JPS63255851A - Production of optical recording medium - Google Patents
Production of optical recording mediumInfo
- Publication number
- JPS63255851A JPS63255851A JP9160587A JP9160587A JPS63255851A JP S63255851 A JPS63255851 A JP S63255851A JP 9160587 A JP9160587 A JP 9160587A JP 9160587 A JP9160587 A JP 9160587A JP S63255851 A JPS63255851 A JP S63255851A
- Authority
- JP
- Japan
- Prior art keywords
- recording layer
- org
- optical recording
- complex
- recording medium
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004544 sputter deposition Methods 0.000 claims abstract description 9
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000010408 film Substances 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 14
- 125000002524 organometallic group Chemical group 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 238000007738 vacuum evaporation Methods 0.000 claims description 5
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical group N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 150000004696 coordination complex Chemical class 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004528 spin coating Methods 0.000 abstract description 2
- 238000002310 reflectometry Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、透明基板上に設けた有機金属錯体を含む記録
層にレーザー光を照射することにより、ピット形成また
は相変化により記録を行う光記録媒体の製造方法に関す
るものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method of recording using a laser beam that performs recording by pit formation or phase change by irradiating a recording layer containing an organometallic complex provided on a transparent substrate with a laser beam. The present invention relates to a method of manufacturing a recording medium.
［従来の技術］
レーザー光照射によるピット形成や相変化を利用したデ
ジタル光記録が行われているが、記録層として金属やそ
の他の良熱伝導性材料を使用した場合には、レーザー光
照射によって記録層に与えられた熱が周囲に伝わること
から、十分な加熱のためには大きなエネルギーを与えね
ばならない。[Prior art] Digital optical recording is performed using pit formation and phase change caused by laser light irradiation, but when metal or other thermally conductive materials are used as the recording layer, laser light irradiation Since the heat applied to the recording layer is transmitted to the surrounding area, a large amount of energy must be applied to achieve sufficient heating.
このことは、記録時の効率を下げる要因になっている。This is a factor that reduces efficiency during recording.
一方、記録層として半導体レーザーの発振波長域に大き
な吸収帯をもつ有機金属錯体を使用することにより、こ
のような熱拡散の問題を解決することができる。しかし
ながら、有機金属錯体は金属単体などとは異なり、真空
蒸着などのドライプロセスを用いて薄膜化することは難
しい。しだがっで、有機金属錯体からなる記録層を作製
するときには、有機金属錯体を一旦溶媒に溶かし、これ
を用いてスピンコード等の方法により基板上に塗布しな
けらばならない。On the other hand, such a problem of thermal diffusion can be solved by using an organic metal complex having a large absorption band in the oscillation wavelength range of the semiconductor laser as the recording layer. However, unlike simple metals, organometallic complexes are difficult to form into thin films using dry processes such as vacuum evaporation. However, when producing a recording layer made of an organometallic complex, the organometallic complex must be dissolved in a solvent and then applied onto a substrate using a method such as a spin code.
ところが、有機金属錯体はかならずしも良溶性ではない
ので、基板上に厚く塗布することは難しい。そこで、塗
布溶液にポリマーを加えて粘度を上げることにより基板
上に厚く塗ることなどが考えられるが、この場合には単
位体積当りの吸光度が減少するため、記録層表面での反
射率も減少し、記録や読取りの際のトラッキングが難し
くなり、またＳＮ比も小さくなる。ここでＳＮ比とは、
記録前後での反射光強度の劣化弁と、雑音強度の比をい
う。However, since organometallic complexes are not necessarily highly soluble, it is difficult to coat them thickly on a substrate. Therefore, it is possible to add a polymer to the coating solution to increase the viscosity and coat the substrate thickly, but in this case, the absorbance per unit volume decreases, so the reflectance on the surface of the recording layer also decreases. , tracking during recording and reading becomes difficult, and the signal-to-noise ratio also decreases. Here, the SN ratio is
This refers to the ratio between the deterioration of reflected light intensity before and after recording and the noise intensity.
本発明に近い公知技術としては特開昭６０−８３０２９
号公報などが提案されているが、上記問題点の解決には
未だ至っていない。As a known technology close to the present invention, Japanese Patent Application Laid-Open No. 60-83029
Although the above-mentioned problems have been proposed, the above-mentioned problems have not yet been solved.
［本発明が解決しようとする問題点］
本発明はこのような問題点を改善するため、透明基板上
に金属薄膜をまず形成し、次いで錯体形成能のめる有機
アクセプター性化合物を反応させることにより、光吸収
性の有機金属錯体からなる記録層を容易に形成する製造
方法を提供することを目的とする。[Problems to be Solved by the Present Invention] In order to improve these problems, the present invention first forms a metal thin film on a transparent substrate, and then reacts it with an organic acceptor compound that enhances the ability to form a complex. An object of the present invention is to provide a manufacturing method for easily forming a recording layer made of a light-absorbing organometallic complex.
［問題点を解決するための手段］ 上記目的を達成するため本発明は下記の構成からなる。[Means for solving problems] In order to achieve the above object, the present invention consists of the following configuration.
「透明基板上に光吸収性有機金属錯体からなる記録層を
設けた光記録媒体であって、まず透明基板上に金属薄膜
を真空蒸着法またはスパッタリング法により形成し、該
金属膜と錯体形成能のある有機アクセプター性化合物を
含む溶液とを反応させることにより、光記録層を形成す
ることを特徴とする光記録媒体の製造方法。Ｊ
まず、光記録媒体の支持材となる透明基板としては、ガ
ラス、ポリカーボネート、アクリル系樹脂などを用いる
ことができるが、堅牢で透明性の高い材料であればいか
なるものを使用しても良い。``An optical recording medium in which a recording layer made of a light-absorbing organometallic complex is provided on a transparent substrate, in which a thin metal film is first formed on the transparent substrate by vacuum evaporation or sputtering; A method for producing an optical recording medium, characterized in that an optical recording layer is formed by reacting with a solution containing an organic acceptor compound. Glass, polycarbonate, acrylic resin, etc. can be used, but any material that is robust and highly transparent may be used.
また、この基板上には記録または読取りを行う際のレー
ザー光ガイド用のグループが形成されていてもよい。更
に、また、この基板上には、反射率や透過率の制御、基
板表面の保護などを目的とした層が設けられていてもよ
い。Further, a group for guiding laser light during recording or reading may be formed on this substrate. Furthermore, a layer may be provided on the substrate for the purpose of controlling reflectance and transmittance, protecting the substrate surface, and the like.
次に、透明基板上に真空蒸着法またはスパッタリング法
により薄膜化される金属としては、アルカリ金属、アル
カリ土類金属、遷移金属、稀土類金属などを用いること
ができるが、有機アクセプター性化合物と反応して錯体
を形成するものであればいかなるものであってもよい。Next, as the metal to be formed into a thin film on the transparent substrate by vacuum evaporation or sputtering, alkali metals, alkaline earth metals, transition metals, rare earth metals, etc. can be used, but they react with organic acceptor compounds. Any substance may be used as long as it forms a complex.
また、２種類以上の金属からなる、合金であってもよい
。薄膜化される金属として合金を用いる場合には、蒸着
源、またはスパッタリング源として合金を用いることも
できるし、共蒸着などの手法により蒸着やスパッタリン
グの過程で合金を形成させることもできる。Moreover, an alloy consisting of two or more types of metals may be used. When an alloy is used as the metal to be made into a thin film, the alloy can be used as a vapor deposition source or a sputtering source, or the alloy can be formed during the vapor deposition or sputtering process by a method such as co-evaporation.
有機アクセプター性化合物としては、７．７．８．８−
テトラシアノキノジメタン、テトラシアノエチレン、ク
ロラニル、および、これらの誘導体などを用いることが
できるが、透明基板上に薄膜化した金属と反応して錯体
を形成するものであればいかなるものであってもよい。As the organic acceptor compound, 7.7.8.8-
Tetracyanoquinodimethane, tetracyanoethylene, chloranil, and their derivatives can be used, but any substance that reacts with the metal formed into a thin film on a transparent substrate to form a complex can be used. Good too.
透明基板上への有機金属錯体膜の形成は、次の２段階に
分けて行う。すなわち、まず基板上に金属薄膜を設け、
これど有機アクセプター性化合物の溶液とを反応させて
、基板上で有機金属錯体膜を合成する。Formation of the organometallic complex film on the transparent substrate is performed in the following two steps. That is, first, a metal thin film is provided on the substrate,
This is reacted with a solution of an organic acceptor compound to synthesize an organometallic complex film on the substrate.
本発明方法によれば、難溶性の有機金属錯体を原料とし
なくて済むので、均質な記録層を低コストで作成するこ
とができる。またバインダーポリマーを必要としないの
で、記録膜の反射率が高く、ＳＮ比が向上する。According to the method of the present invention, since it is not necessary to use a poorly soluble organometallic complex as a raw material, a homogeneous recording layer can be produced at low cost. Furthermore, since a binder polymer is not required, the reflectance of the recording film is high and the S/N ratio is improved.
上記において、第１段階で基板上に金属薄膜を真空蒸着
、またはスパッタリングで設けるのは、記録膜を構成す
る化合物の原料を基板上に均一に形成するためである。In the above, the reason why the metal thin film is provided on the substrate in the first step by vacuum deposition or sputtering is to uniformly form the raw material of the compound constituting the recording film on the substrate.
本発明において、記録層である有機金属鏡体の厚みは、
真空蒸着、またはスパッタリング法で設ける金属薄膜の
厚みにより決定される。好ましい金属薄膜の厚みは０．
０１〜１０μｍであり、特に好ましくは０．０３〜２μ
ｍの範囲である。In the present invention, the thickness of the organometallic mirror serving as the recording layer is
It is determined by the thickness of the metal thin film provided by vacuum evaporation or sputtering. The preferred thickness of the metal thin film is 0.
01 to 10 μm, particularly preferably 0.03 to 2 μm
m range.
本発明方法において、基板上に形成された金属薄膜と有
機アクセプター性化合物の反応は、金属原子の酸化と、
有機アクセプターの還元、または金属原子と有機アクセ
プター性化合物間での共有結合の形成を伴って進行する
。In the method of the present invention, the reaction between the metal thin film formed on the substrate and the organic acceptor compound includes oxidation of metal atoms,
It proceeds with the reduction of the organic acceptor or the formation of a covalent bond between the metal atom and the organic acceptor compound.
たとえば金属原子（Ｍと略す）と７．７．８．８−テト
ラシアノキノジメタン（ＴＣＮＱ＞との反応は次の一般
式のようになる。For example, the reaction between a metal atom (abbreviated as M) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) is expressed by the following general formula.
ｍＭ＋ （ｋｍ＋ｎ＞ＴＣＮＱ ｋ＋ →Ｍ ｍＴＣＮＱ−ｋｆｆｌ−ＴＣＮＱ。mm+ (km+n>TCNQ k+ →M mTCNQ-kffl-TCNQ.
（ただしに、 ｍ、 ｎは整数である。）テトラシアノ
エチレン、クロラリルの場合も同様でおる。(However, m and n are integers.) The same applies to tetracyanoethylene and chloralyl.
上記において金属が銅、または銀の場合は下記のとおり
となる。In the above case, if the metal is copper or silver, it will be as follows.
Ｃｕ＋ＴＣＮＱ−＋Ｃｕ ＴＣＮＱ−ＡＣ＋＋ＴＣＮ
Ｑ→ＡＣＩ ＴＣＮＱ−［実施例］
以下実施例に基づいて説明する。なお本発明は実施例に
限定されるものではない。Cu+TCNQ-+Cu TCNQ-AC++TCN
Q→ACI TCNQ-[Example] The following will be explained based on an example. Note that the present invention is not limited to the examples.
実施例１
アクリル樹脂基板上に、真空度１０’Ｔｏ ｒ ｒで銅
を５Ｑｎｍの厚みになるように真空蒸着した。Example 1 Copper was vacuum deposited on an acrylic resin substrate at a vacuum degree of 10' Torr to a thickness of 5 Q nm.
この、表面に銅薄膜を有するアクリル板を、７，７゜８
．８−テトラシアノキノジメタンのメタノール溶液（濃
度１ミリモル／リットル）に浸したところ、銅と７．７
．８．８−テトラシアノキノジメタンはすみやかに反応
し、錯体を形成した。この際、錯体膜は均一であり、ア
クリル板からの剥離はおこらなかった。このようにして
作製した、銅−７，７，８，８−テトラシアノキノジメ
タン鏡体膜の光吸収スペクトルを第１図に示す。This acrylic plate with a copper thin film on its surface was held at 7.7°8
．． When immersed in a methanol solution of 8-tetracyanoquinodimethane (concentration 1 mmol/liter), copper and 7.7
．． 8.8-tetracyanoquinodimethane reacted quickly to form a complex. At this time, the complex film was uniform and did not peel off from the acrylic plate. The optical absorption spectrum of the copper-7,7,8,8-tetracyanoquinodimethane mirror film produced in this way is shown in FIG.
第１図の横軸は光の波長、縦軸は錯体膜の吸光度でおる
。半導体レーザーの発振波長域であるＢＱＱｎｍ付近に
大きな吸収体をもつことがわかる。In FIG. 1, the horizontal axis represents the wavelength of light, and the vertical axis represents the absorbance of the complex film. It can be seen that there is a large absorber near BQQnm, which is the oscillation wavelength range of semiconductor lasers.
このようにして作成した錯体膜に、波長８３０ｎｍ、強
度１０ｍＷ／平方ミクロンのレーザー光を照射したとこ
ろ、良好なピットが形成できた。When the complex film thus prepared was irradiated with a laser beam having a wavelength of 830 nm and an intensity of 10 mW/square micron, good pits were formed.
実施例２
ガラス基板上に、真空度１０’Ｔｏ ｒ ｒで銀を５０
ｎｍの厚みになるように真空蒸着した。この、表面に銀
薄膜を有するガラス板を、７，７，８．８−テトラシア
ノキノジメタンのメタノール溶液（濃度１ミリモル／リ
ットル〉に浸したところ、銀と７，７゜８．８−テトラ
シアノキノジメタンはすみやかに反応し、鏡体を形成し
た。この際、錯体膜は均一でおり、ガラス板からの剥離
はおこらなかった。このようにして作製した、銀−７，
７，８，８−テトラシアノキノジメタン錯体の光吸収ス
ペクトルを第２図に示す。Example 2 50% silver was deposited on a glass substrate at a vacuum level of 10'Torr.
Vacuum deposition was performed to a thickness of nm. When this glass plate with a thin silver film on its surface was immersed in a methanol solution (concentration 1 mmol/liter) of 7,7,8.8-tetracyanoquinodimethane, the difference between silver and 7,7°8.8- Tetracyanoquinodimethane reacted quickly to form a mirror body.At this time, the complex film was uniform and did not peel off from the glass plate.Silver-7, produced in this way,
The optical absorption spectrum of the 7,8,8-tetracyanoquinodimethane complex is shown in FIG.
第２図の横軸は光の波長、縦軸は錯体膜の吸光度である
。半導体レーザーの発振波長域で必る８００ｎｍ付近に
大きな吸収体をもつことがわかる。The horizontal axis in FIG. 2 is the wavelength of light, and the vertical axis is the absorbance of the complex film. It can be seen that there is a large absorber near 800 nm, which is the oscillation wavelength range of semiconductor lasers.
このようにして作成した錯体膜に、波長８３０ｎｍ、強
度１０ｍＷ／平方ミクロンのレーザー光を照射したとこ
ろ、良好なピットが形成できた。When the complex film thus prepared was irradiated with a laser beam having a wavelength of 830 nm and an intensity of 10 mW/square micron, good pits were formed.
［本発明の効果］
本発明の方法を用いることにより、スピンコード法など
を用いて有機金属錯体を直接基板上に塗布する場合に比
べて、良好な膜質の記録層を作製することができる。ま
た、反応溶媒は比較的極性の小さなものでよいことから
、基板表面を犯ざないものを選択して用いることができ
る。[Effects of the Present Invention] By using the method of the present invention, it is possible to produce a recording layer with better film quality than when applying an organometallic complex directly onto a substrate using a spin-coating method or the like. Furthermore, since the reaction solvent may have relatively low polarity, a solvent that does not damage the substrate surface can be selected and used.
第１図は本発明の方法により作製した銅−テトラシアノ
キノジメタン膜の光吸収スペクトルでおる。
第２図は本発明の方法により作製した銀−テトラシアノ
キノジメタン膜の光吸収スペクトルである。FIG. 1 shows a light absorption spectrum of a copper-tetracyanoquinodimethane film produced by the method of the present invention. FIG. 2 is a light absorption spectrum of a silver-tetracyanoquinodimethane film produced by the method of the present invention.
Claims (3)
層を設けた光記録媒体であつて、まず透明基板上に金属
薄膜を真空蒸着法またはスパッタリング法により形成し
、該金属膜と錯体形成能のある有機アクセプター性化合
物を含む溶液とを反応させることにより、光記録層を形
成することを特徴とする光記録媒体の製造方法。(1) An optical recording medium in which a recording layer made of a light-absorbing organometallic complex is provided on a transparent substrate, in which a thin metal film is first formed on the transparent substrate by vacuum evaporation or sputtering, and the metal film and the complex are formed on the transparent substrate by vacuum deposition or sputtering. 1. A method for producing an optical recording medium, comprising forming an optical recording layer by reacting with a solution containing an organic acceptor compound capable of forming an optical recording medium.
テトラシアノキノジメタン、または７、７、８、８−テ
トラシアノキノジメタン誘導体であることを特徴とする
特許請求の範囲第（１）項に記載の光記録媒体の製造方
法。(2) The organic acceptor compound is 7,7,8,8-
The method for producing an optical recording medium according to claim (1), wherein the optical recording medium is tetracyanoquinodimethane or a 7,7,8,8-tetracyanoquinodimethane derivative.
徴とする特許請求の範囲第（１）項に記載の光記録媒体
の製造方法。(3) The method for manufacturing an optical recording medium according to claim (1), wherein the metal thin film is a silver thin film or a copper thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9160587A JPS63255851A (en) | 1987-04-14 | 1987-04-14 | Production of optical recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9160587A JPS63255851A (en) | 1987-04-14 | 1987-04-14 | Production of optical recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63255851A true JPS63255851A (en) | 1988-10-24 |
Family
ID=14031196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9160587A Pending JPS63255851A (en) | 1987-04-14 | 1987-04-14 | Production of optical recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63255851A (en) |
-
1987
- 1987-04-14 JP JP9160587A patent/JPS63255851A/en active Pending
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