JP2002289097A - Method of manufacturing aperture grill - Google Patents
Method of manufacturing aperture grillInfo
- Publication number
- JP2002289097A JP2002289097A JP2001085146A JP2001085146A JP2002289097A JP 2002289097 A JP2002289097 A JP 2002289097A JP 2001085146 A JP2001085146 A JP 2001085146A JP 2001085146 A JP2001085146 A JP 2001085146A JP 2002289097 A JP2002289097 A JP 2002289097A
- Authority
- JP
- Japan
- Prior art keywords
- aperture grill
- molybdenum
- iron
- plating
- kgf
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はめっき法により作製
されるアパチャーグリルの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an aperture grill manufactured by a plating method.
【０００２】[0002]
【従来の技術】従来アパチャーグリルは、鋼板にレジス
ト層を形成しストライプ状のスリット形状をパターニン
グした後、塩化第二鉄溶液でエッチングを施し、多数の
スリットを形成し、その後レジストを除去するエッチン
グ法で製造されている。しかしながら近年、高精密、高
精細の画面が要求されるディスプレー用のカラー受像管
に内装するアパチャーグリルは、この画面に対応するよ
うに電子ビーム通過部であるスリットのピッチが極めて
微細なものが使用されるようになってきた。このため、
従来のエッチング法で作製されたアパチャーグリルでは
寸法精度における不良品の発生率が高く、製品歩留まり
が低く、また廃エッチング液の廃液処理に手間がかかる
などの欠点もあった。2. Description of the Related Art Conventionally, an aperture grill is formed by forming a resist layer on a steel plate, patterning a striped slit shape, etching with a ferric chloride solution to form a number of slits, and then removing the resist. Manufactured by law. However, in recent years, the aperture grille installed in color picture tubes for displays that require high-precision, high-definition screens has a very fine pitch of slits, which are electron beam passage sections, corresponding to this screen. It has come to be. For this reason,
The aperture grille manufactured by the conventional etching method has disadvantages such as a high occurrence rate of defective products in dimensional accuracy, a low product yield, and a troublesome treatment of a waste etching solution.
【０００３】これに対して最近では、めっき法によるア
パチャーグリルの製造が試みられている。このアパチャ
ーグリルは、導体基板上にレジスト層を形成し、パター
ニングした後、露出した導体基板表面部に電気鉄めっき
を施した後、該導体基板を外的な応力などにより歪ませ
て、電気鉄めっきを皮膜の端の部分を剥離し、その部分
よりめっき皮膜全体を剥離して製造される。On the other hand, recently, an attempt has been made to manufacture an aperture grill by a plating method. This aperture grill is formed by forming a resist layer on a conductor substrate, patterning the same, applying an electric iron plating to the exposed surface of the conductor substrate, and distorting the conductor substrate by external stress or the like. The plating is manufactured by peeling the end portion of the film and peeling the entire plating film from the portion.
【０００４】一方、アパチャーグリルは電子ビームの反
射を抑制するため、テレビフレームに装着した後、黒化
処理という工程で鉄部を四三酸化鉄として黒染めする。
この黒化処理は約４７５℃で行われるが、通常のめっき
法により作製されたアパチャーグリルは高温引張強度が
弱いためしばしば断線が発生する。特に最近では、高精
細化が進み、アパチャーグリルの製造が非常に微細にな
っているため、僅かな応力でも局所的に集中すると断線
が発生し歩留まりが低くなるという問題がある。そこ
で、電気めっき法で作製されるアパチャーグリルの耐熱
強度の改良が検討されており、中でもモリブデンを含有
する鉄あるいは鉄系合金を主体としたアパチャーグリル
は非常に有力である。On the other hand, in order to suppress the reflection of the electron beam, the aperture grill is mounted on a television frame, and then the iron portion is blackened as ferric oxide in a blackening process.
This blackening treatment is performed at about 475 ° C., but the aperture grill produced by the usual plating method often has a disconnection due to a low high-temperature tensile strength. In particular, recently, since the definition of the aperture grill has been advanced and the production of the aperture grill has become extremely fine, there is a problem that even if a slight stress is locally concentrated, disconnection occurs and the yield decreases. Therefore, improvement of the heat resistance of the aperture grill produced by the electroplating method has been studied. Among them, the aperture grill mainly composed of iron or an iron-based alloy containing molybdenum is very effective.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、めっき法で
作製されるアパチャーグリルにおいて、耐熱強度の改良
に有力なモリブデンを含有する鉄あるいは鉄系合金のめ
っき法による製造方法を提案することを目的とするもの
である。SUMMARY OF THE INVENTION The present invention proposes a method of producing an iron or iron-based alloy containing molybdenum by plating, which is effective for improving the heat resistance of an aperture grill produced by plating. It is the purpose.
【０００６】[0006]
【課題を解決するための手段】本発明は、アパチャーグ
リルの黒化処理に相当する熱処理を施しても、破断に至
ることのない耐熱強度を有したモリブデンを含有する鉄
あるいは鉄系合金からなるアパチャーグリルをめっき法
により製造する方法であり、その要旨は、モリブデンを
含有する鉄あるいは鉄系合金の単独および該金属層を含
む多層構造からなるアパチャーグリルをめっき法により
製造する方法において、前記金属層を塩化第一鉄を主成
分とする電気鉄めっき液にモリブデン酸塩またはモリブ
デン−クエン酸錯イオンを添加することにより得ること
を特徴とし、また前記電気鉄めっき液中に添加するモリ
ブデン酸塩量またはモリブデン−クエン酸錯イオン量
を、それぞれモリブデンイオン濃度として１ｍｇ／Ｌ以
上で６００ｍｇ／Ｌ以下、１ｍｇ／Ｌ以上で５００ｍｇ
／Ｌ以下とすることを特徴とするものである。SUMMARY OF THE INVENTION The present invention comprises a molybdenum-containing iron or iron-based alloy having a heat resistant strength which does not cause breakage even when subjected to a heat treatment corresponding to a blackening treatment of an aperture grill. A method of manufacturing an aperture grill by a plating method, the gist of which is that a method of manufacturing an aperture grill having a multilayer structure including a single layer of molybdenum-containing iron or an iron-based alloy and a multilayer structure including the metal layer by the plating method. The layer is obtained by adding molybdate or molybdenum-citrate complex ion to an electric iron plating solution containing ferrous chloride as a main component, and the molybdate added to the electric iron plating solution is provided. Amount or molybdenum-citrate complex ion amount as molybdenum ion concentration of 1 mg / L or more and 600 mg / L Below, 500mg at 1mg / L or more
/ L or less.
【０００７】[0007]
【発明の実施の形態】テレビフレームへのアパチャーグ
リルの装着は、テレビフレームに荷重をかけて変形させ
た状態で抵抗加熱溶接により行われる。その後、荷重を
除去するとアパチャーグリルのテープ部には約２０ｋｇ
ｆ／ｍｍ２の張力がかかることになる。通常鉄単体の場
合、常温での引張強度は３０〜４０ｋｇｆ／ｍｍ２であ
り、アパチャーグリルをフレームに装着する際に断線は
殆ど発生しないが、黒化処理が行われる４７５℃の高温
領域では、鉄単体の引張強度は約１５ｋｇｆ／ｍｍ２ま
で低下する。高温領域では、クリープなどによる応力緩
和はあるものの引張強度の低下により断線の発生率は高
くなる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The mounting of an aperture grille on a television frame is performed by resistance heating welding while the television frame is deformed by applying a load. After that, when the load is removed, about 20 kg is added to the tape of the aperture grill.
A tension of f / mm 2 will be applied. In the case of ordinary iron alone, the tensile strength at room temperature is 30 to 40 kgf / mm 2 , and almost no disconnection occurs when the aperture grill is mounted on the frame. However, in the high temperature region of 475 ° C. where the blackening process is performed, The tensile strength of iron alone drops to about 15 kgf / mm 2 . In the high temperature region, although the stress is relaxed due to creep or the like, the rate of occurrence of disconnection increases due to a decrease in tensile strength.
【０００８】このような問題を解決する手段として、モ
リブデンを含有した鉄あるいは鉄系合金を用いることで
耐熱強度を改良する方法がある。このとき、鉄あるいは
鉄系合金に含有するモリブデンの量は少なくとも０．０
１重量％以上必要とされる。As a means for solving such a problem, there is a method of improving heat resistance by using molybdenum-containing iron or an iron-based alloy. At this time, the amount of molybdenum contained in the iron or iron-based alloy is at least 0.0
1% by weight or more is required.
【０００９】本発明は、めっき法でモリブデンを含有し
た鉄あるいは鉄系合金層を作製するため種々の検討を行
った結果、塩化第一鉄を主成分とする電気鉄めっき液に
モリブデン酸塩またはモリブデン−クエン酸錯イオンを
添加することによってこの目的を達成できることを見出
し、本発明を完成するに至った。According to the present invention, as a result of conducting various studies for producing an iron or iron-based alloy layer containing molybdenum by a plating method, molybdate or molybdate is added to an electric iron plating solution containing ferrous chloride as a main component. It has been found that this object can be achieved by adding a molybdenum-citrate complex ion, and the present invention has been completed.
【００１０】前記電気鉄めっき液中の鉄イオン濃度は通
常２００ｇ／Ｌ前後であり、この液にモリブデシ酸塩を
微量添加した場合、めっき皮膜中に含有されるモリブデ
ンの量は添加量にほぼ比例する。本発明では、前記電気
鉄めっき液にモリブデン酸塩またはモリブデン−クエン
酸錯イオンを添加するが、モリブデン酸塩またはモリブ
デン−クエン酸錯イオンは、電気鉄めっき液中に安定な
イオンの状態で存在し、さらに電気めっきの際、誘起共
析によって効率的に皮膜中に取込まれることが期待でき
る。The iron ion concentration in the electric iron plating solution is usually around 200 g / L. When a small amount of molybdenum salt is added to this solution, the amount of molybdenum contained in the plating film is almost proportional to the amount added. I do. In the present invention, molybdate or molybdenum-citrate complex ion is added to the electric iron plating solution, and the molybdate or molybdenum-citrate complex ion is present in the electric iron plating solution in a stable ion state. In addition, it can be expected that at the time of electroplating, it is efficiently incorporated into the film by induced eutectoid.
【００１１】本発明において、前記電気鉄めっき液中の
モリブデンイオン濃度を１ｍｇ／Ｌ以上で６００ｍｇ／
Ｌ以下としたのは、１ｍｇ／Ｌ未満ではめっき皮膜中に
含有するモリブデンの量が０．０１重量％未満となり十
分な耐熱強度が得られず、他方、６００ｍｇ／Ｌを超え
るとめっき皮膜が脆くなり割れを生じ易く、黒化処理以
前の工程でアパチャーグリルのテープ部に断線が発生す
るためである。また、モリブデン−クエン酸錯イオン濃
度を１ｍｇ／Ｌ以上で５００ｍｇ／Ｌ以下としたのは、
前記と同様、モリブデン−クエン酸錯イオン濃度が１ｍ
ｇ／Ｌ未満ではめっき皮膜中に含有するモリブデン−ク
エン酸の量が０．０１重量％未満となり十分な耐熱強度
が得られず、他方、モリブデン−クエン酸錯イオン濃度
が５００ｍｇ／Ｌより大きくなるとめっき皮膜が脆くな
り割れを生じ易く、黒化処理以前の工程でアパチャーグ
リルのテープ部に断線が発生するためである。なお、本
発明で用いるモリブデン酸塩は特に限定されないが、モ
リブデン酸二ナトリウム二水和物や七モリブデン酸六ア
ンモニウム四水和物が経済性の点で好ましい。また、モ
リブデン−クエン酸錯イオンの添加方法としては特に限
定されず、予め所定量のモリブデン酸塩とクエン酸ある
いはクエン酸塩を水溶液中で溶解、混合し、錯イオンを
形成させた後、添加するなどの方法でよい。[0011] In the present invention, the concentration of molybdenum ion in the electric iron plating solution is set to 1 mg / L to 600 mg / L.
When the content is less than 1 mg / L, the amount of molybdenum contained in the plating film is less than 0.01% by weight and sufficient heat resistance cannot be obtained. On the other hand, when it exceeds 600 mg / L, the plating film becomes brittle. This is because cracks easily occur, and the tape portion of the aperture grill is disconnected in a step before the blackening treatment. Further, the molybdenum-citrate complex ion concentration was set to 1 mg / L or more and 500 mg / L or less because
As described above, the concentration of the molybdenum-citrate complex ion is 1 m.
When the amount is less than g / L, the amount of molybdenum-citric acid contained in the plating film is less than 0.01% by weight, and sufficient heat resistance cannot be obtained. This is because the plating film becomes brittle and easily cracks, and the tape portion of the aperture grill is disconnected in a step before the blackening treatment. The molybdate used in the present invention is not particularly limited, but disodium molybdate dihydrate and hexaammonium hexamolybdate tetrahydrate are preferable in terms of economy. The method for adding the molybdenum-citrate complex ion is not particularly limited, and a predetermined amount of molybdate and citric acid or citrate are dissolved and mixed in an aqueous solution in advance to form a complex ion. Or other methods.
【００１２】[0012]
【実施例】実施例１ ６５×６５ｃｍのチタン板の全面に厚さ１５μｍの感光
性レジストフィルムをラミネートし、レジスト層を形成
した後、幅１４０μｍ、縦方向長さ２１０ｍｍ、間隔１
１０μｍのスリットをもつ写真製板用マスクを載置した
後、露光を行い、現像し、パターニングを施した。つぎ
に表１に示す液組成および条件で、露出したチタン板表
面に電気銅めっきを行い、続いて表２に示す液組成およ
び条件で電気鉄めっきを行い、該チタン板表面に銅、鉄
を順に３、４２μｍ形成した。その後、レジスト層を剥
離し、アパチャーグリルをチタン板から剥ぎ取った後、
電着物の銅層を選択的に溶解除去することによって、テ
ープ断面形状がリベット状となるアパチャーグリルを得
た。得られたアパチャーグリルをテープ部に２０ｋｇｆ
／ｍｍ２の張力を印加しながら黒化処理に相当する４７
５℃、３０分間の熱処理を行ったが、断線は全く発生し
なかった。このとき、作製した鉄皮膜中のモリブデン含
有量は０．０１重量％であり、４７５℃、アルゴン雰囲
気中、歪速度０．５ｍｍ／ｍｉｎ．での引張試験を行っ
た結果、引張強度は２１ｋｇｆ／ｍｍ２であった。EXAMPLE 1 A photosensitive resist film having a thickness of 15 .mu.m was laminated on the entire surface of a titanium plate of 65.times.65 cm to form a resist layer, and then a width of 140 .mu.m, a longitudinal length of 210 mm and an interval of 1 mm.
After placing a photolithographic mask having a 10 μm slit, exposure was performed, developed, and patterned. Next, with the liquid composition and conditions shown in Table 1, the exposed titanium plate surface was subjected to electrolytic copper plating, and subsequently, with the liquid composition and conditions shown in Table 2, electrolytic iron plating was performed, and copper and iron were deposited on the titanium plate surface. 3, 42 μm were formed in this order. Then, after peeling the resist layer and peeling the aperture grill from the titanium plate,
By selectively dissolving and removing the copper layer of the electrodeposit, an aperture grill having a rivet-shaped tape cross section was obtained. 20 kgf of the obtained aperture grill on the tape
/ Mm 2 while applying a tension of 47, corresponding to the blackening process.
Heat treatment was performed at 5 ° C. for 30 minutes, but no disconnection occurred. At this time, the molybdenum content in the produced iron film was 0.01% by weight, and the strain rate was 0.5 mm / min. As a result, a tensile strength was 21 kgf / mm 2 .
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【表２】 [Table 2]
【００１５】実施例２ 実施例１において電気鉄めっきを表３に示す液組成およ
び条件で行った以外は、実施例１と同様な手順でアパチ
ャーグリルを得た。得られたアパチャーグリルをテープ
部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理
に相当する４７５℃、３０分間の熱処理を行ったが、断
線は全く発生しなかった。このとき、作製した鉄皮膜中
のモリブデン含有量は０．４重量％であり、４７５℃、
アルゴン雰囲気中、歪速度０．５ｍｍ／ｍｉｎ．での引
張試験を行った結果、引張強度は２８ｋｇｆ／ｍｍ２で
あった。Example 2 An aperture grill was obtained in the same manner as in Example 1, except that the electroplating was carried out with the liquid composition and conditions shown in Table 3. The obtained aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes corresponding to a blackening treatment while applying a tension of 20 kgf / mm 2 to the tape portion, but no disconnection occurred. At this time, the molybdenum content in the produced iron film was 0.4% by weight,
In an argon atmosphere, the strain rate was 0.5 mm / min. As a result, a tensile strength was 28 kgf / mm 2 .
【００１６】[0016]
【表３】 [Table 3]
【００１７】実施例３ 実施例１において電気鉄めっきを表４に示す液組成およ
び条件で行った以外は、実施例１と同様な手順でアパチ
ャーグリルを得た。得られたアパチャーグリルをテープ
部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理
に相当する４７５℃、３０分間の熱処理を行ったが、断
線は全く発生しなかった。このとき、作製した鉄皮膜中
のモリブデン含有量は５重量％であり、４７５℃、アル
ゴン雰囲気中、歪速度０．５ｍｍ／ｍｉｎ．での引張試
験を行った結果、引張強度は３０ｋｇｆ／ｍｍ２であっ
た。Example 3 An aperture grill was obtained in the same manner as in Example 1 except that the electric iron plating was performed under the liquid composition and conditions shown in Table 4. The obtained aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes corresponding to a blackening treatment while applying a tension of 20 kgf / mm 2 to the tape portion, but no disconnection occurred. At this time, the molybdenum content in the prepared iron film was 5% by weight, and the strain rate was 0.5 mm / min. As a result, the tensile strength was 30 kgf / mm 2 .
【００１８】[0018]
【表４】 [Table 4]
【００１９】実施例４ 実施例１において電気鉄めっきを表５に示す液組成およ
び条件で行った以外は、実施例１と同様な手順でアパチ
ャーグリルを得た。得られたアパチャーグリルをテープ
部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理
に相当する４７５℃、３０分間の熱処理を行ったが、断
線は全く発生しなかった。このとき、作製した鉄皮膜中
のモリブデン含有量は０．５重量％であり、４７５℃、
アルゴン雰囲気中、歪速度０．５ｍｍ／ｍｉｎ．での引
張試験を行った結果、引張強度は２８ｋｇｆ／ｍｍ２で
あった。Example 4 An aperture grill was obtained in the same manner as in Example 1 except that the electric iron plating was performed under the liquid composition and conditions shown in Table 5. The obtained aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes corresponding to a blackening treatment while applying a tension of 20 kgf / mm 2 to the tape portion, but no disconnection occurred. At this time, the molybdenum content in the produced iron film was 0.5% by weight,
In an argon atmosphere, the strain rate was 0.5 mm / min. As a result, a tensile strength was 28 kgf / mm 2 .
【００２０】[0020]
【表５】 [Table 5]
【００２１】実施例５ 実施例１と同様な手順でチタン板にパタ−ニングを施
し、表１に示す液組成および条件で、露出したチタン板
表面に電気銅めっきを行い、続いて表３に示す液組成お
よび条件で電気鉄めっきを、表６に示す液組成および条
件で電気ニッケルめっきを行い、再度表３に示す液組成
および条件で電気鉄めっきを行い、該チタン板表面に
銅、鉄、ニッケル、鉄を順にそれぞれ３μｍ、１０μ
ｍ、４μｍ、２８μｍ形成した。その後、レジスト層を
剥離し、アパチャーグリルをチタン板から剥ぎ取った
後、電着物の銅層を選択的に溶解除去することによっ
て、テープ断面形状がリベット状となるアパチャーグリ
ルを得た。得られたアパチャーグリルをテープ部に２０
ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理に相当す
る４７５℃、３０分間の熱処理を行ったが、断線は全く
発生しなかった。このとき、作製した鉄皮膜中のモリブ
デン含有量は０．４重量％であり、４７５℃、アルゴン
雰囲気中、歪速度０．５ｍｍ／ｍｉｎ．での引張試験を
行った結果、引張強度は２５ｋｇｆ／ｍｍ２であった。Example 5 Patterning was performed on a titanium plate in the same procedure as in Example 1. Electroless copper plating was performed on the exposed surface of the titanium plate with the liquid composition and conditions shown in Table 1, and then Table 3 Electric iron plating was performed under the liquid composition and conditions shown in the table, and nickel electroplating was performed under the liquid composition and conditions shown in Table 6, and again electric iron plating was performed under the liquid composition and conditions shown in Table 3. , Nickel and iron in order of 3 μm and 10 μm, respectively.
m, 4 μm, and 28 μm. Thereafter, the resist layer was peeled off, the aperture grill was peeled off from the titanium plate, and then the copper layer of the electrodeposit was selectively dissolved and removed to obtain an aperture grill having a rivet-shaped tape cross section. Put the obtained aperture grill on the tape
Heat treatment was performed at 475 ° C. for 30 minutes corresponding to the blackening treatment while applying a tension of kgf / mm 2 , but no disconnection occurred. At this time, the molybdenum content in the prepared iron film was 0.4% by weight, and the strain rate was 0.5 mm / min. As a result, a tensile strength was 25 kgf / mm 2 .
【００２２】[0022]
【表６】 [Table 6]
【００２３】比較例１ 実施例１において電気鉄めっきを表７で示す液組成およ
び条件で行った以外、すなわちモリブデン酸塩の添加を
行わなかった以外は、実施例１と同様な手順でアパチャ
ーグリルを得た。得られたアパチャーグリルをテープ部
に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理に
相当する４７５℃、３０分間の熱処理を行ったが、断線
を発生するものがあり歩留まりは約４０％であった。こ
のとき、４７５℃、アルゴン雰囲気中、歪速度０．５ｍ
ｍ／ｍｉｎ．での引張試験を行った結果、引張強度は１
５ｋｇｆ／ｍｍ２であった。COMPARATIVE EXAMPLE 1 An aperture grill was prepared in the same manner as in Example 1 except that the electroplating was carried out in the same manner as in Example 1 except that the electroplating was carried out under the conditions shown in Table 7, ie, no molybdate was added. I got The obtained aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes, which corresponds to a blackening treatment, while applying a tension of 20 kgf / mm 2 to the tape portion. However, there was a case where disconnection occurred and the yield was about 40%. there were. At this time, at 475 ° C. in an argon atmosphere, the strain rate was 0.5 m.
m / min. As a result of conducting a tensile test, the tensile strength was 1
It was 5 kgf / mm 2 .
【００２４】[0024]
【表７】 [Table 7]
【００２５】比較例２ 実施例１において電気鉄めっきを表８で示す液組成およ
び条件で行った以外は、実施例１と同様な手順でアパチ
ャーグリルを得た。得られたアパチャーグリルをテープ
部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理
に相当する４７５℃、３０分間の熱処理を行ったが、断
線を発生するものがあり、歩留まりは約６０％であっ
た。このとき、作製した鉄皮膜中のモリブデン含有量は
０．００８重量％であり、４７５℃、アルゴン雰囲気
中、歪速度０．５ｍｍ／ｍｉｎ．での引張試験を行った
結果、引張強度は１７ｋｇｆ／ｍｍ２であった。Comparative Example 2 An aperture grill was obtained in the same manner as in Example 1, except that the electroplating was carried out in the same manner as in Example 1, except that the electroplating was carried out under the conditions shown in Table 8. The obtained aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes corresponding to a blackening treatment while applying a tension of 20 kgf / mm 2 to the tape portion, but there was a case where disconnection occurred, and the yield was about 60%. Met. At this time, the content of molybdenum in the produced iron film was 0.008% by weight, and the strain rate was 0.5 mm / min. As a result of the tensile test, the tensile strength was 17 kgf / mm 2 .
【００２６】[0026]
【表８】 [Table 8]
【００２７】比較例３ 実施例１において電気鉄めっきを表９で示す液組成およ
び条件で行った以外は、実施例１と同様な手順でレジス
ト剥離まで行った。しかし、チタン板から剥ぎ取る際に
僅かな応力でテープ部の一部に折れが発生し、断線に至
ったため、陰極線管を作製することができなかった。こ
のとき、作製した鉄皮膜中のモリブデン含有量は６重量
％であった。Comparative Example 3 The procedure of Example 1 was repeated, except that the iron plating was carried out under the same composition and conditions as those shown in Table 9, until the resist was removed. However, when the tape was peeled off from the titanium plate, a slight stress caused a part of the tape to be broken, resulting in disconnection, so that a cathode ray tube could not be manufactured. At this time, the molybdenum content in the produced iron film was 6% by weight.
【００２８】[0028]
【表９】 [Table 9]
【００２９】実施例６ ６５×６５ｃｍのチタン板の全面に厚さ１５μｍの感光
性レジストフィルムをラミネートし、レジスト層を形成
した後、幅１４０μｍ、縦方向長さ２１０ｍｍ、間隔１
１０μｍのスリットをもつ写真製板用マスクを載置した
後、露光を行い、現像し、パターニングを施した。つぎ
に表１０に示す液組成および条件で、露出したチタン板
表面に電気銅めっきを行い、続いて表１１に示す液組成
および条件で電気鉄めっきを行い、該チタン板表面に
銅、鉄を順にそれそれ３μｍ、４２μｍ形成した。その
後、レジスト層を剥離し、アパチャーグリルをチタン板
から剥ぎ取った後、電着物の銅層を選択的に溶解除去す
ることによって、テープ断面形状がリベット状となるア
パチャーグリルを得た。得られたアパチャーグリルをテ
ープ部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化
処理に相当する４７５℃、３０分間の熱処理を行った
が、断線は全く発生しなかった。このとき、作製した鉄
皮膜中のモリブデン含有量は０．０１重量％であり、４
７５℃、アルゴン雰囲気中、歪速度０．５ｍｍ／ｍｉ
ｎ．での引張試験を行った結果、引張強度は２１ｋｇｆ
／ｍｍ２であった。Example 6 A photosensitive resist film having a thickness of 15 μm was laminated on the entire surface of a titanium plate having a size of 65 × 65 cm, and a resist layer was formed.
After placing a photolithographic mask having a slit of 10 μm, exposure was performed, developed, and patterned. Next, with the liquid composition and conditions shown in Table 10, the exposed titanium plate surface was subjected to electrolytic copper plating, and subsequently, with the liquid composition and conditions shown in Table 11, electric iron plating was performed, and copper and iron were deposited on the titanium plate surface. 3 μm and 42 μm were formed in this order. Thereafter, the resist layer was peeled off, the aperture grill was peeled off from the titanium plate, and then the copper layer of the electrodeposit was selectively dissolved and removed to obtain an aperture grill having a rivet-shaped tape cross section. The obtained aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes corresponding to a blackening treatment while applying a tension of 20 kgf / mm 2 to the tape portion, but no disconnection occurred. At this time, the molybdenum content in the produced iron film was 0.01% by weight,
75 ° C, argon atmosphere, strain rate 0.5mm / mi
n. As a result of a tensile test, the tensile strength was 21 kgf
/ Mm 2 .
【００３０】[0030]
【表１０】 [Table 10]
【００３１】[0031]
【表１１】 [Table 11]
【００３２】実施例７ 実施例６において電気鉄めっきを表１２に示す液組成お
よび条件で行った以外は、実施例６と同様な手順でアパ
チャーグリルを得た。得られたアパチャーグリルをテー
プ部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処
理に相当する４７５℃、３０分間の熱処理を行ったが、
断線は全く発生しなかった。このとき、作製した鉄皮膜
中のモリブデン含有量は０．４重量％であり、４７５
℃、アルゴン雰囲気中、歪速度０．５ｍｍ／ｍｉｎ．で
の引張試験を行った結果、引張強度は２８ｋｇｆ／ｍｍ
２であった。Example 7 An aperture grill was obtained in the same manner as in Example 6, except that the electric iron plating was performed under the liquid composition and conditions shown in Table 12. The obtained aperture grill was subjected to heat treatment at 475 ° C. for 30 minutes corresponding to blackening while applying a tension of 20 kgf / mm 2 to the tape portion.
No disconnection occurred. At this time, the molybdenum content in the produced iron film was 0.4% by weight,
° C, in an argon atmosphere, at a strain rate of 0.5 mm / min. As a result of conducting a tensile test, the tensile strength was 28 kgf / mm
It was 2 .
【００３３】[0033]
【表１２】 [Table 12]
【００３４】実施例８ 実施例６において電気鉄めっきを表１３に示す液組成お
よび条件で行った以外は実施例６と同様な手順でアパチ
ャーグリルを得た。得られたアパチャーグリルをテープ
部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理
に相当する４７５℃、３０分間の熱処理を行ったが、断
線は全く発生しなかった。このとき、作製した鉄皮膜中
のモリブデン含有量は５重量％であり、４７５℃、アル
ゴン雰囲気中、歪速度０．５ｍｍ／ｍｉｎ．での引張試
験を行った結果、引張強度は３０ｋｇｆ／ｍｍ２であっ
た。Example 8 An aperture grill was obtained in the same manner as in Example 6, except that the electric iron plating was performed under the liquid composition and conditions shown in Table 13. The obtained aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes corresponding to a blackening treatment while applying a tension of 20 kgf / mm 2 to the tape portion, but no disconnection occurred. At this time, the molybdenum content in the prepared iron film was 5% by weight, and the strain rate was 0.5 mm / min. As a result, the tensile strength was 30 kgf / mm 2 .
【００３５】[0035]
【表１３】 [Table 13]
【００３６】実施例９ 実施例６において電気鉄めっきを表１４に示す液組成お
よび条件で行った以外は実施例６と同様な手順でアパチ
ャーグリルを得た。得られたアパチャーグリルをテープ
部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理
に相当する４７５℃、３０分間の熱処理を行ったが、断
線は全く発生しなかった。このとき、作製した鉄皮膜中
のモリブデン含有量は０．５重量％であり、４７５℃、
アルゴン雰囲気中、歪速度０．５ｍｍ／ｍｉｎ．での引
張試験を行った結果、引張強度は２８ｋｇｆ／ｍｍ２で
あった。Example 9 An aperture grill was obtained in the same manner as in Example 6, except that the electroplating was performed using the liquid composition and conditions shown in Table 14. The obtained aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes corresponding to a blackening treatment while applying a tension of 20 kgf / mm 2 to the tape portion, but no disconnection occurred. At this time, the molybdenum content in the produced iron film was 0.5% by weight,
In an argon atmosphere, the strain rate was 0.5 mm / min. As a result, a tensile strength was 28 kgf / mm 2 .
【００３７】[0037]
【表１４】 [Table 14]
【００３８】実施例１０ 実施例６と同様な手順でチタン板にパタ−ニングを施
し、表１０に示す液組成および条件で、露出したチタン
板表面に電気銅めっきを行い、続いて表１２に示す液組
成および条件で電気鉄めっきを、表１５に示す液組成お
よび条件で電気ニッケルめっきを行い、再度表１２に示
す液組成および条件で電気鉄めっきを行い、該チタン板
表面に銅、鉄、ニッケル、鉄を順にそれぞれ３μｍ、１
０μｍ、４μｍ、２８μｍ形成した。その後、レジスト
層を剥離し、アパチャーグリルをチタン板から剥ぎ取っ
た後、電着物の銅層を選択的に溶解除去することによっ
て、テープ断面形状がリベット状となるアパチャーグリ
ルを得た。得られたアパチャーグリルをテープ部に２０
ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理に相当す
る４７５℃、３０分間の熱処理を行ったが、断線は全く
発生しなかった。このとき、作製した鉄皮膜中のモリブ
デン含有量は０．４重量％であり、４７５℃、アルゴン
雰囲気中、歪速度０．５ｍｍ／ｍｉｎ．での引張試験を
行った結果、引張強度は２５ｋｇｆ／ｍｍ２であった。Example 10 Patterning was performed on a titanium plate in the same procedure as in Example 6, and the exposed titanium plate surface was subjected to electrolytic copper plating with the liquid composition and conditions shown in Table 10; Electric iron plating was performed with the liquid composition and conditions shown in Table 15, and electro-nickel plating was performed with the liquid composition and conditions shown in Table 15, and again electric iron plating was performed with the liquid composition and conditions shown in Table 12. , Nickel and iron in order of 3 μm, 1
0 μm, 4 μm, and 28 μm were formed. Thereafter, the resist layer was peeled off, the aperture grill was peeled off from the titanium plate, and then the copper layer of the electrodeposit was selectively dissolved and removed to obtain an aperture grill having a rivet-shaped tape cross section. Put the obtained aperture grill on the tape
Heat treatment was performed at 475 ° C. for 30 minutes corresponding to the blackening treatment while applying a tension of kgf / mm 2 , but no disconnection occurred. At this time, the molybdenum content in the produced iron film was 0.4% by weight, and the strain rate was 0.5 mm / min. As a result, the tensile strength was 25 kgf / mm 2 .
【００３９】[0039]
【表１５】 [Table 15]
【００４０】比較例４ 実施例６において電気鉄めっきを表１６で示す液組成お
よび条件で行った以外、すなわちモリブデン酸塩の添加
を行わなかった以外は、実施例６と同様な手順でアパチ
ャーグリルを得た。前記アパチャーグリルをテープ部に
２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処理に相
当する４７５℃、３０分間の熱処理を行ったが、断線を
発生するものがあり歩留まりは約４０％であった。この
とき、４７５℃、アルゴン雰囲気中、歪速度０．５ｍｍ
／ｍｉｎ．での引張試験を行った結果、引張強度は１５
ｋｇｆ／ｍｍ２であった。COMPARATIVE EXAMPLE 4 An aperture grill was prepared in the same manner as in Example 6, except that the electroplating was carried out in the same manner as in Example 6, except that the electroplating was carried out under the conditions shown in Table 16, ie, no molybdate was added. I got The aperture grill was subjected to a heat treatment at 475 ° C. for 30 minutes corresponding to a blackening process while applying a tension of 20 kgf / mm 2 to the tape portion, but there was a case where disconnection occurred and the yield was about 40%. . At this time, at 475 ° C. in an argon atmosphere, the strain rate was 0.5 mm.
/ Min. As a result of the tensile test, the tensile strength was 15
kgf / mm 2 .
【００４１】[0041]
【表１６】 [Table 16]
【００４２】比較例５ 実施例６において電気鉄めっきを表１７で示す液組成お
よび条件で行った以外は、実施例６と同様な手順でアパ
チャーグリルを得た。得られたアパチャーグリルをテー
プ部に２０ｋｇｆ／ｍｍ２の張力を印加しながら黒化処
理に相当する４７５℃、３０分間の熱処理を行ったが、
断線を発生するものがあり、歩留まりは約６０％であっ
た。このとき、作製した鉄皮膜中のモリブデン含有量は
０．００８重量％であり、４７５℃、アルゴン雰囲気
中、歪速度０．５ｍｍ／ｍｉｎ．での引張試験を行った
結果、引張強度は１７ｋｇｆ／ｍｍ２であった。Comparative Example 5 An aperture grill was obtained in the same manner as in Example 6, except that the electroplating was carried out in the same manner as in Example 6, except that the electric iron plating was performed under the conditions shown in Table 17. The obtained aperture grill was subjected to heat treatment at 475 ° C. for 30 minutes corresponding to blackening while applying a tension of 20 kgf / mm 2 to the tape portion.
In some cases, disconnection occurred, and the yield was about 60%. At this time, the content of molybdenum in the produced iron film was 0.008% by weight, and the strain rate was 0.5 mm / min. As a result of the tensile test, the tensile strength was 17 kgf / mm 2 .
【００４３】[0043]
【表１７】 [Table 17]
【００４４】比較例６ 実施例６において電気鉄めっきを表１８で示す液組成お
よび条件で行った以外は、実施例６と同様な手順でレジ
スト剥離まで行った。しかし、チタン板から剥ぎ取る際
に僅かな応力でテープ部の一部に折れが発生し、断線に
至ったため、陰極線管を作製することができなかった。
このとき、作製した鉄皮膜中のモリブデン含有量は６重
量％であった。Comparative Example 6 The same procedure as in Example 6 was carried out until the resist was stripped, except that the electric iron plating was performed under the liquid composition and conditions shown in Table 18 in Example 6. However, when the tape was peeled off from the titanium plate, a slight stress caused a part of the tape to be broken, resulting in disconnection, so that a cathode ray tube could not be manufactured.
At this time, the molybdenum content in the produced iron film was 6% by weight.
【００４５】[0045]
【表１８】 [Table 18]
【００４６】[0046]
【発明の効果】以上説明した通り、本発明に係るめっき
法によって得られたアパチャーグリルは、十分な耐熱強
度を有するため、テレビフレームに装着した後の黒化処
理での断線を防止することが可能となり、かつ生産性高
くアパチャーグリルを製造することができるという優れ
た効果を奏する。As described above, since the aperture grill obtained by the plating method according to the present invention has a sufficient heat-resistant strength, it is possible to prevent disconnection in the blackening process after being mounted on a television frame. This makes it possible to produce an aperture grill with high productivity, which is an excellent effect.
Claims (2)
金の単独および該金属層を含む多層構造からなるアパチ
ャーグリルをめっき法により製造する方法において、前
記金属層を塩化第一鉄を主成分とする電気鉄めっき液に
モリブデン酸塩またはモリブデン−クエン酸錯イオンを
添加することにより得ることを特徴とするアパチャーグ
リルの製造方法。1. A method of manufacturing an aperture grill having a multilayer structure including a single layer of molybdenum-containing iron or an iron-based alloy and a metal layer including the metal layer, wherein the metal layer is mainly composed of ferrous chloride. A method for producing an aperture grill, which is obtained by adding molybdate or molybdenum-citrate complex ion to an electric iron plating solution.
酸塩量またはモリブデン−クエン酸錯イオン量が、それ
ぞれモリブデンイオン濃度として１ｍｇ／Ｌ以上で６０
０ｍｇ／Ｌ以下、１ｍｇ／Ｌ以上で５００ｍｇ／Ｌ以下
であることを特徴とする請求項１記載のアパチャーグリ
ルの製造方法。2. When the amount of molybdate or the amount of molybdenum-citrate complex ion added to the electric iron plating solution is 1 mg / L or more as the concentration of molybdenum ion, respectively, 60
The method for producing an aperture grill according to claim 1, wherein the amount is 0 mg / L or less, 1 mg / L or more and 500 mg / L or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001085146A JP2002289097A (en) | 2001-03-23 | 2001-03-23 | Method of manufacturing aperture grill |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001085146A JP2002289097A (en) | 2001-03-23 | 2001-03-23 | Method of manufacturing aperture grill |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002289097A true JP2002289097A (en) | 2002-10-04 |
Family
ID=18940706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001085146A Pending JP2002289097A (en) | 2001-03-23 | 2001-03-23 | Method of manufacturing aperture grill |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002289097A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015527481A (en) * | 2012-06-11 | 2015-09-17 | スタムフォード・ディバイセズ・リミテッド | Method of manufacturing an aperture plate for a nebulizer |
| US10279357B2 (en) | 2014-05-23 | 2019-05-07 | Stamford Devices Limited | Method for producing an aperture plate |
| US10508353B2 (en) | 2010-12-28 | 2019-12-17 | Stamford Devices Limited | Photodefined aperture plate and method for producing the same |
-
2001
- 2001-03-23 JP JP2001085146A patent/JP2002289097A/en active Pending
Cited By (11)
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|---|---|---|---|---|
| US10508353B2 (en) | 2010-12-28 | 2019-12-17 | Stamford Devices Limited | Photodefined aperture plate and method for producing the same |
| US10662543B2 (en) | 2010-12-28 | 2020-05-26 | Stamford Devices Limited | Photodefined aperture plate and method for producing the same |
| US11389601B2 (en) | 2010-12-28 | 2022-07-19 | Stamford Devices Limited | Photodefined aperture plate and method for producing the same |
| US11905615B2 (en) | 2010-12-28 | 2024-02-20 | Stamford Devices Limited | Photodefined aperture plate and method for producing the same |
| JP2015527481A (en) * | 2012-06-11 | 2015-09-17 | スタムフォード・ディバイセズ・リミテッド | Method of manufacturing an aperture plate for a nebulizer |
| US9981090B2 (en) | 2012-06-11 | 2018-05-29 | Stamford Devices Limited | Method for producing an aperture plate |
| US10512736B2 (en) | 2012-06-11 | 2019-12-24 | Stamford Devices Limited | Aperture plate for a nebulizer |
| US11679209B2 (en) | 2012-06-11 | 2023-06-20 | Stamford Devices Limited | Aperture plate for a nebulizer |
| US10279357B2 (en) | 2014-05-23 | 2019-05-07 | Stamford Devices Limited | Method for producing an aperture plate |
| US11440030B2 (en) | 2014-05-23 | 2022-09-13 | Stamford Devices Limited | Method for producing an aperture plate |
| US11872573B2 (en) | 2014-05-23 | 2024-01-16 | Stamford Devices Limited | Method for producing an aperture plate |
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