layer 10 as shown in FIG. That is, as shown in FIG. 4, a rolled joined body 1A is prepared (FIG. 4 (a)), and the carrier layer 10 in the rolled joined body 1A is peeled off (FIG. 4 (b)).
  • a rolled joined body 1C can be obtained (FIG. 4C).
  • the rolled bonded body 1 ⁇ / b> C having a two-layer structure has an ultrathin metal layer 20 having a thickness accuracy of 0.5 ⁇ m or more and 20 ⁇ m or less, and the ultrathin metal layer 20 is not cracked or wrinkled.
  • a rolled joined body 1C includes mobile electronic devices, various electronic devices such as PCs, electronic members for transportation equipment such as automobiles, covers for electronic members for home appliances, housings, cases, reinforcing members, heat radiation / electromagnetic wave shields, etc. It can be suitably used as a molded product such as a functional member.
  • an ultrathin metal layer having excellent thickness accuracy can be laminated, it is possible to form a fine circuit by selective etching, and it can be used as a substrate for a fine electronic circuit.
  • the rolled joined body 1D shown in FIG. 5 includes a peelable first carrier layer 10A, a first ultrathin metal layer 20A, a second ultrathin metal layer 20B, and a peelable second carrier layer 10B in this order. It is a rolled bonded body having a laminated four-layer structure.
  • the thickness of the first ultrathin metal layer 20A and the second ultrathin metal layer 20B is 0.5 ⁇ m or more and 20 ⁇ m or less, preferably 1 ⁇ m or more and 12 ⁇ m or less, more preferably 1 ⁇ m or more and 7 ⁇ m or less.
  • the peelable first carrier layer 10A and the peelable second carrier layer 10B are respectively a first carrier layer body 11A and a first peel layer 12A, and a second carrier layer body 11B and It is comprised from the 2nd peeling layer 12B.
  • the configurations of the carrier layer main body, the release layer, and the ultrathin metal layer are as described in the first embodiment.
  • FIG. 6 is a diagram for explaining a manufacturing process of the rolled joined body according to the fourth embodiment.
  • the rolled joined body 1D according to the fourth embodiment first includes a peelable first carrier layer 10A and a first ultrathin metal layer 20A having a thickness of 0.5 ⁇ m to 20 ⁇ m.
  • a method for manufacturing a rolled joined body according to the fifth embodiment of the present invention will be described with reference to FIG.
  • a first ultrathin metal layer 20A having a thickness of 0.5 ⁇ m to 20 ⁇ m and a second ultrathin metal layer 20B having a thickness of 0.5 ⁇ m to 20 ⁇ m are laminated.
  • It is a rolled joined body having a two-layer structure.
  • This rolled joined body 1E can be obtained from a rolled joined body 1D provided with a first carrier layer 10A and a second carrier layer 10B as shown in FIG. That is, as shown in FIG. 7, a rolled joined body 1D is prepared (FIG.
  • the rolled joined body 1E has two ultra-thin metal layers having a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less and excellent in thickness accuracy.
  • Such a rolled joined body 1E can be used as an ultrathin electromagnetic shielding material, a current collector foil for a negative electrode of a secondary battery, or the like by utilizing its thinness.
  • the ultra-thin metal layer is copper, it can be applied as a heat dissipation member or heat transport device for electronic devices or their members by utilizing its high and thin thermal conductivity, thereby dissipating heat. It is possible to achieve high strength and space saving by using a metal layer while taking advantage of the properties.
  • an ultra-thin metal layer having excellent thickness accuracy can be laminated, a fine circuit can be formed by selective etching, and it can be used as a substrate for a fine electronic circuit.
  • Example 1 First, a laminate in which a copper layer having a thickness of 5 ⁇ m is provided on a carrier layer body made of electrolytic copper and having a thickness of 18 ⁇ m via an organic release layer (carboxybenzotriazole (CBTA) or the like) having a thickness of about 50 nm as a release layer, A 50 ⁇ m aluminum foil (1N30) was prepared, and the surfaces of the copper layer and the aluminum foil were roll-bonded to produce a target rolled bonded body. When performing rolling joining, the surface of the copper layer and the aluminum foil was sputter-etched to activate the surface.
  • CBTA carboxybenzotriazole
  • Sputter etching for the copper layer was performed under conditions of 0.3 Pa, plasma output 400 W, 5 minutes, and sputter etching for the aluminum foil was performed under conditions of 0.3 Pa, plasma output 400 W, 5 minutes. Carried out.
  • the line load at the time of pressure welding is 1.0 t / cm (333 MPa), and the rolling reduction ratio due to surface activated bonding is 0%.
  • Example 2 A rolled joined body was prepared in the same manner as in Example 1 except that a laminate composed of a carrier layer and a copper layer using an inorganic release layer (nickel layer, chromate layer, etc.) having a thickness of about 30 nm was rolled and joined as the release layer. Obtained.
  • an inorganic release layer nickel layer, chromate layer, etc.
  • Example 1 A rolled bonded body was obtained in the same manner as in Example 1 except that the surfaces of the copper layer and the aluminum foil were rolled and bonded together by surface activation bonding, followed by heat treatment at 380 ° C. for 1 hour.
  • Example 2 A rolled bonded body was obtained in the same manner as in Example 2 except that the surfaces of the copper layer and the aluminum foil were rolled and bonded together by surface activation bonding, followed by heat treatment at 380 ° C. for 1 hour.
  • the peel strength at the interface (cladding interface) between the copper layer and the aluminum foil, and the carrier peel strength between the carrier layer and the copper layer was measured.
  • the peel strength in this example and comparative example refers to a value measured using 180 ° peel strength (also referred to as 180 ° peel strength).
  • a test piece having a width of 20 mm was prepared from the rolled joined bodies obtained in Examples 1 and 2 and Comparative Examples 1 and 2.
  • the carrier layer side or the ultrathin copper layer side is fixed, and the force required to peel the other layer when pulled to the opposite side 180 ° is measured. N / 20 mm was used as the unit.
  • a reinforcing tape was attached to the ultrathin copper layer side so as not to be cut during the peel strength measurement.
  • the peel strength at the clad interface was larger than the peel strength of the carrier layer, and the peel strength of the carrier layer was 0.1 N / 20 mm or more and 1 N / It was maintained at a low value of less than 20 mm.
  • the carrier layer can be peeled from the ultra-thin copper layer, and the carrier layer functions as a protective layer / support for the copper layer.
  • a very thin copper layer could be formed on the aluminum foil.
  • the adhesion strength increased so that the heat treatment did not allow separation at the interface between the carrier layer and the copper layer. This is presumably because the carrier layer and the release layer, and the ultrathin metal layer and the release layer were mutually diffused and alloyed by the heat treatment. Alternatively, there is a possibility that the adhesion strength is further increased by the mutual diffusion of the carrier layer and the ultrathin metal layer through the release layer. Therefore, a rolled joined body having a two-layer structure in which an extremely thin copper layer on an aluminum foil is formed cannot be obtained.
  • Example 3 First, a laminate in which a copper layer having a thickness of 5 ⁇ m is provided on a carrier layer body made of electrolytic copper and having a thickness of 18 ⁇ m via an organic release layer (carboxybenzotriazole (CBTA) or the like) having a thickness of about 50 nm as a release layer, A 50 ⁇ m stainless steel foil (SUS316) was prepared, and the surfaces of the copper layer and the stainless steel foil were roll-bonded to produce a target rolled bonded body. When performing rolling joining, the surface of the copper layer and the stainless steel foil was sputter-etched to activate the surface.
  • CBTA carboxybenzotriazole
  • Sputter etching for the copper layer was performed under conditions of 0.3 Pa, plasma output 700 W, 5 minutes, and sputter etching for the stainless steel foil was performed under conditions of 0.3 Pa, plasma output 700 W, 20 minutes. Carried out.
  • the line load at the time of pressure welding is 1.0 t / cm (333 MPa), and the rolling reduction ratio due to surface activated bonding is 0%.
  • Example 4 A rolled joined body was produced in the same manner as in Example 3 except that a laminate comprising a carrier layer and a copper layer using an inorganic release layer (nickel layer, chromate layer, etc.) having a thickness of about 30 nm was rolled and joined as the release layer. Obtained.
  • an inorganic release layer nickel layer, chromate layer, etc.
  • Example 3 A rolled bonded body was obtained in the same manner as in Example 3 except that the surfaces of the copper layer and the stainless steel foil were rolled and bonded together by surface activation bonding, followed by heat treatment at 380 ° C. for 1 hour.
  • Example 4 A rolled bonded body was obtained in the same manner as in Example 4 except that the surfaces of the copper layer and the stainless steel foil were rolled and bonded together by surface activation bonding, followed by heat treatment at 380 ° C. for 1 hour.
  • the peel strength at the clad interface is larger than the peel strength of the carrier layer, and the peel strength of the carrier layer is less than 1 N / 20 mm. Specifically, it was maintained at a low value in the vicinity of 0.1 N / 20 mm to 0.25 N / 20 mm. As a result, only the carrier layer can be peeled from the ultra-thin copper layer, and the carrier layer functions as a protective layer / support for the copper layer. A very thin copper layer could be formed on the stainless steel foil.
  • Example 5 First, a laminate in which a carrier layer body made of electrolytic copper having a thickness of 18 ⁇ m is provided with a copper layer having a thickness of 5 ⁇ m via an inorganic release layer (such as a nickel layer and a chromate layer) having a thickness of about 30 nm as a release layer, and a thickness of 15 ⁇ m.
  • the stainless steel foil SUS304 was prepared, and the surfaces of the copper layer and the stainless steel foil were rolled and joined together to produce the intended rolled joined body. When performing rolling joining, the surface of the copper layer and the stainless steel foil was sputter-etched to activate the surface.
  • Sputter etching for the copper layer was performed under conditions of 0.3 Pa and plasma output of 700 W for 10 minutes, and sputter etching for the stainless steel foil was performed under conditions of 0.3 Pa and plasma output of 700 W for 20 minutes. Carried out.
  • the line load at the time of pressure welding is 0.5 t / cm (167 MPa), and the rolling reduction by surface activated bonding is 0% in all cases.
  • Example 5 For the rolled joined body obtained in Example 5, the peel strength at the interface between the copper layer and the stainless steel foil (cladding interface) and the carrier peel strength between the carrier layer and the copper layer (peel strength of the carrier layer) were measured. did. Moreover, the occurrence state of swelling in the release layer was evaluated. The evaluation results are shown in Table 3.
  • the peel strength at the cladding interface is larger than the peel strength of the carrier layer, and the peel strength of the carrier layer is as low as 0.1 N / 20 mm or less. It was maintained. As a result, only the carrier layer can be peeled from the ultra-thin copper layer, and the carrier layer functions as a protective layer / support for the copper layer. A very thin copper layer could be formed on the stainless steel foil.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un corps colaminé dans lequel une couche métallique ultramince est stratifiée sur un autre métal sans formation de rides ni rupture. Un corps colaminé, dans lequel au moins trois couches sont stratifiées, comprend une couche de support 10 qui peut être décollée, une couche métallique ultramince 20 et une feuille métallique 30, et ledit corps colaminé est caractérisé en ce que la couche métallique ultramince 20 a une épaisseur de 0,5 à 20 µm.
PCT/JP2019/010002 2018-03-14 2019-03-12 Corps colaminé et son procédé de production WO2019176937A1 (fr)

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KR1020207023866A KR102573723B1 (ko) 2018-03-14 2019-03-12 압연 접합체 및 그 제조 방법
CN201980008337.8A CN111727087B (zh) 2018-03-14 2019-03-12 轧制接合体及其制造方法
US16/977,672 US11999131B2 (en) 2018-03-14 2019-03-12 Roll-bonded laminate and method for producing the same

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JP2018047241 2018-03-14
JP2018-047241 2018-03-14
JP2018120889A JP7085419B2 (ja) 2018-03-14 2018-06-26 圧延接合体及びその製造方法
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CN113036086A (zh) * 2019-12-24 2021-06-25 广州方邦电子股份有限公司 一种电池极片的制备方法、电池极片及锂电池

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JPS5570490A (en) * 1978-11-20 1980-05-27 Mitsubishi Metal Corp Production of clad plate
JP2000117319A (ja) * 1998-10-20 2000-04-25 Daido Steel Co Ltd クラッド材の製造方法
JP2002127298A (ja) * 2000-10-18 2002-05-08 Toyo Kohan Co Ltd 多層金属積層板及びその製造方法
JP2002232096A (ja) * 2000-11-01 2002-08-16 Visteon Global Technologies Inc エッチング処理したトリ−メタル回路用のクラッド材料構造
WO2010055612A1 (fr) * 2008-11-12 2010-05-20 東洋鋼鈑株式会社 Procede de fabrication de substrat stratifie metallique pour la formation d'element a semi-conducteur et substrat stratifie metallique pour la formation d'element a semi-conducteur
JP2014223657A (ja) * 2013-05-17 2014-12-04 昭和電工株式会社 多層クラッド材の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5570490A (en) * 1978-11-20 1980-05-27 Mitsubishi Metal Corp Production of clad plate
JP2000117319A (ja) * 1998-10-20 2000-04-25 Daido Steel Co Ltd クラッド材の製造方法
JP2002127298A (ja) * 2000-10-18 2002-05-08 Toyo Kohan Co Ltd 多層金属積層板及びその製造方法
JP2002232096A (ja) * 2000-11-01 2002-08-16 Visteon Global Technologies Inc エッチング処理したトリ−メタル回路用のクラッド材料構造
WO2010055612A1 (fr) * 2008-11-12 2010-05-20 東洋鋼鈑株式会社 Procede de fabrication de substrat stratifie metallique pour la formation d'element a semi-conducteur et substrat stratifie metallique pour la formation d'element a semi-conducteur
JP2014223657A (ja) * 2013-05-17 2014-12-04 昭和電工株式会社 多層クラッド材の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113036086A (zh) * 2019-12-24 2021-06-25 广州方邦电子股份有限公司 一种电池极片的制备方法、电池极片及锂电池

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