TW202204644A - Titanium material for metal foil production, method for producing titanium material for metal foil production, and metal foil production roller The plurality of the voltage ratio of two adjacent positions among the positions is 0.95 or more and 1.05 or less - Google Patents

Abstract

In the titanium material of the present invention, when a pair of energized electrode probes are brought into contact to supply a constant current, and a pair of potential detection probes are brought into contact with the surface at a fixed probe interval to measure voltages at a plurality of positions on the surface, the plurality of the voltage ratio of two adjacent positions among the positions is 0.95 or more and 1.05 or less.

Description

Titanium material for metal foil production, method for producing titanium material for metal foil production, and metal foil production roller

The present invention relates to a titanium material for metal foil production, a method for producing the titanium material for metal foil production, and a metal foil production roll.

In many cases, copper foil is used as a raw material for wiring of wiring boards such as multilayer wiring boards and flexible wiring boards, and conductive parts of electronic parts such as current collectors of lithium ion batteries.

The copper foil used for the said use can be manufactured by the following method, for example. In a copper sulfate solution obtained by dissolving copper raw materials in a sulfuric acid solution, insoluble metals such as lead or titanium are placed as anodes and cathodes. Rollers with a width of 1 m or more and a diameter of several m are rotated and the copper is continuously deposited on the drum. . And the deposited copper was continuously peeled off, and it was wound up into a roll shape. Copper foil can be manufactured by the above.

As the material of the roller, titanium is generally used from the viewpoints of excellent corrosion resistance and excellent releasability of copper foil. However, even when a titanium material with excellent corrosion resistance is used, if the copper foil is produced for a long time, the surface of the titanium material constituting the roller will gradually be affected by corrosion in the copper sulfate solution. Then, the state of the roller surface affected by corrosion is transferred to the copper foil when the copper foil is produced.

Corrosion of metal materials is known to be caused by various internal factors such as the crystal structure, crystal orientation, defects, segregation, processing strain and residual strain of the metal material caused by the metal structure, resulting in the state of corrosion and corrosion. to varying degrees. A roller using a metal material with an inhomogeneous metal structure between parts will become unable to maintain the homogeneous surface state of the roller when it is affected by corrosion along with the manufacture of copper foil, and an uneven surface will be generated on the surface of the roller. . The uneven surface produced on the surface of the drum can be recognized as a pattern. Among the patterns caused by the above-mentioned inhomogeneous metal structures, those caused by macroscopic structures with a large area and which can be identified with the naked eye are called "macroscopic patterns". Moreover, the macroscopic pattern produced on the surface of the drum is also transferred to the copper foil when the copper foil is produced.

Therefore, in order to manufacture copper foil with high precision and uniform thickness, it is important to make the metal structure of the titanium material constituting the drum homogeneous to achieve homogeneous corrosion of the drum, thereby reducing the macroscopic appearance caused by the inhomogeneous macroscopic structure. .

In order to suppress the macroscopic appearance, Patent Document 1 proposes a titanium plate for use in a roll for producing electrolytic Cu foil, characterized in that it contains Cu: 0.15% or more and less than 0.5%, and oxygen: more than 0.05% and in the mass %. 0.20% or less and Fe: 0.04% or less, and the rest is composed of titanium and unavoidable impurities, and the titanium plate is composed of α-phase homogeneous and fine recrystallized structure with an average crystal grain size of less than 35µm.

Patent Document 2 proposes a titanium plate for use in a roll for producing electrolytic Cu foil, characterized in that it contains Cu: 0.3 to 1.1%, Fe: 0.04% or less, oxygen: 0.1% or less, and hydrogen: 0.006% in mass % Hereinafter, the average crystal grain size is 8.2 or more, and the Vickers hardness is 115 or more and 145 or less; in the part of the titanium plate parallel to the plate surface, the aggregate structure is such that the total area of the crystal grains existing in the following elliptical range When A is A and the total area of crystal grains outside it is B, the area ratio A/B is 3.0 or more, and the ellipse range is from the rolling plane and from the normal direction (ND axis) of the α phase ( 0001) plane pole diagram, the inclination angle of the normal line of the (0001) plane is ±45° in the rolling width direction (TD) as the long axis, and ±25° in the final rolling direction (RD) is taken as the long axis. The range of the short axis. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2009-41064 Patent Document 2: Japanese Patent Laid-Open No. 2012-112017

The problem to be solved by the invention However, the titanium plate used for the roll for producing the electrolytic Cu foil described in Patent Document 1 or Patent Document 2 contains elements such as Fe, and these elements are easily distributed to the liquid phase side during the solidification process during the production of the titanium plate. Therefore, segregation of the chemical composition of the titanium plate described above is likely to occur, that is, unevenness is likely to occur. If the chemical composition is uneven, the titanium plate will corrode unevenly during the metal foil manufacturing process, resulting in a macroscopic pattern on the titanium plate, and the macroscopic pattern may be transferred to the manufactured metal foil.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a titanium material for metal foil production, a method for producing a titanium material for metal foil production, and a metal foil production roll, the titanium material for metal foil production being used for metal foil production The generation of macroscopic patterns can be suppressed in the case of a roll for foil manufacturing.

means of solving problems The inventors of the present invention have focused on the fact that the macroscopic appearance of the metal foil manufacturing roller in the state of being polished and the macroscopic appearance caused by the heterogeneous corrosion during use are caused by the chemical properties of the metal material. The composition, or crystal structure, crystal orientation, defects, segregation, processing strain and residual strain are affected by various endoplasmic factors caused by the metal structure. Then, it was found that the macroscopic pattern can be suppressed when the electrical resistance of each part of the surface of the titanium material for metal foil production satisfies a predetermined condition, and the present invention was finally completed.

The present invention completed based on the above knowledge has the following gist. (1) The first aspect of the present invention is a titanium material for metal foil manufacturing, which has the following chemical composition: Contains in mass %: Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, Al: 0% or more and 7.0% or less, N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 1.000% or less, Fe: 0% or more and 0.500% or less, Cr: 0% or more and 0.500% or less, Ni: 0% or more and 0.090% or less, Cu: 0% or more and 1.5% or less and Mo: 0% or more and 0.750% or less, and The remainder contains Ti and impurities; and The total content of Fe, Cr and Ni is more than 0% and less than 0.500%; When a pair of energized electrode probes are brought into contact with a titanium material to supply a constant current, and a pair of potential detection probes are brought into contact with the surface at fixed probe intervals to measure the voltages at a plurality of positions on the surface, the voltages at the plurality of positions are The voltage ratio of two adjacent positions is 0.95 or more and 1.05 or less. (2) The titanium material for metal foil production described in the above (1) may contain Fe, Cr, Ni and Mo, The Ni content is 0 mass % or more and 0.090 mass % or less, and The Mo content is 0.5 times or more and 1.2 times or less with respect to the total content of Fe, Cr, and Ni on a mass basis. (3) The titanium material for metal foil production described in the above (1) or (2) may also contain, in mass %: N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 0.400% or less, Fe: 0.02% or more and 0.500% or less, Ni: 0% or more and 0.090% or less and Cu: 0% or more and 1.5% or less. (4) The titanium material for metal foil production described in the above (1) may contain, in mass %, one or two or more elements consisting of the following groups in a total amount of 0.2% or more and 5.0% or less: Sn: 0.2% or more and 2.0% or less, Zr: 0.2% or more and 5.0% or less and Al: 0.2% or more and 3.0% or less; and may also contain: N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 1.000% or less and Fe: 0% or more and 0.500% or less. (5) The titanium material for metal foil production described in the above (1) may contain more than 1.8 mass % and 7.0 mass % or less of Al; and In terms of mass %, when the Al content is [Al%], the Zr content is [Zr%], the Sn content is [Sn%], and the O content is [O%], the Al equivalent represented by the following formula (1) Aleq can be 7.0 mass % or less: Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] Formula (1). (6) The titanium material for metal foil manufacturing described in any one of the above (1) to (5) may be a titanium material for metal foil manufacturing rollers.

(7) A second aspect of the present invention is a method for producing a titanium material for metal foil production, comprising the following steps: a step of producing a titanium ingot using a continuous casting method in which molten titanium is poured into a In a coolable casting mold with upper and lower openings, and heating the liquid surface of the molten titanium in the casting mold, cooling the titanium through the casting mold to solidify it, and using a clamp to pull the solidified titanium downward; The above-mentioned titanium ingot is heated to a temperature of 750°C or higher and lower than the β transformation point, and rolled so that the reduction ratio is 90% or higher to produce a rolled sheet; and 600°C or higher and 750°C or lower Heat treatment for 20 minutes or more and 120 minutes or less at the same temperature, and cooling from the heat treatment temperature to 500°C at an average cooling rate of 20°C/min or more, and cooling from the heat treatment temperature to 10°C/min or less at an average cooling rate. Steps at temperatures below 300°C. (8) The method for producing a titanium material for metal foil production described in (7) above may further include a step of hot-working the titanium ingot to produce a flat blank; and in the step of producing a rolled sheet, the flat blank is used. Rolling was performed in place of the aforementioned titanium ingot. (9) In the method for producing a titanium material for metal foil production described in the above (7) or (8), the casting means may be an electron beam melting method; in the electron beam melting method, an electron beam is applied to the inner space of the casting mold The irradiation amount is 150 W/cm ² or less, and the melting rate of the titanium is 2.5 ton/h or less, and the titanium is irradiated with the electron beam to melt the titanium. (10) In the method for producing a titanium material for metal foil production according to (9) above, the ratio of the horizontal cross-sectional area of the inner space of the mold to the inner circumference of the horizontal cross-section of the mold and X in unit cm is the same as the above In the electron beam melting method, the irradiation amount of the electron beam and the Y in unit W/cm ² can also satisfy the relationship of the following formula (2), Y=-3.8X+(135±25) ・・・ formula (2). (11) In the method for producing a titanium material for metal foil production according to (7) or (8) above, the casting means may be a plasma melting method; the amount of plasma irradiation into the casting mold in the plasma melting method It is 380 W/cm ² or less, and the melting rate of the titanium is 2.5 ton/h or less, and the titanium may be melted by irradiating the titanium with the plasma. (12) In the method for producing a titanium material for metal foil production described in (7) to (11) above, in the horizontal cross section of the inner space of the casting mold, the ratio of the area per unit cm ² of the horizontal cross section to the perimeter per cm It can be 7.5cm or more and 22.5cm or less.

(13) The third aspect of the present invention is a metal foil manufacturing roll, which has: The titanium material for metal foil manufacturing described in the above (6) is coated along the outer peripheral surface of the cylindrical inner drum; and The welded portion is disposed on the butted portion of the titanium material.

Invention effect As described above, according to the above aspect of the present invention, when the titanium material for metal foil production is used in a roll for metal foil production, the occurrence of macroscopic patterns can be suppressed.

Form for carrying out the invention Hereinafter, preferred embodiments of the present invention will be described in detail. ＜Background＞ First, before describing the titanium material for metal foil production of the present embodiment, the background of the present inventors focusing on the voltage on the surface of the titanium material for metal foil production will be described. In order to manufacture a metal foil with high precision and a uniform thickness, such as copper foil, by using a metal foil manufacturing roller using titanium as a material, it is important to make the chemical composition and metal structure of the titanium material constituting the metal foil manufacturing roller homogeneous to prevent the The macroscopic appearance of the titanium surface and the homogeneous corrosion of the roller can reduce the macroscopic appearance caused by the inhomogeneous macroscopic structure. The present inventors found that by making the conductivity of the titanium material surface uniform, the macroscopic pattern can be significantly suppressed, and the occurrence of the macroscopic pattern caused by uneven corrosion of the titanium material surface during the copper foil manufacturing process can be significantly suppressed.

Factors that will change the conductivity of the surface of titanium materials for metal foil manufacturing include inhomogeneity of chemical composition, and inhomogeneity of metal structure such as strain, crystal structure, and crystal orientation distribution. Therefore, the resistivity of the surface of titanium material for metal foil manufacturing can be comprehensively displayed due to various endoplasmic factors caused by chemical composition, crystal structure, crystal orientation, defects, segregation, processing strain and residual strain.

For example, regarding the chemical composition, it can be estimated that the resistivity (µΩ·cm) of the surface of the titanium material for metal foil production is positively related to the total concentration of O, N, and C, the total concentration of Fe, Cr, Ni, and Mo, and the hydrogen concentration, respectively. a correlation. The resistivity of the portion with these elements segregated is higher than that of the portion without segregation. The inventors of the present invention have found that among the intrinsic factors, segregation in particular affects the resistivity of the surface of the titanium material for metal foil production.

In addition, for example, regarding the metal structure, it is presumed that the resistivity (µΩ·cm) of the surface of the titanium material for metal foil production has a positive first-order correlation with the amount of strain. In addition, it is presumed that the resistivity (µΩ·cm) of the surface of the titanium material for metal foil production has a negative first-order correlation with the current direction and the angle formed by the c-axis of the α-phase crystal structure. In addition, it is presumed that the resistivity (µΩ·cm) of the surface of the titanium material for metal foil production is also proportional to the reciprocal of the crystal grain size in the metal structure (inversely proportional to the crystal grain size). In addition, the resistivity (µΩ·cm) of the surface of the titanium material for metal foil production is of course also related to the surface temperature of the titanium material for metal foil production.

From the above, it can be presumed that the resistivity (µΩ·cm) of the surface of the titanium material for metal foil production is related to the main internal factor that produces the macroscopic pattern. Therefore, by grasping the resistance of each part of the surface of the titanium material for metal foil production, it is possible to grasp the variation of the endoplasmic factor of each part of the surface of the titanium material for metal foil production. The above is the background that the present inventors paid attention to the voltage on the surface of the titanium material for metal foil production.

<Titanium material for metal foil manufacturing> Based on the above knowledge and knowledge, the inventors of the present invention have finally invented a titanium material for metal foil production, which can suppress the occurrence of macroscopic patterns when used in a metal foil production roll. In the titanium material for metal foil production of the present embodiment, a pair of energized electrode probes are brought into contact to supply a constant current, and a pair of potential detection probes are brought into contact with the surface at a fixed probe interval to measure voltages at a plurality of positions on the surface , the voltage ratio of two adjacent positions among the plurality of positions is 0.95 or more and 1.05 or less. In particular, this kind of titanium material suppresses segregation, and suppresses the generation of macroscopic appearance. Hereinafter, the titanium material for metal foil manufacture of this embodiment is demonstrated in detail.

(voltage ratio) In the titanium material for metal foil production of the present embodiment, the voltage ratio of two adjacent positions among a plurality of positions on the surface is 0.95 or more and 1.05 or less. When the voltage ratio of two adjacent positions among the plurality of positions is 0.95 or more and 1.05 or less, the two adjacent positions are homogeneous with each other. As a result, macroscopic patterns do not exist in adjacent positions, and generation of macroscopic patterns can also be suppressed when metal foil is produced. On the other hand, when the voltage ratio of two adjacent positions among the plurality of positions is less than 0.95 or more than 1.05, the two positions are not homogeneous with each other, and a macroscopic pattern exists on the surface of the titanium material. In addition, when the voltage ratio of two adjacent positions among the plurality of positions is less than 0.95 or greater than 1.05, the conductivity is uneven due to inhomogeneity. There will be differences in the corrosion rate between the parts, resulting in a macroscopic appearance.

In the titanium material for metal foil production of the present embodiment, the voltage ratio of two adjacent positions among the plurality of positions is ideally 95% or more of 0.95 or more and 1.05 or less, and more preferably 98% or more of the voltage ratio is 0.95 or more. and below 1.05. Thereby, the titanium material for metal foil production is homogeneous in a wide range, and the macroscopic pattern can be further suppressed.

In the titanium material for metal foil production of the present embodiment, it is more desirable that the voltages at two adjacent positions among the plurality of positions are 0.95 or more and 1.05 or less. When the voltage ratio of the adjacent two positions is 0.95 or more and 1.05 or less, the titanium material for metal foil manufacturing has no macroscopic pattern in all parts, and this titanium material for metal foil manufacturing is used. In the case of metal foil production, it is still possible to suppress the occurrence of macroscopic patterns in a wide area of the surface of the titanium material for metal foil production.

Here, with reference to FIGS. 1 and 2 , a method for measuring the voltage at each location in the titanium material for metal foil production according to the present embodiment will be described. FIG. 1 is a schematic diagram for explaining an inspection method of a titanium material for metal foil manufacturing or a metal foil manufacturing roller according to an embodiment of the present invention. 2 is a schematic view of the surface of the titanium material for metal foil production, showing an example of the arrangement of the energized electrode probe and the potential detection probe in the inspection method of the titanium material for metal foil production or the metal foil production drum of the present embodiment.

First, as shown in FIG. 1 , a pair of energized electrode probes 20A and 20B are brought into contact with the surface 11 of the titanium material 10 for metal foil production, and a constant current I is supplied. Thereby, a constant current I flows between a-a' contacted by the energized electrode probes 20A, 20B of the surface 11, and a predetermined potential difference is generated.

Next, the paired potential detection probes 30A and 30B are brought into contact at a probe interval L with respect to a plurality of positions on the surface 11 to which the constant current I is supplied, thereby detecting a plurality of voltages V ₁ at the plurality of positions on the surface 11 ~V _n . The paired potential detection probes 30A, 30B can be repeatedly made to contact the surface 11 one by one to detect a plurality of voltages V ₁ -V _n , or a plurality of pairs can be simultaneously contacted with the surface 11 to detect a plurality of voltages V ₁ ~V _n .

Here, the probe interval L is not particularly limited, and can be determined, for example, depending on the size of the macroscopic pattern. In the experience of the present inventors, the macroscopic shape is about 2 to 3 mm. Furthermore, the present inventors found that when the probe interval L is 3% or more of the macroscopic pattern, the difference in voltage from other parts can be detected sufficiently and meaningfully. Therefore, the probe interval L is, for example, 67 mm or less, and preferably 33 mm or less.

In addition, the probe interval L can be determined, for example, depending on the average crystal grain size of the titanium material 10 for metal foil production. That is, the electrical resistance of the surface 11 of the titanium material 10 for metal foil manufacture is also influenced by the number of crystal grain boundaries of the titanium material 10 for metal foil manufacture in the measurement site|part. Therefore, the surface 11 preferably includes a sufficient number of crystal grain boundaries within the probe interval L from the viewpoint of averaging the effect of the crystal grain boundaries on the resistance.

For example, when the crystal grain size observed on the surface 11 falls within the range of 20 to 40 µm, about 50 to 100 crystal grain boundaries exist in the macroscopic pattern of 2 mm. Considering the effect of separation on resistance due to the macroscopic pattern and the effect of the number of crystal grain boundaries, it is preferable that at least about 125 crystal grain boundaries exist on the surface 11 within the probe interval L. From the above viewpoint, the probe interval L is, for example, 125 times or more the average crystal grain size, and preferably 140 times or more.

As described above, the probe interval L between bi-bi' (i is an integer selected from 1 to n) contacted by the potential detection probes 30A and 30B can be determined by the average crystal grain size and/or the titanium material 10 for metal foil manufacturing. Or the size of the giant view. When considering both the average grain size and the size of the macroscopic pattern, the probe spacing L is preferably 125 times or more and 67 mm or less of the average grain size, and preferably 140 times or more and 33 mm. the following.

The resistance of each part of the surface of the titanium material for metal foil production corresponds to the voltage of each part that is generated when a constant current I is supplied. Therefore, by measuring the voltages V1 to Vn of the parts b1-b1' to bn-bn' between a and a' contacted by the energized electrode probes 20A and 20B of the surface 11 and comparing them, it is possible to Grasp the variation of endoplasmic factors in various parts of the surface of titanium materials for metal foil manufacturing. Furthermore, by comparing the voltages V ₁ to V _n of the parts b1 - b1 ' to bn-bn', the uniformity of corrosion and the quality of the metal foil manufacturing roll can be evaluated.

For example, in FIG. 1, when there is an inhomogeneous portion 12 such as a macroscopic pattern in the portion bn-bn', the voltage _Vn of the portion bn-bn' is detected as a value different from that of the other portions, and it can be grasped from this The site bn-bn' has the case where the uneven site 12 exists.

In addition, the arrangement of the positions bi-bi' (i is an integer selected from 1 to n) for measuring the voltage V _i is between a-a' as shown in FIG. The part bi-bi' and the part bm-bm' (m is an integer selected from 1-n) of another measurement object are arrange|positioned along the board width direction of the titanium material for metal foil manufacture.

After detecting the voltage at the site bi-bi', the pair of energized electrode probes 20A and 20B are moved from the straight line L1 in the direction perpendicular to the plate width direction, and are brought into contact with each other. The voltages V ₁ ' to V _n ' of the positions c1-c1' to cn-cn' arranged on the straight line L2 parallel to the straight line L1 are measured at the positions moved away from the straight line L1. The interval between the straight line L1 and the straight line L2 is not particularly limited, and for example, it is preferable to set it as the same depending on the difference in the macroscopic pattern and the size of the defect that are considered to be problems.

By appropriately repeating the above steps, a plurality of voltages V ₁ to V _n are detected for a plurality of positions of the surface 11 to which the constant current I is supplied.

Next, the voltage ratio of two adjacent positions among the plurality of positions is calculated. Specifically, for example, in FIG. 2 , the voltage V _i of the part bi-bi' (i is an integer selected from 1 to n) is the same as that of the adjacent parts b(i-1)-b(i-1)', respectively Compare the voltage V _i-1 of V i-1 with the voltage V _i +1 of the part b(i+1)-b(i+1)' to calculate V _i /V _i-1 and V _i+1 /V _i (or V _i-1 /V _i and V _i /V _i+1 ). So far, the method of calculating the voltage ratio of two adjacent positions on the surface of the titanium material for metal foil production has been described.

(chemical components) The titanium material for metal foil production of the present embodiment has the following chemical composition: In mass %, Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, Al: 0% or more and 5.0% or less 7.0% or less, N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 1.000% or less, Fe: 0% or more and 0.500% or less, Cr: 0% or more and 0.500% or less, Ni: 0% or more and 0.090% or less, Cu: 0% or more and 1.5% or less, and Mo: 0% or more and 0.750 % or less, and the remainder is Ti and impurities; and the total content of Fe, Cr, and Ni is 0% or more and 0.500% or less.

The titanium material for metal foil production of the present embodiment may contain Fe, Cr, or Ni. Fe, Cr, and Ni are β-phase stabilizing elements, so when Fe, Cr, and Ni are contained, the β-phase is easily formed. Since the β phase corrodes more preferentially than the α phase, when a titanium roller having a titanium material containing the β phase on the surface is used to manufacture a metal foil, the β phase corrodes preferentially, resulting in a macroscopic pattern on the surface of the roller. As a result, the macroscopic pattern may be transferred to the metal foil. Therefore, Fe, Cr, and Ni are preferably as few as possible. For example, the total content of Fe, Cr, and Ni is preferably 0 mass % or more and 0.500 mass % or less.

It is known that if the concentrations of Fe, Cr and Ni are high, they form compounds with Ti. Fe, Cr, and Ni form TiFe, TiCr ₂ , and Ti ₂ Ni together with Ti, for example. Among them, compared with Fe and Cr, Ni is more likely to form a compound of Ti. Therefore, in the temperature region where Ni and Ti can be diffused during hot rolling and annealing, a precursor stage, which is a stage before Ti ₂ Ni is formed, is formed at an early stage, and a micro region where Ni is concentrated is formed. When the Ni-concentrated microscopic region is formed, the hardness of the surface of the titanium material is uneven, and uneven polishing is likely to occur. As a result, it is easy to produce a macroscopic appearance. In order to suppress the Ni concentration as described above, the Ni content is, for example, 0 mass % or more and 0.090 mass % or less. The Ni content is preferably 0.012 mass % or more. The reason for this is that, as a special phenomenon, when a very small amount of Ni is contained, recrystallization tends to occur, and a metal structure with a uniform overall thickness, such as an equiaxed structure or recrystallization, is easily obtained during heating in the rolling step or in the heat treatment step. organization. In addition, the Ni content is preferably 0.070 mass % or less.

In addition, Cu also combines with Ti to form Ti ₂ Cu. The degree to which Cu is easily combined with Ti is the same as that of Fe and Cr.

The Fe content is, for example, 0.02 mass % or more and 0.500 mass % or less. Although Fe, Cr, and Ni are as few as possible as described above, the Fe content may be, for example, 0.040 mass % or more.

In addition, Fe, Cr, and Ni are elements whose distribution amount to the liquid phase is larger than that to the solid phase during the solidification of titanium. Therefore, these elements are elements that are easily segregated in the titanium material. If these elements segregate and cause the chemical composition to be inhomogeneous, the surface state of the titanium material will be inhomogeneous.

In order to reduce the inhomogeneity of the above-mentioned chemical components, the titanium material for metal foil production of the present embodiment preferably contains Mo. Mo, like Fe, Cr, and Ni, is a β-phase stabilizing element, but unlike these elements, it is an element that distributes more to the solid phase than to the liquid phase during the solidification of titanium. By containing Mo, the chemical components in the titanium material are homogenized, and the conductivity of the surface of the titanium material becomes uniform. As a result, the surface state of the titanium material is homogeneous, and the generation of macroscopic patterns can be further suppressed.

The Mo content is preferably 0.5 times or more and 1.2 times or less with respect to the total content in mass % of Fe, Cr, and Ni. When the Mo content is 0.5 times or more and 1.2 times or less the total content in mass % of Fe, Cr, and Ni, the chemical composition is homogeneous and the surface state is homogeneous, and the generation of macroscopic patterns can be suppressed. In addition, when the Mo content is 0.5 times or more and 1.2 times or less with respect to the total content in mass % of Fe, Cr, and Ni, the formation of the β phase can be suppressed so that the difference in corrosion rate between the α phase and the β phase does not appear. degree of influence. As a result, the etching behavior of titanium and the electrodeposition state of copper in the electrolytic solution for metal foil production can be more stabilized. The Mo content is preferably 0.7 times or more the total content in mass % of Fe, Cr, and Ni. Moreover, it is preferable that Mo content is 1.0 times or less with respect to the total content in mass % of Fe, Cr, and Ni.

For example, when the Fe content of the titanium material is 0.0300 mass %, the Cr content is 0.010 mass %, and the Ni content is 0.020 mass %, the total content of Fe, Cr and Ni is 0.060 mass %. Therefore, the Mo content at this time is preferably 0.030 mass % or more and 0.072 mass % or less. In addition, Mo does not necessarily need to be contained, so the lower limit of the Mo content is 0 mass %.

Moreover, the titanium material for metal foil manufacture of this embodiment may contain O, N, C and H.

O contributes to improving the strength of titanium and contributes to increasing the surface hardness. However, if the strength of the titanium material becomes too high, it will be difficult to grind the titanium material when it is made into a drum. Therefore, when O is contained in the titanium material for metal foil production, the O content is preferably 1.000 mass % or less. The O content is preferably 0.120 mass % or less, more preferably 0.065 mass % or less, and still more preferably 0.055 mass % or less.

The solid solution limit of N in α-Ti is smaller than that of O, so it tends to form nitrides together with Ti. When nitrides are formed, unevenness due to grinding or unevenness due to corrosion during use may occur on the surface of the drum. Therefore, it is advisable to suppress N content as much as possible. The N content can be, for example, 0.100 mass % or less, and preferably 0.020 mass % or less.

The solid solution limit of C in α-Ti is also smaller than that of O, so it tends to form carbides together with Ti. When carbides are formed, unevenness due to grinding or unevenness due to corrosion during use may occur on the surface of the drum as in the case of nitrides. Therefore, C content should be suppressed as much as possible. The C content can be, for example, 0.080 mass % or less, and preferably 0.020 mass % or less.

H will form hydrides with Ti. When a hydride is formed, the titanium plate may become brittle. In addition, a macroscopic pattern may occur due to hydrides. Therefore, H should be suppressed as much as possible. The H content is preferably 0.013 mass % or less.

O, N, and C are elements that, like Mo, are more distributed to the solid phase than to the liquid phase during the solidification of titanium. Therefore, the content of Mo can also be determined in consideration of the content of O, N, and C.

The titanium material for metal foil manufacture of this embodiment may contain at least one of Cu, Sn, Zr, or Al.

In the chemical composition of the titanium material for metal foil production in the present embodiment, the remainder may be Ti and impurities. Specific examples of the impurities include Cl, Na, Mg, Si, and Ca mixed in the refining step, and Nb, Ta, and V mixed from scraps, and so on. As long as the total amount of impurities is 0.5% by mass or less, there is no problem. Degree.

In the present embodiment, as described above, the V series is contained as an impurity. The V series is an element that delays recrystallization. When too much V is contained, it becomes difficult to obtain a metal structure with a uniform thickness throughout, such as an equiaxed structure or a recrystallized structure, during heating in the rolling step or in the heat treatment step. Therefore, V is not added in this embodiment.

More specifically, in consideration of impurities and the like that may be contained, the titanium material for metal foil production according to the present embodiment may contain, for example, by mass %: N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less and O: 0% or more and 0.400% or less.

In addition, the titanium material for metal foil production of the present embodiment contains, for example, Fe, Cr, Ni, and Mo, The Ni content is 0 mass % or more and 0.090 mass % or less, and The Mo content is 0.5 times or more and 1.2 times or less with respect to the total content of Fe, Cr, and Ni on a mass basis.

Moreover, the titanium material for metal foil manufacture of this embodiment may contain, for example, in mass %: N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 0.400% or less, Fe: 0.02% or more and 0.500% or less, Ni: 0% or more and 0.090% or less and Cu: 0% or more and 1.5% or less, and The remainder contains Ti and impurities.

In addition, the titanium material for metal foil production of the present embodiment may contain, for example, by mass %, one or two or more kinds of elements consisting of the following groups in a total amount of 0.2% or more and 5.0% or less: Sn: 0.2% or more and 2.0% or less, Zr: 0.2% or more and 5.0% or less and Al: 0.2% or more and 3.0% or less, and contains: N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 1.000% or less and Fe: 0% or more and 0.500% or less, and The remainder contains Ti and impurities.

In addition, the titanium material for metal foil production of the present embodiment contains, for example, more than 1.8 mass % and 7.0 mass % or less of Al, and the remainder contains Ti and impurities, and In terms of mass %, when the Al content is [Al%], the Zr content is [Zr%], the Sn content is [Sn%], and the O content is [O%], the Al equivalent represented by the following formula (1) Aleq is 7.0 mass % or less: Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] Formula (1).

In addition, although the lower limit of the content of each element described above is 0 mass %, it goes without saying that the titanium material for metal foil production of the present embodiment may not contain each of the above-mentioned elements. The chemical composition of the titanium material for metal foil production of the present embodiment has been described above.

The above-described titanium material for metal foil production of the present embodiment has a voltage ratio of 0.95 or more and 1.05 or less at two adjacent positions among the plurality of positions on the surface, so the influence of the chemical composition of the adjacent parts is homogeneous. As a result, the macroscopic pattern does not exist in the adjacent portion, and the generation of the macroscopic pattern can also be suppressed when the metal foil is produced.

In addition, the macroscopic pattern can be observed by polishing the surface of the titanium plate with #800 sandpaper, and then etching the surface with a solution of 10% by mass of nitric acid and 5% by mass of hydrofluoric acid. Figures 3 and 4 show photographs of the surface of the titanium material having a macroscopic appearance as an example. 3 and 4 are photographs of mutually different titanium plates. The "macroscopic pattern" refers to the following parts: the part where there are rib-like shapes of several mm in length along the rolling direction and the parts are different in color. For example, in FIG. 4, a macroscopic pattern of the shape shown in FIG. 4(B) is generated at the position indicated by the arrow in FIG. 4(A). If the titanium material produces such a macroscopic pattern, the macroscopic pattern will eventually be transferred to the manufactured metal foil.

As described above, the titanium material for metal foil manufacturing of the present embodiment can sufficiently suppress the generation of macroscopic patterns when used in a metal foil manufacturing roll, and is therefore suitable as a material for a metal foil manufacturing roll. Therefore, the present invention also relates to a metal foil manufacturing roller made of the titanium material for metal foil manufacturing of the present invention on one side. The above-mentioned metal foil manufacturing roll suppresses the generation of macroscopic patterns, and can manufacture high-quality copper foil.

5 and 6, the use of the metal foil manufacturing roller made of the titanium material for metal foil manufacturing of the present invention will be described. FIG. 5 is a schematic diagram of a copper foil manufacturing apparatus, which shows a usage state of a metal foil manufacturing roller, and FIG. 6 is a schematic diagram showing a metal foil manufacturing roller according to an embodiment of the present invention. For example, as shown in FIG. 5, the copper foil manufacturing apparatus 100 is provided with: an electrolytic tank 110 in which a copper sulfate solution is stored; an electrodeposition drum 120 is provided in the electrolytic tank 110 so that a part of it is immersed in the copper sulfate solution; and electrodes The plate 130 is immersed in the copper sulfate solution in the electrolytic tank 110 and is disposed opposite to the outer peripheral surface of the electrodeposition drum 120 at predetermined intervals. By applying a voltage between the electrodeposition roller 120 and the electrode plate 130 , the copper foil F is electrodeposited on the outer peripheral surface of the electrodeposition roller 120 to be generated. The copper foil F having a predetermined thickness is peeled off from the metal foil production drum 120 by the winding unit 140 , and is wound around the winding roll 160 while being guided by the guide roll 150 .

The electrodeposition drum 120 includes: a cylindrical inner drum 121; a titanium material 122 for metal foil production of the present embodiment, which is coated along the outer peripheral surface of the inner drum 121; The butt joint part of the titanium material 122 ; the side plate 124 , which is arranged on the side surface of the inner drum; and the rotating shaft 125 . The metal foil manufacturing roll of the present embodiment is constituted by the metal foil manufacturing titanium material 122 of the present embodiment and the welding part 123. The metal foil manufacturing titanium material 122 is a part of the electrodeposition roll 120 and extends along the cylindrical shape. The outer peripheral surface of the inner drum 121 is covered, and the welding part 123 is arranged at the butting part of the titanium material 122 for metal foil production. The side plates 124 are coated on both ends in the axial direction of the inner drum 121 and the titanium material 122 for metal foil production. In addition, the rotation shaft 125 is provided on the side plate 124 so as to be coaxial with the central axis A of the inner drum 121 .

The metal foil manufacturing roller of this embodiment can be manufactured by a known method. For example, the titanium sheet for metal foil manufacturing of this embodiment is stretched and arranged on the outer surface of the inner roller, and the titanium material for metal foil manufacturing processed into a cylindrical shape is welded. are manufactured with 2 opposite ends.

The ruler of the metal foil manufacturing roll of this embodiment is not specifically limited, For example, the diameter may be 1 m or more, 2 m or more, or 5 m or less.

The above-mentioned metal foil manufacturing roll suppresses the generation of macroscopic patterns, and can manufacture high-quality copper foil.

The titanium material for metal foil production of the present embodiment described above can be produced by any method, for example, the production method of the titanium material for metal foil production of the present embodiment described below.

<Manufacturing method of titanium material for metal foil manufacturing> Next, the manufacturing method of the titanium material for metal foil manufacture of this embodiment is demonstrated. The method for producing a titanium material for metal foil production according to the present embodiment includes the following steps: a step of producing a titanium ingot by a continuous casting method in which molten titanium is poured into a coolable mold with upper and lower openings. , and heat the molten titanium level in the casting mold, cool the titanium through the casting mold to solidify it, and use a clamp to pull the solidified titanium downward; heat it to above 750°C and lower than the β metamorphosis The step of manufacturing a rolled sheet by rolling with a reduction ratio of 90% or more; and, performing a heat treatment at a temperature of 600°C or more and 750°C or less for 20 minutes or more and 120 minutes or less. , and cooling from the heat treatment temperature to 500°C at an average cooling rate of 20°C/min or more, and cooling from the heat treatment temperature to a temperature below 300°C at an average cooling rate of 10°C/min or less.

(Manufacturing steps of titanium ingot) First, titanium having the above-mentioned chemical composition is melted by an electron beam melting method (EBR: Electron Beam Remelting) or a plasma melting method (PAM: Plasma Arc Melting), and a titanium ingot is produced. EBR is melted by irradiating an electron beam to the melting raw material including titanium from an electron beam gun, and PAM is melted by irradiating a plasma arc to the melting raw material including titanium from a plasma torch. Compared with the vacuum arc melting method (VAR: Vacuum Arc Remelting), which melts the electrode by the arc between the titanium consumable electrode and the molten titanium in the water-cooled copper mold, the EBR or PAM has the molten titanium in the mold. The part of the molten metal, that is, the molten pool is shallow and the solidification speed is fast, so it can reduce the solidification segregation of Fe, Cr, Ni, O, etc. By using a titanium ingot in which solidification segregation is suppressed, the produced titanium material for metal foil production can be homogenized. As a result, the surface state of the titanium material is homogeneous, and the occurrence of macroscopic patterns can be suppressed.

For the melting of titanium, in order to stabilize the depth and shape of the molten pool, the heat distribution into the titanium liquid surface in the casting mold should be uniform and stable. Melting method (EBR). Hereinafter, the electron beam melting method (EBR) and the plasma melting method (PAM) used in the manufacturing method of the titanium material for metal foil manufacturing according to the present embodiment will be described in detail, respectively.

[Electron Beam Melting (EBR)] The electron beam melting method is a method for producing an ingot by melting metals such as titanium by electron beams emitted from an electron gun in a vacuum, and pouring the melted metal into a mold such as a water-cooled copper mold to solidify it. Generally, an ingot is continuously cast while being drawn out using a bottomless casting mold. At this time, it is performed by irradiating an electron beam to the molten soup surface in a casting_mold|template, maintaining the liquid level in a casting_mold|template by heating.

In order to stabilize the depth and shape of the molten pool and maintain the liquid level, it is advisable to divide the output power of the electron beam irradiated into the mold by the area of the mold, that is, the irradiation amount per unit area is 150W/ ^cm2 . Titanium is melted below and under the conditions that the melting rate is 2.5 ton/h or less. The melting rate is preferably 0.5~2.0t/h.

[Plasma Melting (PAM)] The plasma melting method is a method in which metals such as titanium are melted by a plasma arc emitted from a plasma torch in an inert gas environment such as an argon atmosphere, and the melted metal is poured into a casting mold such as a water-cooled copper mold. It is solidified to make an ingot. Generally, an ingot is continuously cast while being drawn out using a bottomless casting mold. At this time, it is performed by irradiating a plasma arc to the molten soup surface in a casting_mold|template, and maintaining the liquid level in a casting_mold|template.

In order to stabilize the depth and shape of the molten pool and maintain the liquid level, it is advisable to divide the output power of the plasma irradiated into the mold by the area inside the mold, that is, the irradiation amount per unit area is below 380W/cm ² and Titanium is melted under the condition that the melting rate is below 2.5 ton/h. The melting rate is preferably 0.5~2.0t/h.

An example of the horizontal cross section of the mold 40 used for EBR or PAM is shown in FIGS. 7 and 8 . The circular mold 40A shown in FIG. 7 and the rectangular mold 40B shown in FIG. 8 are representative examples of horizontal cross-sections of molds used for EBR or PAM. In this horizontal cross section, the ratio of the area per unit cm ² of the inner space 41A of the casting mold 40A and the inner space 41B of the casting mold 40B to the perimeter per cm, that is, the area/perimeter length, is preferably 7.5 cm or more and 22.5 cm or less. Thereby, the cooling rate of the titanium molten metal by the casting mold becomes large, and solidification segregation can be suppressed more. The area/perimeter is preferably below 15.0cm, more preferably below 11.0cm, and the casting mold with such area/perimeter can obviously suppress solidification segregation. From the viewpoint of productivity, the area/perimeter length is substantially preferably 7.5 cm or more. Also, when the horizontal cross section is rectangular, for example, the four corners C are chamfered to form a polygon. Therefore, the area and the perimeter are calculated in consideration of the shape shown in FIG. 8 . Moreover, the thickness of a casting_mold|template is not specifically limited, For example, it may be less than 300 mm.

As described above, the EBR can easily move the electron beam irradiation position, so it is suitable for maintaining the shape of the molten noodle and the molten pool in the mold stable. Therefore, by using electron beam melting, and setting the irradiation amount per unit area (Y) in accordance with the area/perimeter (X) in the electron beam output power irradiated into the mold to the range of the formula (2), it is possible to The shape of the molten noodle and the molten pool in the mold can be maintained more stable. Y=-3.8X+(135±25) ・・・Formula (2)

(Flat embryo manufacturing steps) The method for producing a titanium material for metal foil production according to the present embodiment includes a flat blank manufacturing step of hot-working a titanium ingot to produce a flat blank. In the step of producing a rolled sheet, the above-mentioned flat blank is preferably used instead of the titanium ingot. rolling. For example, flat billets may also be produced from titanium ingots by forging under heat treatment or block rolling by known methods prior to rolling, if desired. This step can be performed when a cylindrical ingot is cast, or when it is necessary to adjust the thickness, width, etc. even if it is a rectangular ingot. By using this flat blank, it is possible to roll more uniformly in the rolling step, so that the metal structure can be made more uniform.

(rolling step) Next, the produced titanium ingot is directly rolled, or the flat billet that has been hot-worked into a rolling shape as required is rolled to produce a rolled sheet. In this step, the billet to be rolled is heated to a temperature higher than 750° C. and lower than the β transformation point, and rolling is performed so that the reduction ratio becomes 90% or higher. The heating temperature and the reduction ratio will be described below.

The heating temperature in this step is above 750°C and below the β transformation point. By heating to a temperature of 750° C. or higher and lower than the β transformation point, the metal structure can be sufficiently equiaxed, and the macroscopic pattern of the rolled sheet can be prevented. The rolling temperature is preferably above 200°C. In addition, the rolling temperature is preferably (β transformation point-50)°C or lower.

The reduction ratio in this step is more than 90%. By setting the reduction ratio to 90% or more, the coarse crystal grains can be sufficiently refined and the metallographic structure of the rolled sheet can be equiaxed, thereby preventing the occurrence of macroscopic patterns. The higher the reduction ratio in this step, the better the structure will be, so it only needs to be determined according to the required product size and the characteristics of the manufacturing mill.

In addition, by heating the titanium ingot to a temperature of 750°C or higher and lower than the β transformation point, and rolling it so that the reduction ratio is 90% or higher, recrystallization nuclei can be introduced into the entire rolled sheet homogeneously and sufficiently. .

Here, the "β transformation point" in this embodiment means the boundary temperature at which the α phase starts to be generated when the titanium alloy is cooled from the β phase single-phase region. The beta metamorphosis point can be obtained from the state diagram. State diagrams can be obtained by, for example, CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry). Specifically, the integrated thermodynamic calculation system Thermo-Calc of Thermo-Calc Sotware AB and a predetermined database (TI3) can be used to obtain the state diagram of the titanium alloy by the CALPHAD method to calculate the β transformation point.

(heat treatment step) Next, the rolled sheet is subjected to heat treatment at a temperature of 600° C. or more and 750° C. or less for 20 minutes or more and 120 minutes or less, and is cooled from the heat treatment temperature to 500° C. at an average cooling rate of 20° C./min or more, and is The average cooling rate of 10°C/min or less is cooling from the heat treatment temperature to a temperature of 300°C or less. By performing heat treatment at a temperature of 600° C. or higher and 750° C. or lower for 20 minutes or more and 120 minutes or less, a homogeneous recrystallized structure can be formed in the entire rolled sheet. In addition, if the average cooling rate from the heat treatment temperature to 500°C is 20°C/min or more, the element distribution driven by the formation of the second phase generated during the cooling process can be reduced, and the microscopic composition caused by the element distribution can be suppressed. Variation in distribution. In addition, by cooling from the heat treatment temperature to a temperature of 300° C. or less at a rate of 10° C./min or less, residual strain due to thermal shrinkage caused by cooling can be reduced. As a result, a titanium plate with high homogeneity in which the component distribution and residual strain are homogeneous can be obtained.

(check step) For the titanium material obtained through the heat treatment step, the above method can also be used for inspection to check the homogeneity of the surface.

The chemical composition and metal structure of the titanium material produced by the method for producing a titanium material for metal foil production of the present embodiment are homogenized. Accordingly, in the titanium material produced by the method for producing a titanium material for metal foil production of the present embodiment, the paired potential detection probes are fixed on the surface of the titanium material to which a pair of energized electrode probes is in contact with the surface and supplied with a constant current. Among the plurality of voltages detected by the probes contacting the plurality of positions on the surface at intervals, the voltage ratio of the adjacent two positions is 0.95 or more and 1.05 or less. As a result, when the titanium material manufactured by the manufacturing method of the titanium material for metal foil manufacture of this embodiment is used for the roller for metal foil manufacture, generation|occurrence|production of a macroscopic pattern can be suppressed. The manufacturing method of the titanium plate of the present embodiment has been described above.

In addition, the titanium material for metal foil manufacturing of this embodiment is shrink-fitted on the inner drum as described above, and then the surface is ground to become the top skin of the metal foil manufacturing drum. If the load at the time of grinding varies, the amount of strain introduced directly under the surface of the drum may vary. If the amount of strain varies, the resistivity of the surface of the metal foil manufacturing roll may sometimes change. Therefore, the fluctuation range of the load at the time of polishing the metal foil to manufacture the drum is preferably 10% or less, preferably 5% or less, and more preferably 3% or less.

Moreover, the metal foil manufactured by using the metal foil manufacturing roll made of the titanium material for metal foil manufacturing is not specifically limited, For example, copper foil, nickel foil, aluminum foil, iron foil, etc. are mentioned.

Hereinafter, an Example is shown and embodiment of this invention is demonstrated concretely. In addition, the Example shown below is only an example of this invention, and this invention is not limited to the following example.

[Example 1] (manufacturing titanium) First, a plurality of titanium raw materials having different chemical compositions were prepared, and the titanium raw materials were melted by the melting methods shown in Tables 1 to 6 to produce a titanium ingot.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

In the electron beam melting method, the electron beam irradiated into the mold is adjusted according to the shape of the mold so that the irradiation amount (Y) per unit area falls within the range of the formula (2) according to the area/perimeter (X) of the mold output power, and take the approximate central value of formula (2) as its target value. However, although the electron beam irradiation output power was partially changed from the central value of the formula (2), the electron beam irradiation amount in the electron beam melting method was all set to 150 W/cm ² or less. In addition, all the melting rates were performed so as to be 2.5 ton/h or less, and the target value was set to 1.0 ton/h. Y=-3.8X+(135±25) ・・・Formula (2)

In the plasma melting method, the output power of the plasma irradiated into the mold is all set to 380 W/cm ² or less. In addition, all the melting rates were performed so as to be 2.5 ton/h or less, and the target value was set to 1.0 ton/h.

In the vacuum arc melting method, a water-cooled copper mold with a bottom (no openings below) of 750 mm in diameter is used, and electrodes made of a titanium raw material are melted.

The molds for casting molten titanium were those shown in Tables 1 to 6. "Horizontal cross-sectional shape of the inner space of the mold" shown in Tables 1 to 6 is a rough shape of the horizontal cross-section of the mold in the inner space of the mold, and "Details of the cross-section of the mold" shows the diameter R and the short side of the horizontal cross-section of the inner space of the mold. A, long side B, corner C, and its area and perimeter. In addition, the "irradiation dose" in Tables 1 to 6 refers to the irradiation dose per unit area in the casting mold when the ingot manufacturing method is EBR and PAM.

For the produced titanium ingot, when it is cylindrical and 750 mmφ, and when it is rectangular and has a thickness of 350 mm or more, after trimming the surface of the casting by cutting or the like, hot forging is performed to make a thickness of 250 mm. flat embryo. When the ingot is rectangular and has a thickness of 260 mm or less, hot forging is not performed, but the surface of the ingot is trimmed by cutting or the like. This etc. are heated to 800 degreeC, and rolling is performed at a reduction ratio of 90% or more, and the rolled sheet of thickness 8-15mm is manufactured. Then, after heat treating the rolled sheet at a temperature of 700°C for 30 minutes, the average cooling rate from the heat treatment temperature to 500°C was 20°C/min and the average cooling rate from the heat treatment temperature to 300°C was 10°C/min. The method is used to cool the rolled sheet after heat treatment to produce a plate-shaped titanium material. In addition, temperature control is performed by airflow and a heater.

(Manufacturing of metal foil manufacturing drum) After the produced titanium material is made into a tubular shape, it is shrink-fitted to a cylindrical titanium material (inner roll) and the surface thereof is ground to produce an electrodeposition roll. The fluctuation range of the load at the time of polishing is set to be 10% or less.

(Analysis/Assessment) The average chemical composition, voltage ratio, and macroscopic appearance were evaluated for the titanium materials of each Example and Comparative Example. Also, the voltage ratio was evaluated for electrodeposition rollers made of these titanium materials.

Regarding the average chemical composition, O and N were analyzed by an inert gas melting method using an analyzer (machine name ON736) manufactured by LECO JAPAN CORPORATION. Specifically, O is analyzed by a non-dispersive infrared absorption method, and N is analyzed by a thermal conduction method. The C series was analyzed by an infrared absorption method using an analyzer (machine name CS444) manufactured by LECO JAPAN CORPORATION. Regarding H, the analysis was performed by the thermoconductive method using an analysis machine (machine name EMGA-800M) manufactured by Horiba Seisakusho Co., Ltd. Fe, Ni, Cr and Mo were analyzed by ICP emission spectrometry using an analyzer (device name ICPS8100) manufactured by Shimadzu Corporation.

The voltage ratio was calculated and evaluated as follows. A pair of energized electrode probes were brought into contact with the surface of the titanium material to supply a constant current. Next, the paired potential detection probes were arranged at a probe interval of 30 mm as shown in FIG. 2 , and the paired potential detection probes were brought into contact with the surface of the titanium material in the direction of the straight line L1 to measure the voltage. Next, the energized electrode probes were moved 30 mm in the direction perpendicular to the straight line L1, and the paired potential detection probes were brought into contact along the straight line L2 to measure the voltage. The above procedure was repeated, the voltage on the surface of the titanium material was measured, and the voltage ratio of the adjacent positions was calculated from the measured voltage.

The evaluation of the voltage ratio is based on the ratio of the data whose voltage ratio is less than 0.95 or more than 1.05 to the total number of data of the calculated voltage ratio, and is evaluated in the following manner.

Excellent (A): The ratio of data with a voltage ratio less than 0.95 or greater than 1.05 to the total number of data with the calculated voltage ratio is less than 2% Good (B): The ratio of data with a voltage ratio of less than 0.95 or greater than 1.05 to the total number of data with the calculated voltage ratio is 2% or more and less than 5% Acceptable (C): The ratio of the data with the voltage ratio less than 0.95 or greater than 1.05 to the total number of data with the calculated voltage ratio is 5% or more

Furthermore, with respect to the example of the above-mentioned evaluation being excellent (A), evaluation was performed as follows depending on the value of the calculated voltage ratio.

Excellent (AAA): All voltage ratios are above 0.98 and below 1.02 except for voltage ratios less than 0.95 or greater than 1.05 Better (AA): All voltage ratios are above 0.97 and below 1.03 except for voltage ratios less than 0.95 or greater than 1.05 (excluding excellent cases) Best (A): All voltage ratios are above 0.95 and below 1.05 except for data with voltage ratios less than 0.95 or greater than 1.05 (excluding excellent and better cases)

For the macroscopic pattern, the surfaces of 20 50×100 mm titanium plates of each of the invention examples and comparative examples were ground with #800 sandpaper, and then the surfaces were etched with 10% nitric acid and 5% hydrofluoric acid solution. observed. Next, a rib-like pattern having a length of 3 mm or more was generated as a macroscopic pattern, and the evaluation was performed in the following manner depending on the generation rate.

Excellent (A): The production ratio is less than 0.05 pieces/piece Good (B): The production ratio is greater than 0.05 pieces/piece and less than 0.15 pieces/piece Acceptable (C): The production ratio is greater than 0.15 pieces/piece The above evaluation results are listed in Tables 7-12.

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

As shown in Tables 1 to 12, for titanium materials produced using ingots melted with EBR or PAM, if the area/perimeter is 22.5 cm or less, the voltage ratio is less than 0.95 or greater than 1.05 for the calculated data. The ratio of the total number of data of the voltage ratio is less than 2%, and, except for the data of the voltage ratio less than 0.95 or more than 1.05, all the voltage ratios are above 0.95 and below 1.05. Moreover, such a titanium material suppresses the macroscopic appearance of the surface. The horizontal cross-section of the casting mold in the inner space of the casting mold used to manufacture the ingot, if the area/perimeter of the cross-section is 15.0 cm or less, the data of the voltage ratio less than 0.95 or more than 1.05 to the total number of data of the calculated voltage ratio The ratio is less than 2%, and all voltage ratios are above 0.97 and below 1.03, except for data with voltage ratios below 0.95 or above 1.05. Moreover, this titanium material suppresses the macroscopic appearance of the surface. If the above area/perimeter is 11.0 cm or less, the ratio of the data with a voltage ratio of less than 0.95 or more than 1.05 to the total number of data of the calculated voltage ratio is less than 2%, and the data other than the voltage ratio of less than 0.95 or more than 1.05 , all voltage ratios are above 0.98 and below 1.02. Moreover, this titanium material extremely suppresses the macroscopic appearance of the surface.

In addition, when the Mo content is 0.5 times or more and 1.2 times or less with respect to the total content of Fe, Cr and Ni, the ratio of the data of the voltage ratio less than 0.95 or more than 1.05 to the total number of data of the calculated voltage ratio is less than 2%, And, except for the data with the voltage ratio less than 0.95 or more than 1.05, all the voltage ratios are above 0.98 and below 1.02. Moreover, this titanium material extremely suppresses the macroscopic appearance of the surface.

In addition, the evaluation results of the voltage ratio of the metal foil manufacturing rollers produced are the same as the evaluation results of the voltage ratio of the titanium material, and the evaluation results of the macroscopic pattern on the surface of the roller are also the same as the evaluation results of the macroscopic pattern on the surface of the titanium material. . Therefore, it turns out that the manufacturing process which manufactures a roll from a metal foil has little influence by the intrinsic factor of the titanium material for metal foil manufacture.

[Example 2] The Al content was changed, and in the same manner as in Example 1, production of a titanium material, production of a metal foil production roll, and analysis/evaluation were performed.

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

[Table 19]

[Table 20]

As shown in Tables 13 to 20, when one or two or more elements consisting of the following groups are contained in mass % in a total of 0.2% or more and 5.0% or less: Sn: 0.2% or more and 2.0% The following, Zr: 0.2% or more and 5.0% or less, Al: 0.2% or more and 3.0% or less, and containing: N: 0% or more and 0.10% or less, C: 0% or more and 0.08% or less, H : 0% or more and 0.015% or less, O: 0% or more and 1.0% or less, and Fe: 0% or more and 0.500% or less, and the voltage ratio of two adjacent positions among the plurality of positions is 0.95 or more and Below 1.05, in this case, the macroscopic pattern of the surface is suppressed. In addition, when Al is contained in an amount of more than 1.8 mass % and 7.0 mass % or less, and Aleq is 7.0 mass % or less, the macroscopic pattern of the surface is suppressed.

In addition, the evaluation results of the voltage ratio of the metal foil manufacturing rollers produced are the same as the evaluation results of the voltage ratio of the titanium material, and the evaluation results of the macroscopic pattern on the surface of the roller are also the same as the evaluation results of the macroscopic pattern on the surface of the titanium material. .

[Example 3] When the titanium ingots shown in Tables 21 and 22 are rectangular and have a thickness of 350 mm or more, after trimming the surface of the ingot by cutting or the like, hot forging is performed to produce a flat ingot with a thickness of 250 mm. When the ingot is rectangular and has a thickness of 260 mm or less, hot forging is not performed, but the surface of the casting is trimmed by cutting or the like. Then, titanium materials were produced according to the rolling conditions, heat treatment and cooling conditions shown in Tables 23 to 25. Moreover, the manufacture, analysis/evaluation of the metal foil manufacturing roll were performed, and these were performed by the same method as Example 1.

The β transformation points shown in Tables 22-25 are the values calculated by obtaining the state diagram of the titanium alloy by the CALPHAD method using the integrated thermodynamic calculation system Thermo-Calc of Thermo-Calc Sotware AB and a predetermined database (TI3).

[Table 21]

[Table 22]

[Table 23]

[Table 24]

[Table 25]

As shown in Tables 21 to 25, the titanium ingot is heated to a temperature of 750°C or higher and lower than the β transformation point, and rolled so that the reduction ratio becomes 90% or higher, and then the temperature is 600°C or higher and 750°C or lower. heat treatment at a temperature of 20 minutes or more and 120 minutes or less, and cool from the heat treatment temperature to 500°C at an average cooling rate of 20°C/min or more, and cool from the heat treatment temperature to 500°C at an average cooling rate of 10°C/min or less. The titanium material is produced at a temperature of 300° C. or lower, and in the case of the above, the titanium material is one that suppresses the macroscopic appearance of the surface.

In addition, the evaluation results of the voltage ratio of the metal foil manufacturing rollers produced are the same as the evaluation results of the voltage ratio of the titanium material, and the evaluation results of the macroscopic pattern on the surface of the roller are also the same as the evaluation results of the macroscopic pattern on the surface of the titanium material. .

[Example 4] As shown in Tables 26 and 27, a titanium ingot was produced by changing the dose of electron beam irradiation into the inner space of the mold, the dose of plasma irradiation into the mold, and the melting rate. "Irradiation dose" in Tables 26 and 27 refers to the dose of electron beam irradiated to the inner space of the mold when the titanium ingot production method is electron beam melting, and refers to the electron beam irradiation dose to the inner space of the mold when the titanium ingot production method is plasma melting. The amount of plasma exposure in the mold.

For the produced titanium ingot, when it is cylindrical and 750 mmφ, and when it is rectangular and has a thickness of 350 mm or more, after trimming the surface of the casting by cutting or the like, hot forging is performed to make a thickness of 250 mm. flat embryo. When the ingot is rectangular and has a thickness of 260 mm or less, hot forging is not performed, but the surface of the ingot is trimmed by cutting or the like. This etc. were heated to 800 degreeC, and the rolled sheet of thickness 8mm was manufactured. Then, after heat treating the rolled sheet at a temperature of 700°C for 30 minutes, the average cooling rate from the heat treatment temperature to 500°C was 20°C/min and the average cooling rate from the heat treatment temperature to 300°C was 10°C/min. The method is used to cool the rolled sheet after heat treatment to produce a plate-shaped titanium material. In addition, temperature control is performed by airflow and a heater. The results are shown in Table 28. In addition, the average chemical compositions IG1 to IG9 of the titanium materials shown in Table 28 represent the same average chemical compositions as the symbols IG1 to IG9 shown in Table 22.

[Table 26]

[Table 27]

[Table 28]

As shown in Tables 26 to 28, when the electron beam irradiation dose to the inner space of the mold was 150 W/cm ² or less, and the melting rate was 2.5 ton/h or less, the evaluation results of the voltage ratio and macroscopic shape It is extremely excellent, and it also extremely suppresses the appearance of the giant. In addition, in the plasma melting method, when the amount of plasma irradiation into the mold is 380 W/cm ² or less, and the melting rate is 2.5 ton/h or less, the evaluation results of the voltage ratio and macroscopic pattern are also extremely excellent, and also extremely suppressed. It looks like a giant.

In addition, the evaluation results of the voltage ratio of the metal foil manufacturing rollers produced are the same as the evaluation results of the voltage ratio of the titanium material, and the evaluation results of the macroscopic pattern on the surface of the roller are also the same as the evaluation results of the macroscopic pattern on the surface of the titanium material. .

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited to these examples. It is obvious that a person of ordinary skill in the technical field to which the present invention pertains can devise various modifications or amendments within the scope of the technical ideas described in the scope of the patent application, and knows that these also belong to the technology of the present invention. Scope.

10: Titanium material for metal foil production 11: Surface 12: Inhomogeneous parts 20A, 20B: Electrode probes 30A, 30B: Potential detection probes 40, 40A, 40B: Casting molds 41A, 41B: Internal space 100: Manufacturing of copper foil Apparatus 110: Electrolytic cell 120: Electrodeposition drum 121: Inner drum 122: Titanium material 123: Welding part 124: Side plate 125: Rotating shaft 130: Electrode plate 140: Coiling part 150: Guide roller 160: Coiling roller A: Center Shaft (Fig. 6), Short side (Fig. 8) B: Long side C: Corner F: Copper foil I: Constant current L: Probe interval L ₁ , L ₂ : Line V ₁ to V _n : Voltage a-a ': The interval b1-b1'~bn-bn', c1-c1'~cn-cn': part of the surface contacted by the energized electrode probe

FIG. 1 is a schematic diagram for explaining an inspection method of a titanium material for metal foil manufacturing or a metal foil manufacturing roller according to an embodiment of the present invention. 2 is a schematic view of the surface of the titanium material for metal foil production, showing the arrangement of the energized electrode probes and the potential detection probes in the method for inspecting the titanium material for metal foil production or the metal foil production drum according to an embodiment of the present invention An example. FIG. 3 is a micrograph showing an example of the macroscopic pattern observed on the surface of the titanium material after corrosion. Fig. 4 is a microscope photograph showing an example of the macroscopic pattern observed on the surface of the titanium plate after corrosion, and is a reference image in which the macroscopic pattern is emphasized in order to show the position of the macroscopic pattern. FIG. 5 is a schematic diagram of a copper foil manufacturing apparatus, which shows a usage state of one of the metal foil manufacturing rolls. Fig. 6 is a schematic diagram showing a metal foil manufacturing roll according to an embodiment of the present invention. Fig. 7 is a cross-sectional view showing an example of a horizontal cross-section of a mold used in the electron beam melting method or the plasma arc melting method. Fig. 8 is a cross-sectional view showing another example of a horizontal cross-section of a mold used in the electron beam melting method or the plasma arc melting method.

10: Titanium for metal foil manufacturing

11: Surface

12: Inhomogeneous parts

20A, 20B: Energized electrode probes

30A, 30B: Potential detection probe

I: constant current

L: probe spacing

V ₁ ~V _n : Voltage

a-a': The interval of the surface contacted by the energized electrode probe

b1-b1'~bn-bn': part

Claims (13)

A titanium material for metal foil manufacturing has the following chemical composition: Contains in mass %: Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, Al: 0% or more and 7.0% or less, N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 1.000% or less, Fe: 0% or more and 0.500% or less, Cr: 0% or more and 0.500% or less, Ni: 0% or more and 0.090% or less, Cu: 0% or more and 1.5% or less and Mo: 0% or more and 0.750% or less, and The remainder consists of Ti and impurities; and The total content of Fe, Cr and Ni is more than 0% and less than 0.500%; When a pair of energized electrode probes are brought into contact with a titanium material to supply a constant current, and a pair of potential detection probes are brought into contact with the surface at fixed probe intervals to measure the voltages at a plurality of positions on the surface, the voltages at the plurality of positions are The voltage ratio of two adjacent positions is 0.95 or more and 1.05 or less. If the titanium material for metal foil manufacturing of claim 1 contains Fe, Cr, Ni and Mo, The Ni content is 0 mass % or more and 0.090 mass % or less, and The Mo content is 0.5 times or more and 1.2 times or less with respect to the total content of Fe, Cr, and Ni on a mass basis. If the titanium material for metal foil manufacturing of claim 1 or 2, it contains in mass %: N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 0.400% or less, Fe: 0.02% or more and 0.500% or less, Ni: 0% or more and 0.090% or less and Cu: 0% or more and 1.5% or less. As claimed in claim 1, the titanium material for metal foil manufacturing contains, in mass %, one or two or more elements consisting of the following groups, and the total amount is 0.2% or more and 5.0% or less: Sn: 0.2% or more and 2.0% or less, Zr: 0.2% or more and 5.0% or less and Al: 0.2% or more and 3.0% or less; and contains: N: 0% or more and 0.100% or less, C: 0% or more and 0.080% or less, H: 0% or more and 0.0150% or less, O: 0% or more and 1.000% or less and Fe: 0% or more and 0.500% or less. The titanium material for metal foil manufacturing according to claim 1, which contains more than 1.8 mass % and less than 7.0 mass % of Al; and In terms of mass %, when the Al content is [Al%], the Zr content is [Zr%], the Sn content is [Sn%], and the O content is [O%], the Al equivalent represented by the following formula (1) Aleq is 7.0 mass % or less: Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] Formula (1). The titanium material for metal foil manufacturing according to any one of claims 1 to 5, which is a titanium material for metal foil manufacturing rollers. A manufacturing method of titanium material for metal foil manufacturing, comprising the following steps: The step of manufacturing a titanium ingot by a continuous casting method that injects molten titanium into a coolable mold with openings on the upper and lower sides, and heats the molten titanium level in the mold, and Cooling the titanium through the casting mold to solidify it, and using a clamp to pull the solidified titanium downward; The step of heating the aforementioned titanium ingot to a temperature above 750° C. and below the beta transformation point, and rolling so that the reduction ratio reaches 90% or more to produce a rolled sheet; and Perform heat treatment at a temperature of 600°C or higher and 750°C or lower for 20 minutes or more and 120 minutes or less, and cool from the heat treatment temperature to 500°C at an average cooling rate of 20°C/min or more, and at 10°C/min or less. The average cooling rate is the step of cooling from the heat treatment temperature to a temperature below 300°C. The method for producing a titanium material for metal foil production as claimed in claim 7, comprising the step of thermally processing the titanium ingot to produce a flat blank; and In the aforementioned step of manufacturing the rolled sheet, the aforementioned flat billet is used instead of the aforementioned titanium ingot for rolling. The method for producing a titanium material for metal foil production according to claim 7 or 8, wherein the casting means is an electron beam melting method; and the electron beam irradiation dose to the inner space of the mold in the electron beam melting method is 150 W/cm ² or less , and the melting rate of the titanium is 2.5 ton/h or less, and the titanium is irradiated with the electron beam to melt the titanium. The method for producing a titanium material for metal foil production according to claim 9, wherein the ratio of the horizontal cross-sectional area of the inner space of the casting mold to the inner circumference of the horizontal cross-section of the casting mold and X in the unit cm is the same as that in the electron beam melting method. The above-mentioned electron beam irradiation amount and Y in unit W/cm ² satisfy the relationship of the following formula (2), Y=-3.8X+(135±25) ・・・ formula (2). The method for producing a titanium material for metal foil production according to claim 7 or 8, wherein the casting means is a plasma melting method; the plasma irradiation dose into the casting mold in the plasma melting method is 380 W/cm ² or less, and The melting rate of the titanium is 2.5 ton/h or less, and the titanium is irradiated with the plasma to melt the titanium. The method for producing a titanium material for metal foil production according to any one of claims 7 to 11, wherein in the horizontal section of the inner space of the casting mold, the ratio of the area per unit cm ² of the horizontal section to the perimeter per unit cm is 7.5 cm Above and below 22.5cm. A metal foil manufacturing drum having: The titanium material for metal foil production as claimed in claim 6 is coated along the outer peripheral surface of the cylindrical inner drum; and The welded portion is disposed on the butted portion of the titanium material.

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