JP4094395B2 - Titanium plate for electrolytic Cu foil production drum and production method thereof - Google Patents

Description

【００５２】
（実験２）
実験１の試験番号７と全く同じ成分（Ｔｉ−１．１％Ｃｕ−０．０３％Ｆｅ−０．０５％酸素）からなる１５０mm厚のスラブを、表２のスラブ加熱温度の欄に示す温度に加熱し、厚さ１０mmの板に熱間圧延し、表２の焼鈍温度の欄に示す種々の温度で焼鈍した。
その後、実験１と全く同じ方法で、結晶粒径、マクロ模様等を評価した。その結果を表２に示す。ここで、比較のため、実験１の試験番号７の結果も一緒に示してある。この成分のβ変態点、α＋β二相温度域とα単相域の境界温度、α単相域とα＋Ｔｉ₂ Ｃｕ二相温度域の境界温度は、いずれも試験番号７と同じで各々、８６５℃、８２５℃、７３０℃である。
【００５３】
表２において、本発明（３）または（４）に記載の方法、すなわちα＋β二相域にスラブ加熱し圧延し、β変態点以下の温度で焼鈍した、試験番号１４，１７，１８，１９，２０は、いずれも細粒が得られており、板のマクロ模様は◎の判定であった。またピッティングも無く、ドラムに成形後のマクロ模様も○ないし◎の良好な結果であった。特に本発明（４）に記載の、α単相温度域での焼鈍を行った試験番号１８，１９は、ドラムに成形後も◎のマクロ模様判定となっており、本発明２および４の効果が遺憾無く発揮されている。
【００５４】
ここで、試験番号１４および１５は、スラブ加熱温度が本発明（３）に記載の温度範囲からはずれていたが、試験番号１４では、熱間圧延途中に温度が降下し、また試験番号１５では、熱間圧延初期の加工発熱により、いずれもα＋β二相温度域となり、本発明（１）の製品が製造できた。しかし、スラブ加熱をα＋β域で確実に行った試験番号７が◎のマクロ模様判定であったのに対し、これらはいずれも○判定であり、若干品質は劣っていた。
また、焼鈍をβ変態点を超える温度で行った試験番号１６は、著しく拡散の速いβ単相域に加熱されたため、折角α＋β域加熱圧延で蓄積した歪みが一挙に開放されて粒成長してしまい、均質微細組織が得られず、マクロ模様評価は×の判定であった。
【００５５】
【表２】

【００５６】
（実験３）
実験１および２において製造した熱延焼鈍板の中から、Ｔｉ−１．１％Ｃｕ−０．０３％Ｆｅ−０．０５％酸素の成分を有する試験番号７，１７，１９を選定し、これらを脱スケール後、さらに冷間圧延を行い、５mm厚の板とした。その後、表３の、冷延後の焼鈍温度の欄に記載した温度で焼鈍を行い、実験１，２と同じ方法で、結晶粒径やマクロ模様評価を行った。その結果を表３に示す。
【００５７】
表３において、本発明（５）または（６）に記載の方法で製造した板は、いずれも熱延焼鈍板の場合よりも結晶粒径が小さくなっており、板のマクロ模様評価はいずれも◎判定であった。熱延焼鈍板においても◎判定が得られているが、より微細な結晶粒が得られていることから、本材料にて製造したドラムを用いると、さらに緻密で高品質の電解Ｃｕ箔が製造できる。
【００５８】
ここで、試験番号１９は、冷延前の熱延焼鈍板がα単相からなるが、冷延後の焼鈍をα＋Ｔｉ₂ Ｃｕ二相域で行っても、α相からＴｉ₂ Ｃｕ相の析出は著しく遅いためα単相の状態が保持される。そのため本発明（２）が達成され、ドラムに加工しても、なお◎の判定の高品質が得られた。
また試験番号２６，２７は、冷延前には若干の第２相が存在していたが、冷延後の最終焼鈍をα単相域で行ったため、本発明（２）が達成され、ドラムに加工しても、なお◎の判定の高品質が得られた。
【００５９】
【表３】

【００６０】
（実験４）
表４に示した成分からなるインゴットを、実験１と全く同じ方法で厚さ１５０mmのスラブとした。このスラブを表４に示すスラブ加熱温度に加熱し、この温度から７００℃までの範囲内で熱間圧延を行い、厚さ１０mmの熱延板とした。さらに、表４に示す焼鈍温度で、真空クリープ矯正機（ＶＣＦ）を用いて、形状矯正を兼ねて焼鈍を行った。計算状態図から推定した加熱温度及び焼鈍温度における相状態も表４に示した。
【００６１】
上記の厚板の結晶粒径の測定およびマクロ模様の観察を、実験１と全く同じ方法で行った。また、マクロ模様判定が◎、○、△のものについては、ＳＥＭ観察により、ピット状の窪みの有無を観察した。ピット状の窪みとは、直径数μｍの円形または多角形状の孔のことである。マクロ模様判定が◎、○、△であった板については、脱スケール後、冷間で直径２．７ｍの円筒ドラム状に曲げ成形し、この一部から切り出した試験片を、硝沸酸系のマクロ腐食液でエッチングし、マクロ模様の観察を行った。マクロ模様判定が、◎または○で、ピット状の窪みも観察されない良好な材料については、溶接性の試験も行い、研磨後に溶接線が見えるかどうか観察した。
【００６２】
表１の試験番号５と同一成分の表４の試験番号２９は、α＋βニ相域に加熱し、α＋βニ相域温度で熱延したため、板におけるマクロ判定は◎であった。試験番号３０、３１についても、α＋β二相の温度域で熱延を行ったため、板によるマクロ判定は、◎であった。
試験番号３２は、通常の純チタンの場合であり、熱間圧延（スラブ加熱温度８５０℃）、焼鈍（焼鈍温度６３０℃）による製造方法では、板のマクロ模様は×判定であった。また、Ｃｒを０．０３％しか含まない試験番号３３では、熱延時に十分な二相状態が達成されず、マクロ模様判定は△であった。このように通常の純チタンやＣｒ含有量が０．１％未満の場合、α＋β相での熱延が困難であるため、未再結晶部が多く残存し、マクロ模様判定が不十分である。
【００６３】
これに対し、Ｃｒを０．１９％，０．４１％，０．５８％および０．８１％含む、試験番号３４，３６，３８，４０および４１は、いずれも微細均質微細組織が得られ、マクロ評価も◎または○の良好な結果であり、本発明の効果が十分に達成された。
このように、Ｃｒを０．１〜０．９％含有し、α＋β相で熱延すると、熱延後も材料全体が均一な再結晶組織となるため、マクロ模様判定が良好である。
【００６４】
一方、試験番号３５では、Ｆｅの添加量が本発明で規定された０．０４％を超えたため、腐蝕時にピット状の窪みが発生してしまった。試験番号３７では、酸素添加量が本発明で規定された０．１％を超えたため、溶接後、研磨しても溶接線が消えなかった。試験番号３９では、熱延時の温度がβ域であったため、粒成長が著しく結晶粒が粗大化し、均質微細組織が得られず、マクロ模様判定は×であった。焼鈍をβ域で行った試験番号４２についても、同様に結晶粒が粗大化し、均質微細組織が得られず、マクロ判定は×であった。試験番号４３は、Ｃｒの含有量が１．１７％と高い場合であり、マクロ模様判定は△であった。
【００６５】
試験番号４４および４５は、ＣｕとＣｒの両者を含む場合の本発明の実施例であり、α＋β二相域での熱延とα域での焼鈍後、板のマクロ模様判定は◎、ドラムのマクロ模様判定は○であった。試験番号４６は、Ｃｒの含有量が本発明の範囲よりも多く、マクロ模様判定は△であった。
試験番号４７〜５２は、それぞれＭｏ、Ｖ、Ｎｂ、Ｗの１種とＣｕを含有する場合の実施例である。いずれの材料も硬度が若干上昇したことによると思われる研磨後の光沢が多く、表面粗度が小さい材料が得られた。α＋β二相域で熱延後、α域で焼鈍を施した試験番号４７〜５０のマクロ模様は○判定であった。
比較例の試験番号５１および５２では、それぞれＭｏおよびＮｂの添加量が１％を超え、それらの元素の偏析によるマクロ模様が発生し、いずれもマクロ模様は△判定であった。
【００６６】
試験番号５３〜５５は、Ｍｏ、Ｖ、Ｎｂ、Ｗの２種とＣｕを含有する場合の実施例である。これらについても硬度が若干上昇したことによるものと思われる研磨後の光沢が多く、表面粗度が小さい材料が得られた。α＋β二相域で熱延後、α域で焼鈍を施した試験番号５３、５４のマクロ模様は○判定であった。
比較例の試験番号５５では、ＭｏとＮｂの合計添加量が１％を超え、それらの元素の偏析によるマクロ模様が発生し、マクロ模様は△判定であった。
試験番号５６〜６１は、それぞれＭｏ、Ｔａ、Ｖ、Ｎｂ、Ｗ、Ｈｆの１種とＣｒを含有する場合の実施例である。いずれの材料も硬度の若干の上昇に起因すると思われる研磨後の光沢が多く、表面粗度が小さい材料が得られた。α＋β二相域で熱延後、α域で焼鈍を施した試験番号５６〜５９のマクロ模様は○判定であった。比較例の試験番号６０、６１では、それぞれＴａ、Ｈｆの添加量が１％を超え、それらの元素の偏析によるマクロ模様が発生し、いずれもマクロ模様は△判定であった。
【００６７】
試験番号６２〜６４は、Ｍｏ、Ｔａ、Ｎｂ、Ｗの２種とＣｒを含有する場合の実施例である。これらについても硬度が若干上昇したことによるものと思われる、研磨後の光沢が多く、表面粗度が小さい材料が得られた。α＋β二相域で熱延後、α域で焼鈍を施した試験番号６２、６３のマクロ模様は○判定であった。
比較例の試験番号６４では、ＭｏとＮｂの合計添加量が１％を超え、それらの元素の偏析によるマクロ模様が発生し、いずれもマクロ模様は△判定であった。
【００６８】
【表４】

【００６９】
（実験５）
表５に示した成分からなるインゴットを、実験１と全く同じ方法で厚さ１５０mmのスラブとした。このスラブを表５に示すスラブ加熱温度に加熱し、厚さ１０mmの板に熱間圧延した。さらに、表５の焼鈍１の欄に示す焼鈍温度で、真空クリープ矯正機（ＶＣＦ）を用いて、形状矯正を兼ねて焼鈍を行った。計算状態図から推定した焼鈍温度における相状態も表５の焼鈍１の欄に示した。これらを脱スケール後、さらに冷間圧延を行い、５mm厚の板とした。その後、表５の焼鈍２に示した温度で焼鈍を行い、実験１同じ方法で、結晶粒径、マクロ模様判定を行った。表５の焼鈍２の欄に計算状態図から推定した焼鈍温度における相状態も示した。
マクロ模様判定が◎、○、△であったサンプルは、ＳＥＭ観察により、ピット状の窪みの有無を観察し、また冷間で直径２．７ｍの円筒ドラム状に曲げ成形して、試験片を切り出し、マクロ模様の観察を行った。さらに、マクロ模様判定が、◎または○で、ピット状の窪みも観察されない良好な材料については、溶接性の試験も行い、研磨後に溶接線が見えるかどうか観察した。
【００７０】
試験番号６５〜７１、７３〜７５、７７、７９〜８１、８３は、いずれも板のマクロ模様評価、およびドラムのマクロ模様評価ともに◎であり、ピッティングも無く、さらに溶接後の溶接線についても観察されなかった。一方、ＣｕとＣｒの含有量が本発明の規定値よりも多い試験番号７２では、板のマクロ模様評価は△であった。また、試験番号７６、７８、８２、８４では、それぞれＶの添加量、ＴａとＨｆの合計添加量、Ｚｒの添加量、ＺｒとＨｆの合計添加量が本発明の規定値を超えているため、板のマクロ模様評価は△であった。
【００７１】
【表５】

【００７２】
【発明の効果】
以上説明したように、本発明により、マクロ模様が少なく均一微細な板面金属組織を有し、高品質の電解Ｃｕ箔を製造するに適した、電解Ｃｕ箔製造ドラム用チタン板及びその製造方法を、複雑な加工熱処理工程を経ることなく提供することができる。
【図面の簡単な説明】
【図１】ＴｉとＣｕの二元系平衡状態図の一部を示す図である。
【図２】ＴｉとＣｕの二元系平衡状態図の一部を示す図である。
【図３】ＴｉとＣｒの二元系平衡状態図の一部を示す図である。
【図４】α単相のチタン板のミクロ組織を示す図である。
【図５】β相および析出相を有するチタン板のミクロ組織を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a drum titanium material for producing a copper foil (referred to as Cu foil) used for a printed wiring board of an electronic component and the like, and a material having a uniform and dense plate surface metallographic structure It relates to a manufacturing method.
[0002]
[Prior art]
A printed wiring board used by being incorporated in an electronic component is manufactured by bonding a conductive Cu foil on an insulating substrate, printing a wiring pattern on the surface, and removing unnecessary portions by etching.
[0003]
The Cu foil used for this printed wiring board is an electrochemical solution in which a high-grade Cu raw material is dissolved in a sulfuric acid solution, an insoluble metal such as Pb as the anode, the drum as the cathode, and the drum rotating. In particular, it is manufactured by a method in which Cu is continuously electrodeposited on a drum, this is continuously peeled off and wound into a roll. As a material for the drum, titanium has been frequently used in recent years from the viewpoint of excellent corrosion resistance and excellent peelability of Cu foil.
[0004]
By the way, the wiring pattern of electronic parts is extremely fine (width 0.1 to 0.5 mm) and requires high precision and reproducibility, so the surface roughness of Cu foil used for printed wiring is also extremely high precision and homogeneity. Sex is required. Since this surface roughness inherits the surface state of the titanium cathode drum on which the Cu foil was electrodeposited, the surface of the titanium drum is used after highly polished and leveled.
[0005]
However, even a highly corrosion-resistant titanium material is gradually corroded in the electrolyte during use, and the newly appearing surface state is transferred to the Cu foil. It is known that the degree of metal corrosion varies depending on various internal states such as the structure, crystal orientation, defects, segregation, processing strain and residual strain of the metal material. If a drum made of an internal material is corroded during use, a uniform surface state cannot always be maintained. When a non-uniform surface state appears, it is transferred to the copper foil, which causes a problem that Cu foil having a high accuracy and a uniform thickness cannot be manufactured.
[0006]
Titanium materials that can cause inhomogeneous corrosion surface states as described above can be identified by examining the macrostructure in the drum titanium plate. The macro structure in metallography can be obtained by etching using an appropriate acid solution (eg, nitric hydrofluoric acid in the case of titanium) used to reveal a cast or processed structure. This is a structure that appears due to various internal states such as structure, crystal orientation, defects, segregation, processing strain, and residual strain, just like the inhomogeneous structure that occurs during drum use.
[0007]
Among such heterogeneous tissues, those that can be discriminated with the naked eye are called “macro patterns”. In the case of a titanium drum for producing copper foil, the macro structure is dipped in an etching solution of about 10% nitric acid, about 5% boiling acid, and the remaining water for several tens of seconds to several minutes after polishing the surface with sandpaper No. 600. Can be obtained. For some reason, if there is a heterogeneous structure even with a length of several millimeters, these portions are differently etched, and thus are discriminated with the naked eye.
Therefore, homogenizing the macro structure of the raw material titanium material, that is, reducing the so-called “macro pattern” that occurs in the macro structure, achieves uniform corrosion of the drum, and highly accurate and uniform thickness Cu foil. Is essential for manufacturing.
[0008]
As an attempt to homogenize the macro structure of the drum titanium material and reduce the macro pattern, there is a method disclosed in Patent Document 1 below. In this method, the heat treatment conditions are devised to obtain a fine and sized structure, and the macro pattern is reduced. However, the process is complicated, and if the heating temperature and time are not strictly controlled, the grain size must be controlled. There was a problem that growth occurred and it was difficult to obtain a desired effect. Furthermore, there is a problem that handling of the material is complicated and workability is not good.
[0009]
[Patent Document 1]
JP-A-8-144033
[0010]
Patent Document 2 below also discloses an attempt to reduce the macro pattern by devising the thermomechanical processing conditions. However, this method is also complicated in the process, and its condition management is also complicated.
[0011]
[Patent Document 2]
Japanese Patent Publication No. 3-28505
[0012]
Further, in Patent Document 3 below, in order to refine and homogenize the structure, a slab having a recrystallized structure fraction exceeding 90% is hot-rolled at a total reduction ratio exceeding 15 and annealed. Is disclosed. However, with this method, the macro pattern is improved, but there is a problem that the crystal grains become slightly coarser and the appearance looks somewhat rough. Further improvement is required from the viewpoint of making the crystal grain size finer. It was.
[0013]
[Patent Document 3]
JP-A-11-226608
[0014]
Patent Document 4 listed below discloses a method for obtaining a uniform and dense metal structure by sufficiently introducing mechanical twins by cold rolling and forming a structure having less colony structure by annealing recrystallization. . However, although the combination of cold rolling and annealing by this method is effective in reducing the macro pattern, it requires cold rolling of large-sized thick plates, so it is difficult in terms of equipment and technology. There has been a demand for a new material that is high and can obtain a fine and uniform structure without cold rolling or annealing.
[0015]
[Patent Document 4]
JP 2000-45091 A
[0016]
Also, an attempt to obtain a homogeneous and fine metal structure with few macro patterns can be considered from the viewpoint of composition without relying on thermomechanical processing. For example, if a second phase that is different from the matrix is present, this suppresses crystal grain growth of the matrix main phase, making it easy to obtain a fine structure. For example, when the β phase is generated by adding 0.04% by mass or more, which is a solid solubility limit in titanium, this fine effect is achieved. However, the corrosion resistance of the β-phase enriched with Fe deteriorates significantly, and this part preferentially dissolves in the form of pits in a corrosive environment and is transferred to a Cu foil product. Is not applicable. When Ni is added, Ti₂Ni phase is generated and corrosion resistance is improved, and at the same time, crystal grain refinement is achieved. However, there is a problem that Ni eluted in a corrosive environment is mixed into the Cu foil, which is not preferable.
[0017]
[Problems to be solved by the invention]
In view of the present situation as described above, the present invention has a uniform and fine plate surface metallographic structure with few macro patterns, can be manufactured without relying on complicated processing heat treatment, and can produce high-quality electrolytic Cu foil. It is an object of the present invention to provide a drum titanium material that can be produced and a method for producing the same.
[0018]
[Means for Solving the Problems]
The inventors of the present invention have conducted extensive research on the influence of additive elements on the formation of macrostructures that occur in hot-rolled sheets of various titanium materials, and on the reaction behavior of Cu foil production solutions and various titanium materials. Thus, the present inventors have found a titanium material that can maintain a uniform surface state even when it is corroded in a Cu foil manufacturing solution.
[0019]
  The present invention has been completed based on such findings, and the gist thereof is as follows.
(1) In mass%, Cu: 0.5 to 2.1%, Fe: 0.04% or less, oxygen: 0.1% or less, and the balance consisting of titanium and inevitable impurities,The average crystal grain size is less than 40 μmA titanium plate for an electrolytic Cu foil production drum, characterized by having a homogeneous fine recrystallized structure.
(2) The titanium plate for an electrolytic Cu foil production drum as described in (1) above, wherein the titanium plate comprises an α single phase.
(3) A slab containing Cu: 0.5 to 2.1%, Fe: 0.04% or less, oxygen: 0.1% or less, and the balance of titanium and inevitable impurities in a mass%, α + β two-phase A method for producing a titanium plate for an electrolytic Cu foil production drum, comprising heating to a temperature range, hot rolling, and annealing at a temperature not higher than the β transformation point.
(4) By mass%, a slab containing Cu: 0.5 to 2.1%, Fe: 0.04% or less, oxygen: 0.1% or less, and the balance titanium and inevitable impurities, α + β two-phase A method for producing a titanium plate for an electrolytic Cu foil production drum, comprising heating to a temperature range, hot rolling, and further annealing in an α single phase temperature range.
(5) Subsequent to the method described in (3) or (4) above, further cold rolling is performed, and then annealing is performed at a temperature equal to or lower than the β transformation point. A method for producing a titanium plate.
(6) Following the method described in (3) or (4) above, further cold rolling is performed, and then annealing is performed in an α single phase temperature range, and the titanium for electrolytic Cu foil production drums A manufacturing method of a board.
[0020]
(7) By mass%, containing one or two of Cu: 0.1 to 2.1% and Cr: 0.1 to 0.9%, Fe: 0.04% or less, oxygen: 0.0. Contains less than 1%, the balance is titanium and inevitable impurities,The average crystal grain size is less than 40 μmA titanium plate for an electrolytic Cu foil production drum, characterized by having a homogeneous fine recrystallized structure.
(8) The electrolysis as described in (7) above, further containing 1% or less of one or more of Mo, Ta, V, Zr, Nb, Hf, and W in total by mass% Titanium plate for Cu foil production drum.
(9) The titanium plate for an electrolytic Cu foil production drum as described in (7) or (8) above, comprising an α single phase.
(10) The slab comprising the component described in (7) or (8) is heated to a two-phase temperature range of α + β, hot-rolled, and further annealed at a temperature equal to or lower than the β transformation point. (7) to (9The manufacturing method of the titanium plate for electrolytic Cu foil manufacture drums of any one of 1).
(11) A slab composed of the component described in (7) or (8) above is heated to a two-phase temperature range of α + β, hot-rolled, and further annealed in an α single-phase temperature range. (7) to (9The manufacturing method of the titanium plate for electrolytic Cu foil manufacture drums of any one of 1).
(12) (10) Or (11The method for producing a titanium plate for an electrolytic Cu foil production drum, which is further subjected to cold rolling and subsequently annealing at a temperature not higher than the β transformation point.
(13) (10) Or (11The method for producing a titanium plate for an electrolytic Cu foil production drum, which is further subjected to cold rolling after the method described in) and then annealing in an α single phase temperature range.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
First, the components contained in the present invention will be described. The component content is% by mass.
In the present invention (1), Cu: 0.5 to 2.1%, Fe: 0.04% or less, oxygen: 0.1% or less, and the balance titanium and inevitable impurities.
First, the reason why Fe and oxygen are limited to the above range will be described.
Pure titanium and main titanium alloys have an α phase of hcp structure as the main phase, and oxygen is an alloying element that strengthens this. Since the electrolytic Cu foil production drum is formed into a cylindrical drum by bending the plate cold, the softer one is easier to mold, and the residual stress after molding is smaller and uniform. This residual stress also contributes to the generation of the macro pattern, and in order to reduce this, the oxygen content is set to 0.1% or less in the present invention. The lower limit of the amount of oxygen is not particularly specified, but is usually 0.005% or more as an impurity.
[0022]
Fe is an element that stabilizes the β phase, and the amount of solid solution in the α phase is extremely small and is 0.04% at most even at the temperature at which the most solid solution is formed. If Fe is added in excess of this, a β-phase enriched with Fe will appear, but as described in the section [Prior Art], this β-phase is preferential in a corrosive environment. It dissolves easily in pit-shaped depressions. If such a dent exists on the surface, it is transferred to the Cu foil to be electrodeposited, so that a high-quality Cu foil cannot be produced. Therefore, the Fe content needs to be 0.04% or less. The lower limit of the amount of Fe is not particularly specified, but is usually 0.005% or more as an impurity.
[0023]
Next, the reason why Cu is limited to the range of 0.5 to 2.1% will be described.
As shown in the binary equilibrium diagram of FIG. 1, Cu is around 850 ° C. which is a general hot rolling temperature of titanium material in the Cu concentration range (0.5 to 2.1%) of the present invention. Becomes two phases of α + β. The two-phase structure has a finer structure because crystal grain growth is significantly suppressed as compared with the single-phase structure. Further, it is a well-known fact that the processed recrystallized structure becomes homogeneous and finer as the structure before processing becomes finer. In the present invention, by adding an appropriate amount of Cu, the main hot rolling is possible in a two-phase temperature range, and the final structure is made into a homogeneous fine recrystallized structure to reduce the macro pattern.
[0024]
In order to realize this, the amount of Cu needs to be 0.5 to 2.1%. This is because when Cu is less than 0.5%, it does not become a two-phase around 850 ° C., which is the normal hot rolling heating temperature of titanium, and when Cu exceeds 2.1%, solidification segregation occurs. The macro pattern due to this segregation occurs or Ti₂This is because the material strength increases with the increase of the Cu phase, the processing distortion due to cold forming becomes inhomogeneous, and a macro pattern resulting from this is generated.
[0025]
Of course, once heated to the two-phase temperature range and hot-rolled, depending on the subsequent cooling and annealing conditions, a small amount of Cu-concentrated β phase may remain up to room temperature, or the equilibrium diagram of FIG. As shown, Ti is an equilibrium phase at low temperatures.₂There is also a possibility that a small amount of Cu phase is generated from the β phase. However, these Cu-enriched phases have high corrosion resistance unlike the Fe-enriched β phase, and even when exposed to a corrosive environment such as an electrolytic solution for producing Cu foil, As in the case of the β phase, vigorous preferential dissolution does not occur and the quality of the Cu foil product is not greatly deteriorated.
Further, the amount of these phases is small, and the influence on the workability when the drum is cold-formed is also small. Furthermore, since the drum is used for the purpose of electrodepositing Cu with a copper sulfate electrolyte, even if Cu elutes from the titanium material containing Cu, the Cu is taken into the product Cu foil. The foil is not adversely affected.
[0026]
In the present invention (1), it is essential to have a homogeneous fine recrystallized structure. In order to reduce the macro pattern, it is essential to have a homogeneous microstructure, but if it is not recrystallized, a macro pattern reflecting non-uniform processing strain distribution and unrecrystallized stretch coarse grains will occur. .
Here, the recrystallized structure refers to a structure in which there is no black linear or network-like unrecrystallized structure in the crystal grains, and is hardly seen except at the grain boundaries. The fine structure is an average crystal grain size of less than 40 μm. The crystal grains are shown. Homogeneity corresponds to the size of the drum product, for example, when a sample is taken from an arbitrary part of a 1.5 m × 8 m plate and the microstructure is observed, the optical microscope structure of any sample is finely reconstructed. It means a crystal structure. To confirm that it is homogeneous, test pieces of about 1 cm × 1.5 cm are collected from 3 to 4 places in the width direction end or center on the top and bottom sides adjacent to the longitudinal direction of the drum product. This is done by observing the microstructure of the surface with an optical microscope.
[0027]
For the reasons described above, the titanium material to which Cu of the present invention is added is a material suitable for a drum for producing electrolytic Cu foil.
The inevitable impurities refer to impurity elements that are unavoidable to be mixed into the material in manufacturing processes such as refining, melting, forging, hot rolling, cold rolling, heat treatment, and refining. For example, 0.05 % Or less of nitrogen, carbon, hydrogen, Ni, Cr, Mn, Mg, Sn, Al, V, Si and the like.
[0028]
In the present invention (2), the titanium plate for electrolytic Cu foil production drum of the present invention (1) is made of α single phase. As described in the description of the present invention (1), the Cu-rich β phase and Ti₂Even if a small amount of Cu phase is present, a drum capable of producing a high-quality Cu foil can be produced. The stress / strain distribution is also homogenized, and the corrosion by the electrolytic solution is remarkably uniform, so that a very high quality Cu foil can be manufactured.
[0029]
The titanium plate for an electrolytic Cu foil production drum as described above can be produced, for example, by the method described in (3) to (6) of the present invention. Next, this manufacturing method will be described.
First, in the method described in the present invention (3), the titanium slab was heated in the α + β two-phase temperature range of the titanium material, and hot-rolled in the α + β two-phase temperature range. The purpose of Cu addition in the present inventions (1) and (2) is to make a two-phase temperature range sufficient to obtain a homogeneous microstructure. Therefore, the initial purpose can be achieved by entering this temperature range in the middle of rolling, but if the slab is heated to this temperature range from the beginning, this purpose is surely achieved.
[0030]
Moreover, after hot rolling, it was decided to anneal in a temperature range below the β transformation point of the titanium material. This is a process for obtaining a homogeneous fine recrystallized structure by accelerating recrystallization with a strain accumulated highly by hot rolling in a two-phase state as a nucleus. Therefore, the lower limit of the annealing temperature is preferably the recrystallization temperature.
[0031]
The β transformation point is the temperature at which the β single phase becomes higher at higher temperatures, and when heated to a β single phase region where diffusion is extremely fast, the accumulated strain is released at once and the grains grow. As a result, the effect of α + β two-phase rolling at the corner is lost, and a homogeneous microstructure cannot be obtained. However, in the α + β two-phase region below the β transformation point, since the grain growth is suppressed, a homogeneous fine recrystallized structure can be achieved. In this case, when the material passes through the α single phase region during cooling after annealing, most of the β phase is transformed into the α phase, but the homogeneous microstructure is maintained. Also, especially when the cooling rate is fast, the β phase remains or Ti during the cooling₂Cu phase may be generated, but even if these are generated, the amount is small, and as explained earlier, no severe preferential elution occurs in the electrolytic solution for producing Cu foil, and when the drum is formed, The effect on processability is also minimal. Therefore, the quality of the Cu foil product is not significantly reduced.
[0032]
Also, annealing is performed at α + Ti lower than the α single phase region.₂The same is true when performed in the Cu two-phase temperature range. That is, when passing through the α single phase region during cooling after hot rolling, most of the β phase has already transformed into the α phase, and from the α phase to the Ti phase₂The reaction in which Cu precipitates is extremely slow and requires 100 hours or more, so this reaction does not occur during actual annealing. Therefore, α + Ti₂Even when annealing is performed in the Cu two-phase temperature range, the α phase occupies the majority, and a very small amount of β phase is mixed. In addition, no vigorous preferential elution occurs in the electrolytic solution for producing Cu foil, and the influence on the workability when forming a drum is slight, and the quality of the Cu foil product is not significantly lowered.
[0033]
Α + β two-phase region and α + Ti₂When annealed in the α single phase region in the middle of the Cu two phase region, the β phase and Ti that were mixed after hot rolling₂All the Cu phases become α phases, and a complete α single phase structure is realized. This state is the α + β region and α + Ti₂Compared to annealing in the Cu region, it is easy to grow crystal grains because it is in a single phase state, but because the strain is accumulated in the α + β two-phase region first, it is homogeneous unless the annealing time is unnecessarily prolonged. A fine recrystallized structure can be achieved.
In addition, α + Ti during cooling₂Although passing through the Cu two-phase region, as described above, Ti from the α phase₂Since the precipitation of the Cu phase is very slow, a substantially α single phase state can be achieved at room temperature. Therefore, the titanium plate for the electrolytic Cu foil production drum of the present invention (2) can be produced, and the corrosion by the electrolytic solution becomes extremely homogeneous, and a very high quality Cu foil can be produced. This method is the manufacturing method according to the present invention (4).
[0034]
In the present invention (5), the titanium plate produced by the method described in the present invention (3) or (4) is further cold-rolled and then annealed at a temperature equal to or lower than the β transformation point. This is a technique for achieving a more homogeneous and fine structure by further imparting cold working strain to the titanium plate produced in the present invention (3) or (4) and recrystallizing it again. The annealing is performed at a temperature equal to or lower than the β transformation point as in the case of the present inventions (3) and (4). In particular, when annealing is performed in the α single phase temperature range, the α single phase state can be achieved at room temperature as in the case of the present invention (4). Therefore, the titanium plate for the electrolytic Cu foil production drum of the present invention (2) can be produced, the corrosion by the electrolytic solution becomes very homogeneous, and a very high quality Cu foil can be produced. This method is the production method according to the present invention (6).
[0035]
In the present invention (7), Cu: 0.1 to 2.1%, Cr: one or two of 0.1 to 0.9%, Fe: 0.04% or less, oxygen: 0.1% or less The remainder is composed of titanium and inevitable impurities.
The reasons for limiting Fe and oxygen are the same as in the present invention (1).
The reason for limiting Cu to the range of 0.1 to 2.1% is that, as in the case of the present invention (1), the main hot rolling can be performed in the two-phase temperature range, and the final structure can be homogenously refined. This is to obtain a crystal structure. As shown in the binary equilibrium diagram of FIG. 2, Cu becomes α + β two-phase at 790 to 880 ° C. in the Cu concentration range (0.1 to 2.1%) of the present invention. When Cu is less than 0.1%, the two-phase temperature range of α + β is narrow, and temperature control becomes extremely difficult. Further, when Cu is added in excess of 2.1%, as in the case of the present invention (1), a macro pattern is generated due to solidification segregation and heterogeneity of processing strain due to cold forming.
[0036]
The reason for limiting Cr to 0.1 to 0.9% is the same reason. FIG. 3 shows a Ti—Cr binary phase diagram. In the Cr concentration range (0.1 to 0.9%) of the present invention, the α + β two-phase temperature range is 660 to 870 ° C. If the Cr concentration is less than 0.1%, the temperature range in the α + β two-phase region is narrow, and thus temperature control becomes extremely difficult. On the other hand, when Cr exceeding 0.9% is added, solidification segregation and TiCr₂A macro pattern is generated due to inhomogeneous cold working strain due to an increase in phase.
In addition, when Cu and Cr are contained at the same time, the crystal grains become finer and more uniform. When the total amount of both components exceeds 3%, solidification segregation increases, and macro patterns resulting from this segregation occur, hardness increases excessively, and polishing becomes difficult. It is preferable to do.
[0037]
In the present invention (8), one or more of Mo, Ta, V, Zr, Nb, Hf, and W are contained in order to obtain appropriate hardness and plastic deformability. It is preferable to contain 1% or more. By adding these elements and increasing the hardness moderately, the roughness after polishing is reduced, and a drum material with less micro unevenness can be produced. Mo, Ta, V, and Zr also have a function of improving the corrosion resistance against the sulfuric acid solution. The reason why the total content of one or more of Mo, Ta, V, Zr, Nb, Hf, and W is 1% or less is that if the content is more than this, the macro is caused by segregation of the constituent elements. This is because a pattern is generated, the hardness is excessively increased, and polishing becomes difficult.
[0038]
In the present invention (9), as in the present invention (2), the titanium plate for the electrolytic Cu foil production drum is made of α single phase. In the titanium plate for an electrolytic Cu foil production drum of the present invention (7) or (8), a small amount of β phase and / or precipitated phase may be produced depending on the components and production conditions, as in the description of the present invention (1). There is sex. That is, among Cu and Cr, when Cu is added, the β-phase and / or Ti enriched in Cu₂Cu phase, Cr-rich β phase and / or TiCr when Cr is added₂A phase occurs. In addition, when two types of Cu and Cr are added, a β phase enriched in Cu and Cr and / or a composite precipitated phase of Ti, Cu and Cr (hereinafter referred to as Ti_xCu_yCr_zPhase)).
Even if these β phases and / or precipitated phases are present in a small amount, it is possible to produce a drum capable of producing high-quality Cu foil. Similar to the present invention (2), a very high quality Cu foil can be produced.
[0039]
Here, the α single phase is the structure of the equiaxed crystal shown in FIG. The β phase is a black streak-like phase extending in the lateral direction of the photograph as shown by the arrow 1 in FIG. 5, and the precipitated phase is an equiaxed α phase as shown by the arrow 2 in FIG. It is a black dot-like phase generated at the grain boundary. It is confirmed as follows that the structure is α single phase.
First, 3 to 4 samples of 10 to 20 mm square were collected from the width direction end and center of the part adjacent to the top side and the bottom side of the product plate, the surface was milled, and then sandpaper polishing No. 600 Finishing, observing by etching for several tens of seconds with a nitric acid solution consisting of 10% nitric acid and 3% hydrofluoric acid, and observing each sample for about 5 fields of view at 100 times with an optical microscope, area 3-5 mm²The structure in the range is the α single phase shown in FIG. 4, and the black streak-like phase and the black dot-like phase shown by arrows 1 and 2 in FIG. 5 are not observed.
Here, equiaxed means a structure having crystal grains whose aspect ratio is within 1.4. The measuring method is based on the fact that the average crystal grain size of the test piece collected by the above-described method is measured in a direction of 45 ° with respect to the rolling direction, the width direction, and the rolling direction, and the respective ratios are within 1.4.
[0040]
  The present invention(1) and (7)The average crystal grain size is less than 40 μm because the surface of the electrodeposited copper foil in contact with the titanium drum appears to be slightly rough at 40 μm or more, and is particularly thin copper foil having a thickness of 10 μm or less. This is because the shape is affected. The average grain size is preferably less than 30 μm and the optimum upper limit is less than 20 μm. The crystal grain size is preferably measured by a cutting method.
[0041]
  The present invention (7) to (9The method for producing a titanium plate for an electrolytic Cu foil production drum of) will be described below.
  In the hot rolling of the slab, as in the present inventions (3) and (4), the titanium material is heated to the α + β two-phase temperature region and hot-rolled in the α + β two-phase temperature region. The initial purpose can be achieved if this temperature range is entered during rolling, but if the slab is heated to this temperature range from the beginning, this purpose is surely achieved.
[0042]
  The present invention (10), In the same manner as in the present invention (3), in order to obtain a homogeneous fine recrystallized structure, it was decided to anneal in the temperature range below the β transformation point of the titanium material after hot rolling. The lower limit of the annealing temperature is preferably the recrystallization temperature. The β transformation point is the boundary temperature between the β phase and the α + β phase shown in the Ti—Cu calculation state diagram (FIG. 2) and the Ti—Cr calculation state diagram (FIG. 3).
  In the α + β two-phase region below the β transformation point, since the grain growth is suppressed, a homogeneous fine recrystallization structure can be achieved. During the cooling after annealing, most of the β phase is transformed into the α phase. However, when the cooling rate is fast, the β phase remains, or during the cooling, depending on the components,₂ Cu phase, TiCr₂ Phase or Ti_X Cu_Y Cr_Z A phase may form. However, even if these are produced, they are in a small amount, and as described above, the quality of the Cu foil product is not significantly deteriorated.
[0043]
Also, annealing is performed in a two-phase temperature range lower than the α single phase range, that is, α + Ti.₂Cu two-phase region, α + TiCr₂Two-phase region or α + Ti_xCu_yCr_zIt may be performed in a two-phase region. This two-phase temperature range is a temperature range in which a precipitated phase is present in the α phase in an equilibrium state.₂Cu phase, TiCr₂Phase or Ti_xCu_yCr_zAlthough a phase is present, the reaction in which these precipitate from the α phase is extremely slow and takes 100 hours or more, so this reaction does not occur during actual annealing. Therefore, even when annealing is performed in this two-phase temperature range, the α phase occupies most and a very small amount of β phase is mixed, and the quality of the Cu foil product is not significantly reduced.
[0044]
  The present invention (11), In the same manner as in the present invention (4), after hot rolling, annealing was performed in the α single phase region. In this case, the β phase and Ti that were mixed after hot rolling₂ Cu phase, TiCr₂ Phase or Ti_X Cu_Y Cr_Z All phases are α phases, and a complete α single phase structure is realized. Since this state is a single-phase state, it is easy to grow crystal grains, but since strain is accumulated by hot rolling in the α + β two-phase region, uniform fine recrystallization unless the annealing time is unnecessarily prolonged. The organization can achieve.
  In addition, α + Ti during cooling₂ Cu, α + TiCr₂ Or α + Ti_X Cu_Y Cr_Z As mentioned above, Ti from the α phase₂ Cu phase, TiCr₂ Phase or Ti_X Cu_Y Cr_Z Since the precipitation of the phase is very slow, an α single phase state can be substantially achieved at room temperature. Therefore, a titanium plate for an α single phase electrolytic Cu foil production drum can be produced, and a very high quality Cu foil can be produced.
[0045]
  The present invention (12) In the present invention (10) Or (11) Further, cold rolling was performed on the titanium plate manufactured by the method described above, and then annealing was performed at a temperature equal to or lower than the β transformation point. This is a technique which, like the present invention (5) or (6), attempts to achieve a more homogeneous and fine structure by further applying cold work strain and recrystallizing again. It was decided that the annealing was performed at a temperature below the β transformation point in the present invention (10). Further, when annealing is performed in the α single phase temperature range, the present invention (11As in the case of), the α single phase state can be achieved at room temperature. Therefore, a titanium plate for an α single-phase electrolytic Cu foil production drum can be produced, and the corrosion by the electrolytic solution becomes very homogeneous, and a very high quality Cu foil can be produced. This method is the present invention (13).
[0046]
【Example】
The present invention will be described in more detail with reference to examples.
(Experiment 1)
An ingot composed of the components shown in Table 1 was prepared by melting by vacuum arc twice, and this was ingot rolled into a slab having a thickness of 150 mm. This slab was heated to 850 ° C., hot-rolled in the range of 850 to 700 ° C., hot-rolled to a plate having a temperature thickness of 10 mm, and annealed at 630 ° C. This annealing was performed using a vacuum creep straightener (VCF) as well as shape correction.
[0047]
The test specimen cut out from the above thick plate is ground 2mm in parallel with the plate surface including the black skin part, polished # 600, etched with a nitric acid-based macro corrosive solution, and crystal grains While measuring the diameter, the macro pattern was observed. Moreover, the presence or absence of the pit-shaped hollow was observed by SEM observation. For a plate with a good macro pattern, after descaling, it was bent into a cylindrical drum with a diameter of 2.7 m in the cold, and a test piece cut out from this part was etched with a nitric acid-based macro corrosive solution. The macro pattern was observed.
In addition, macro pattern observation was implemented with respect to three 10cm and 8cm area | regions, and evaluated by the number of macro patterns observed visually. That is, it is a four-stage evaluation: 0 to 1: ◎, 2 to 5: ◯, 6 to 10: Δ, 11 or more: x.
[0048]
In Table 1, test number 1 is the case of normal pure titanium, and the macro pattern was x judgment because it was manufactured by a normal thick plate manufacturing process. On the other hand, in the test number 2 in which Fe is added in a slightly larger amount, the Δ judgment is improved. However, this level is still inadequate. In this material, the β phase enriched with Fe was preferentially dissolved, so pit-like depressions were also observed, which was not preferable as a titanium plate for an electrolytic Cu foil production drum. .
In Test No. 3 and Test No. 4 with Ni added, Ti₂Fine crystal grains were obtained due to the effect of suppressing grain growth of Ni, and the macro pattern evaluation result was ◯. However, this Ti₂Due to the generation of the Ni phase, the strength of the material was increased, the distortion when molded into a drum became non-uniform, and the macro pattern evaluation on the drum was Δ. Further, there is a problem that Ni eluted in a corrosive environment is mixed into the Cu foil, which is not preferable.
[0049]
On the other hand, test numbers 6, 7, 8, and 11, which are examples of the present invention, all obtained homogeneous fine recrystallized grains, and the macro pattern evaluation was a good result of ◎ for the plate and ○ for the drum. Thus, the effects of the present invention have been sufficiently achieved.
[0050]
On the other hand, in test number 5, only a macro pattern determination of Δ was obtained. This is because the Cu addition amount is lower than the lower limit of the present invention, and a sufficient two-phase state was not achieved during hot rolling. Moreover, in test number 9, since the addition amount of Cu exceeded the upper limit of the present invention, solidification segregation became severe and the average particle size was small, but coarse particles were partially mixed, and due to uneven corrosion due to Cu segregation. The macro pattern has been judged as x. In Test No. 10, since the addition amount of Fe exceeded 0.04% defined in the present invention, pit-shaped depressions were generated during corrosion. In Test No. 13, annealing was omitted and a sufficient recrystallized structure was not obtained, and therefore, a macro pattern reflecting non-uniformity in processing strain distribution and stretched coarse grains was generated, resulting in x determination.
[0051]
[Table 1]

[0052]
(Experiment 2)
The temperature shown in the column of slab heating temperature in Table 2 for a slab having a thickness of 150 mm made of exactly the same component (Ti-1.1% Cu-0.03% Fe-0.05% oxygen) as in Test No. 7 of Experiment 1 Then, it was hot-rolled to a 10 mm thick plate and annealed at various temperatures shown in the column of annealing temperature in Table 2.
Thereafter, the crystal grain size, macro pattern, and the like were evaluated in exactly the same manner as in Experiment 1. The results are shown in Table 2. Here, for comparison, the result of test number 7 of Experiment 1 is also shown. Β transformation point of this component, boundary temperature between α + β two-phase temperature region and α single phase region, α single phase region and α + Ti₂The boundary temperatures in the Cu two-phase temperature range are all the same as in test number 7 and are 865 ° C., 825 ° C., and 730 ° C., respectively.
[0053]
In Table 2, the method described in the present invention (3) or (4), that is, slab heating to α + β two-phase region, rolling, annealing at a temperature not higher than β transformation point, test numbers 14, 17, 18, 19, In No. 20, fine grains were obtained, and the macro pattern of the plate was judged as ◎. Moreover, there was no pitting, and the macro pattern after molding on the drum was a good result of ◯ to ◎. In particular, Test Nos. 18 and 19 in which annealing was performed in the α single phase temperature range described in the present invention (4) are macro pattern determinations of ◎ even after forming into a drum, and the effects of the present inventions 2 and 4 Has been demonstrated without regret.
[0054]
Here, in test numbers 14 and 15, the slab heating temperature was out of the temperature range described in the present invention (3), but in test number 14, the temperature dropped during hot rolling, and in test number 15 In the initial stage of hot rolling, both of them were in the α + β two-phase temperature range, and the product of the present invention (1) could be manufactured. However, while the test number 7 in which the slab heating was reliably performed in the α + β region was the macro pattern determination of “◎”, these were all “◯” determination, and the quality was slightly inferior.
In addition, test number 16 in which annealing was performed at a temperature exceeding the β transformation point was heated in the β single phase region where diffusion was extremely fast, so that the strain accumulated in the bending α + β region heating rolling was released all at once and grain growth occurred. As a result, a homogeneous microstructure was not obtained, and the macro pattern evaluation was judged as x.
[0055]
[Table 2]

[0056]
(Experiment 3)
Test numbers 7, 17, and 19 having components of Ti-1.1% Cu-0.03% Fe-0.05% oxygen were selected from the hot-rolled annealed plates produced in Experiments 1 and 2, and these were selected. After descaling, cold rolling was further performed to obtain a 5 mm thick plate. Then, annealing was performed at the temperature described in the column of annealing temperature after cold rolling in Table 3, and the crystal grain size and macro pattern evaluation were performed in the same manner as in Experiments 1 and 2. The results are shown in Table 3.
[0057]
In Table 3, all the plates produced by the method according to the present invention (5) or (6) have a smaller crystal grain size than the case of the hot-rolled annealed plate, and the macro pattern evaluation of the plate is all ◎ It was a judgment. Even in the hot-rolled annealed sheet, ◎ is obtained, but finer crystal grains are obtained. Therefore, when a drum manufactured with this material is used, a denser and higher quality electrolytic Cu foil is manufactured. it can.
[0058]
Here, in test number 19, the hot-rolled annealed plate before cold rolling is composed of an α single phase, but the annealing after cold-rolling is performed by α + Ti.₂Even in the Cu two-phase region, Ti₂Since the precipitation of the Cu phase is extremely slow, the α single phase state is maintained. Therefore, the present invention (2) has been achieved, and even when processed into a drum, a high quality of の is obtained.
In Test Nos. 26 and 27, there was a slight second phase before cold rolling, but since the final annealing after cold rolling was performed in the α single phase region, the present invention (2) was achieved, and the drum Even when processed into high quality, a high quality of ◎ was obtained.
[0059]
[Table 3]

[0060]
(Experiment 4)
An ingot composed of the components shown in Table 4 was made into a slab having a thickness of 150 mm in exactly the same manner as in Experiment 1. This slab was heated to a slab heating temperature shown in Table 4 and hot-rolled within a range from this temperature to 700 ° C. to obtain a hot-rolled sheet having a thickness of 10 mm. Furthermore, annealing was performed at the annealing temperature shown in Table 4 using a vacuum creep straightener (VCF) as well as shape correction. Table 4 also shows the phase states at the heating temperature and annealing temperature estimated from the calculated phase diagram.
[0061]
The measurement of the crystal grain size of the above-mentioned thick plate and the observation of the macro pattern were performed in exactly the same manner as in Experiment 1. In addition, for macro pattern judgments of ◎, ○, and Δ, the presence or absence of pit-like depressions was observed by SEM observation. A pit-shaped depression is a circular or polygonal hole having a diameter of several μm. For the plates with macro pattern judgments of ◎, ○, △, after descaling, they were bent into a cylindrical drum shape with a diameter of 2.7 m in the cold, and a test piece cut out from this part was cut into a nitric acid type The macro pattern was observed by etching with a macro corrosive solution. For a good material having a macro pattern judgment of “◎” or “○” and no pit-like depressions were observed, a weldability test was also conducted to observe whether a weld line could be seen after polishing.
[0062]
Test No. 29 in Table 4 having the same components as Test No. 5 in Table 1 was heated in the α + β two-phase region and hot rolled at the α + β two-phase region temperature. Regarding test numbers 30 and 31, since the hot rolling was performed in the α + β two-phase temperature range, the macro judgment by the plate was “あ っ た”.
The test number 32 is a case of normal pure titanium, and in the manufacturing method by hot rolling (slab heating temperature 850 ° C.) and annealing (annealing temperature 630 ° C.), the macro pattern of the plate was X judgment. In test number 33 containing only 0.03% of Cr, a sufficient two-phase state was not achieved during hot rolling, and the macro pattern judgment was Δ. Thus, when normal pure titanium or Cr content is less than 0.1%, hot rolling in the α + β phase is difficult, so that many unrecrystallized portions remain and the macro pattern determination is insufficient.
[0063]
On the other hand, the test numbers 34, 36, 38, 40 and 41 containing 0.19%, 0.41%, 0.58% and 0.81% Cr each obtained a fine homogeneous microstructure. The macro evaluation was also a good result of ま た は or ○, and the effect of the present invention was sufficiently achieved.
Thus, when Cr is contained in an amount of 0.1 to 0.9% and hot rolled in the α + β phase, the entire material becomes a uniform recrystallized structure even after hot rolling, so that the macro pattern determination is good.
[0064]
On the other hand, in Test No. 35, the amount of Fe added exceeded 0.04% defined in the present invention, and thus pit-shaped depressions were generated during corrosion. In Test No. 37, the amount of oxygen added exceeded 0.1% defined in the present invention, so the weld line did not disappear even after polishing after welding. In Test No. 39, since the temperature at the time of hot rolling was in the β region, the grain growth was remarkable and the crystal grains were coarsened, a homogeneous microstructure was not obtained, and the macro pattern judgment was x. For test number 42 in which annealing was performed in the β region, the crystal grains were similarly coarsened, a homogeneous microstructure was not obtained, and the macro judgment was x. Test No. 43 was when the Cr content was as high as 1.17%, and the macro pattern determination was Δ.
[0065]
Test numbers 44 and 45 are examples of the present invention in the case of containing both Cu and Cr. After hot rolling in the α + β two-phase region and annealing in the α region, the macro pattern judgment of the plate is ◎, The macro pattern judgment was ○. In test number 46, the Cr content was larger than the range of the present invention, and the macro pattern judgment was Δ.
Test numbers 47 to 52 are examples in the case of containing one of Mo, V, Nb, and W and Cu, respectively. Each material had a high gloss after polishing, which was probably due to a slight increase in hardness, and a material with low surface roughness. Macro patterns of test numbers 47 to 50, which were annealed in the α region after hot rolling in the α + β two-phase region, were evaluated as “good”.
In the test numbers 51 and 52 of the comparative examples, the addition amounts of Mo and Nb exceeded 1%, respectively, and a macro pattern due to segregation of those elements was generated, and the macro pattern was a Δ determination.
[0066]
Test numbers 53 to 55 are examples in the case of containing two kinds of Mo, V, Nb, and W and Cu. In these cases, a material having a high gloss after polishing and a small surface roughness, which is considered to be due to a slight increase in hardness, was obtained. The macro patterns of Test Nos. 53 and 54 that were annealed in the α region after hot rolling in the α + β two-phase region were evaluated as “good”.
In test number 55 of the comparative example, the total addition amount of Mo and Nb exceeded 1%, and a macro pattern due to segregation of those elements occurred, and the macro pattern was Δ.
Test numbers 56 to 61 are examples in the case of containing one of Mo, Ta, V, Nb, W, and Hf and Cr. All the materials had a high gloss after polishing, which seems to be caused by a slight increase in hardness, and a material with a small surface roughness. The macro patterns of test numbers 56 to 59 that were annealed in the α region after hot rolling in the α + β two-phase region were evaluated as “good”. In the test numbers 60 and 61 of the comparative examples, the addition amounts of Ta and Hf exceeded 1%, respectively, and a macro pattern due to segregation of those elements was generated.
[0067]
Test numbers 62 to 64 are examples in the case of containing Mo, Ta, Nb, and W and Cr. In these cases, a material having a high gloss after polishing and a small surface roughness, which is considered to be due to a slight increase in hardness, was obtained. The macro patterns of Test Nos. 62 and 63 that were annealed in the α region after hot rolling in the α + β two-phase region were evaluated as “good”.
In the test number 64 of the comparative example, the total addition amount of Mo and Nb exceeded 1%, and a macro pattern due to segregation of those elements occurred.
[0068]
[Table 4]

[0069]
(Experiment 5)
An ingot comprising the components shown in Table 5 was made into a slab having a thickness of 150 mm in exactly the same manner as in Experiment 1. This slab was heated to the slab heating temperature shown in Table 5 and hot-rolled to a 10 mm thick plate. Furthermore, annealing was performed at the annealing temperature shown in the column of annealing 1 in Table 5 using a vacuum creep straightening machine (VCF) also for shape correction. The phase state at the annealing temperature estimated from the calculated phase diagram is also shown in the column of annealing 1 in Table 5. These were descaled and further cold-rolled to form 5 mm thick plates. Then, annealing was performed at the temperature shown in annealing 2 of Table 5, and the crystal grain size and macro pattern were determined by the same method as in Experiment 1. The column of annealing 2 in Table 5 also shows the phase state at the annealing temperature estimated from the calculated phase diagram.
Samples with macro pattern judgments of ◎, ○, and △ were observed by SEM for the presence or absence of pit-like depressions, and were bent into a cylindrical drum shape with a diameter of 2.7 m in a cold manner. Cutting out and observing the macro pattern. Furthermore, for a good material in which the macro pattern judgment was “◎” or “○” and no pit-like depression was observed, a weldability test was also conducted to observe whether a weld line could be seen after polishing.
[0070]
Test numbers 65-71, 73-75, 77, 79-81, 83 are all ◎ for both the macro pattern evaluation of the plate and the macro pattern evaluation of the drum, there is no pitting, and the weld line after welding Was also not observed. On the other hand, in the test number 72 where the contents of Cu and Cr are larger than the specified values of the present invention, the macro pattern evaluation of the plate was Δ. In addition, in Test Nos. 76, 78, 82, and 84, the addition amount of V, the total addition amount of Ta and Hf, the addition amount of Zr, and the total addition amount of Zr and Hf exceed the specified values of the present invention. The macro pattern evaluation of the plate was Δ.
[0071]
[Table 5]

[0072]
【The invention's effect】
As described above, according to the present invention, a titanium plate for an electrolytic Cu foil production drum having a uniform and fine plate surface metallographic structure with few macro patterns and suitable for producing high-quality electrolytic Cu foil and a method for producing the same. Can be provided without going through a complicated heat treatment process.
[Brief description of the drawings]
FIG. 1 shows a part of a binary equilibrium diagram of Ti and Cu.
FIG. 2 is a diagram showing a part of a binary system equilibrium diagram of Ti and Cu.
FIG. 3 is a diagram showing a part of a binary system equilibrium diagram of Ti and Cr.
FIG. 4 is a view showing a microstructure of an α single-phase titanium plate.
FIG. 5 is a view showing a microstructure of a titanium plate having a β phase and a precipitated phase.

Claims (13)

% By mass
Cu: 0.5 to 2.1%,
Fe: 0.04% or less,
A titanium plate for an electrolytic Cu foil production drum, comprising oxygen: 0.1% or less, comprising a balance of titanium and inevitable impurities, and having a homogeneous fine recrystallized structure having an average crystal grain size of less than 40 μm .   The titanium plate for an electrolytic Cu foil production drum according to claim 1, wherein the titanium plate is composed of an α single phase. % By mass
Cu: 0.5 to 2.1%,
Fe: 0.04% or less,
Oxygen: A slab containing 0.1% or less and the balance titanium and inevitable impurities is heated to a two-phase temperature range of α + β, hot-rolled, and further annealed at a temperature below the β transformation point. The manufacturing method of the titanium plate for electrolytic Cu foil manufacturing drums. % By mass
Cu: 0.5 to 2.1%,
Fe: 0.04% or less,
Oxygen: The slab containing 0.1% or less and the balance titanium and inevitable impurities is heated to the α + β two-phase temperature range, hot-rolled, and further annealed in the α single-phase temperature range. A method for producing a titanium plate for an electrolytic Cu foil production drum.   A method for producing a titanium plate for an electrolytic Cu foil production drum, wherein the method further comprises cold rolling after the method according to claim 3 or 4 and then annealing at a temperature not higher than the β transformation point.   5. A method for producing a titanium plate for an electrolytic Cu foil production drum, comprising performing cold rolling after the method according to claim 3 or 4 and then performing annealing in an α single phase temperature range. % By mass
Cu: 0.1 to 2.1%
Cr: 0.1-0.9%
1 type or 2 types of
Fe: 0.04% or less,
A titanium plate for an electrolytic Cu foil production drum, comprising oxygen: 0.1% or less, comprising a balance of titanium and inevitable impurities, and having a homogeneous fine recrystallized structure having an average crystal grain size of less than 40 μm .   8. The electrolytic Cu foil production drum according to claim 7, further comprising 1% or less in total of one or more of Mo, Ta, V, Zr, Nb, Hf, and W by mass%. Titanium plate.   The titanium plate for an electrolytic Cu foil production drum according to claim 7 or 8, comprising an α single phase. The slab containing components according to claim 7 or 8, a second heat phase temperature range of the alpha + beta, and hot rolling, characterized by further annealed at beta transformation point temperature, claim 7-9 The manufacturing method of the titanium plate for electrolytic Cu foil manufacture drums of any one of these. The slab composed of the component according to claim 7 or 8 is heated to an α + β two-phase temperature range, hot-rolled, and further annealed in an α single-phase temperature range. 10. A method for producing a titanium plate for an electrolytic Cu foil production drum according to any one of 9 above. A method for producing a titanium plate for an electrolytic Cu foil production drum, characterized in that, following the method according to claim 10 or 11 , further cold rolling is performed and then annealing is performed at a temperature not higher than the β transformation point. The manufacturing method of the titanium plate for electrolytic Cu foil manufacturing drums which performs cold rolling further after the method of Claim 10 or 11 , and then anneals in alpha single phase temperature range.

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