JPS6246685A - Optical recording medium - Google Patents
Optical recording mediumInfo
- Publication number
- JPS6246685A JPS6246685A JP60187738A JP18773885A JPS6246685A JP S6246685 A JPS6246685 A JP S6246685A JP 60187738 A JP60187738 A JP 60187738A JP 18773885 A JP18773885 A JP 18773885A JP S6246685 A JPS6246685 A JP S6246685A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- recording
- recording medium
- compound
- derivative compound
- 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
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ジアセチレン誘導体化合物の単分子膜、又は
単分子累積膜の光による化学変化若しくは物理変化を利
用して記録を行なう光記録媒体に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an optical recording medium that performs recording using chemical or physical changes caused by light in a monomolecular film or a monomolecular cumulative film of a diacetylene derivative compound. Regarding.
ジアセチレン誘導体化合物を記録層とする記録媒体は従
来から知られている。Recording media having recording layers made of diacetylene derivative compounds have been known for a long time.
例えば、ジアセチレン誘導体化合物の熱変色目−Ｆ＋朋
；七釣イ「ハス
ところで、その明細書中には、いかなるレーザを用いた
か、或いは用いるべきかについては何ら記載がなく、単
にレーザと記載されているに過ぎない。For example, in the case of thermal discoloration of diacetylene derivative compounds -F + Ho; It's just that.
そこで１本発明者等は、種々のレーザを用いて、該記録
媒体に対し、レーザ記録を行い、記録の可否を検討した
。Therefore, the present inventors performed laser recording on the recording medium using various lasers and examined whether recording was possible or not.
その結果、アルゴンレーザ等の大型かつ高出力のレーザ
を用いれば熱変色記録は可能であるが、小型で比較的低
出力の半導体レーザ（波長８００〜８５０ｎｍ）では、
熱変色記録は得られないことが確認された。As a result, thermochromic recording is possible using a large, high-output laser such as an argon laser, but a small, relatively low-output semiconductor laser (wavelength of 800 to 850 nm) cannot
It was confirmed that no thermochromic record was obtained.
ところで、実用面から考えた場合、小型で低出力の半導
体レーザで記録書込みを行い得ることが必要条件である
。However, from a practical point of view, it is a necessary condition that recording and writing can be performed using a small, low-output semiconductor laser.
ジアセチレン誘導体微結晶の粉体からなるものであるた
め１層内の分子分布配向がランダムであり、そのため場
所によっては光の透過性、反射性が異なったり、化学反
応の度合が異なる等の弊害が生じ、高密度記録には必ず
しも適しているとはいえない。Since it is made of diacetylene derivative microcrystal powder, the molecular distribution and orientation within one layer is random, resulting in adverse effects such as different light transmittance and reflectivity depending on the location, and different degrees of chemical reaction. occurs, and is not necessarily suitable for high-density recording.
そこで１本発明は、斯かる従来技術の欠点を解消するた
めになされたものである。Therefore, the present invention has been made in order to eliminate the drawbacks of the prior art.
本発明の目的は、小型軒砥の半導体レーザによるｊＪｚ
込みが可能な光記録媒体を提供することにある。The object of the present invention is to improve jJz using a semiconductor laser for small eaves
The object of the present invention is to provide an optical recording medium that can be recorded.
本発明の別の目的は、高密度、高感度の記録媒体を提供
することにある。Another object of the present invention is to provide a high-density, high-sensitivity recording medium.
本発明の更に別の目的は、安定性、高品質性に優れた記
録媒体を提供することにある。Still another object of the present invention is to provide a recording medium with excellent stability and high quality.
１−記の目的は、以下の本発明によって達成される。 The object 1- is achieved by the present invention as follows.
すなわち本発明は、ジアセチレン誘導体化合物を有する
Ａ層と７ズレニウム塩化合物を有するＢ層を桔層して成
ることを特徴とする光記録媒体である。That is, the present invention is an optical recording medium characterized by comprising a layer A having a diacetylene derivative compound and a layer B having a heptadrenium salt compound.
本発明において、ジアセチレン誘導体化合物を有するＡ
層は記録層として機能し、アズレニウム１ｎ化合物を有
するＢＮは輻射線吸収層として機能する。In the present invention, A containing a diacetylene derivative compound
The layer functions as a recording layer and the BN with azulenium 1n compound functions as a radiation absorbing layer.
本発明に係るジアセチレン誘導体化合物は。The diacetylene derivative compound according to the present invention is as follows.
一般式（１） ％式％（） ｎ：１以との整数 で表わされる。General formula (1) %formula%() n: an integer greater than or equal to 1 It is expressed as
疎水性部位Ｒとしては、例えばアルキル基、ビニル、ビ
ニリデン、エチニル等のオレフィン系炭化水素基、フェ
ニル、ナフチル、アントラニル等の縮合多環フェニル基
、ビフェニル、・ ターフェニル等の鎖状多環フェニル
基、その他の非極性基、カルボキシル基及びその金属塩
若しくはアミン塩、スルホン酸基及びその金属塩若しく
はアミン塩、スルホアミドＪ、（、アミド基、アミノ基
、イミノ基、ヒドロキシ基、４級アミツノよ、オキシア
ミノ基、ジアゾニウム基、グアニジン基、ヒドラジン基
、リン酸基、ケイ酸）、（、アルミン酸基、ニトリル基
、チオアルコールノ、（その他の極性基がある。Examples of the hydrophobic moiety R include alkyl groups, olefinic hydrocarbon groups such as vinyl, vinylidene, and ethynyl, condensed polycyclic phenyl groups such as phenyl, naphthyl, and anthranyl, and chain polycyclic phenyl groups such as biphenyl and terphenyl. , other non-polar groups, carboxyl groups and their metal salts or amine salts, sulfonic acid groups and their metal salts or amine salts, sulfamide J, (, amide groups, amino groups, imino groups, hydroxy groups, quaternary amino groups, There are oxyamino groups, diazonium groups, guanidine groups, hydrazine groups, phosphoric acid groups, silicic acid groups, (, aluminic acid groups, nitrile groups, thioalcohol groups, and other polar groups.
尚、前記ジアセチレン１誘導体化合物は、ポリジアセチ
レン誘導体化合物を含む。Note that the diacetylene 1 derivative compound includes a polydiacetylene derivative compound.
一方、アズレニウム坦化合物としては、例えば以下の式
（ｎ ）〜（ＸＩ）で表わされる化合物か挙げられる。On the other hand, examples of the azulenium support compound include compounds represented by the following formulas (n) to (XI).
（ＩＩ）
（ｍ）
（Ｖ）
（ＶＴ）
（■）
Ｈ３
（■）
（ＩＸ）
（Ｘ）
Ｈ３
（ｍ）
ジアセチレン誘導体化合物を有するＡ層及びアズレニウ
ム１１２化合物を有するＢ層を作成する方法としては、
スピンナー回転塗布法、ローラー塗布法、引上げ塗布法
、スパッタリング法、プラズマ爪合法等がある。そのい
ずれを用いても本発明の目的は達成される。(II) (m) (V) (VT) (■) H3 (■) (IX) (X) H3 (m) As a method for creating layer A having a diacetylene derivative compound and layer B having an azulenium-112 compound teeth,
Examples include a spinner rotation coating method, a roller coating method, a pull-up coating method, a sputtering method, and a plasma claw method. The object of the present invention can be achieved using any of them.
以下１例えばスピンナー回転塗布法を用いて成膜する場
合を説明する。A case in which a film is formed using, for example, a spinner rotation coating method will be described below.
スピンナー回転塗布法は、まず基板中央部に所定の塗布
液を滴下し、次にノ、（板を高速回転させて、遠心力の
作用により膜を均一に塗布する方法である。The spinner rotation coating method is a method in which a predetermined coating liquid is first dropped onto the center of the substrate, and then the plate is rotated at high speed to uniformly coat the film by the action of centrifugal force.
その実施装設としては、スピンナー回転塗布機がある。The implementation equipment is a spinner rotary coater.
本発明に於いては、前記アズレニウム１１！化合物及び
ジアセチレン誘導体化合物を各々適当な揮発性溶媒に溶
かし、塗布液として使用する。In the present invention, the azulenium 11! The compound and the diacetylene derivative compound are each dissolved in a suitable volatile solvent and used as a coating solution.
ジアセチレン誘導体化合物の適当な溶媒としては、例え
ば、クロロホルム、ジクロロメタン、クロロメタン等の
ハロゲン化炭化水素類、ベンゼン、トルエン、キシレン
等の芳香族炭化水素類、シクロヘキサン、ｎ−ヘキサン
等ノ飽和炭化水素類、アセトン等のケトン類、エタノー
ル、メタノール、プロパ／−ル等のアルコール類等があ
る。Suitable solvents for diacetylene derivative compounds include, for example, halogenated hydrocarbons such as chloroform, dichloromethane, and chloromethane, aromatic hydrocarbons such as benzene, toluene, and xylene, and saturated hydrocarbons such as cyclohexane and n-hexane. , ketones such as acetone, and alcohols such as ethanol, methanol, and propyl alcohol.
その中で好適な溶媒として、クロロホルム、ベンゼン、
トルエン等が挙げられる。Among them, suitable solvents include chloroform, benzene,
Examples include toluene.
他方、アズレニウム塩化合物の適当な溶媒としては、例
えば、クロロホルム、ジクロロメタン、クロロメタン等
のハロゲン化炭化水素類、アセトン等のケトン類、エタ
ノール、メタノール、プロパツール等のアルコール類等
が挙げられ、特に好適には、ジクロロメタン、アセトニ
トリル等が挙げられる。On the other hand, suitable solvents for azulenium salt compounds include, for example, halogenated hydrocarbons such as chloroform, dichloromethane, and chloromethane, ketones such as acetone, and alcohols such as ethanol, methanol, and propatool. Suitable examples include dichloromethane and acetonitrile.
回転速度及び塗布液濃度等の調整により、所望の膜厚を
得ることができる。A desired film thickness can be obtained by adjusting the rotation speed, coating solution concentration, etc.
膜厚は、Ａ層（記録層）、Ｂ層（輻射線吸収層）とも５
００人〜２＃Ｌｍが適しており、特に１０００人〜５０
００人が好適である。The film thickness is 5 for both layer A (recording layer) and layer B (radiation absorption layer).
00 people ~ 2#Lm is suitable, especially 1000 people ~ 50 people
00 people is preferred.
尚、基板との密着性を向上させるために、適宜天然又は
合成の高分子からなるバインダーを添加剤として用いる
ことができる。Incidentally, in order to improve the adhesion to the substrate, a binder made of a natural or synthetic polymer can be used as an additive as appropriate.
その他１品質向上等を図るため、適宜、種々のバインダ
ーを用いることもできる。In addition, in order to improve quality, etc., various binders may be used as appropriate.
尚、Ａ層とＢＲの積層の順序については問わない、必要
に応じていずれの形態を選択してもよい。Note that the order in which the A layer and the BR are laminated does not matter, and any form may be selected as required.
つまり、まずＡ層を成膜し、その上にＢ層を積重ねても
よいし、その逆でもよい。That is, layer A may be formed first and layer B may be stacked thereon, or vice versa.
更に、Ａ層とＢ層との間に必要に応じて他の層、例えば
蓄熱層を介在させても良い。Furthermore, another layer, such as a heat storage layer, may be interposed between the A layer and the B layer as necessary.
このようにして基板上にジアセチレン誘導体化合物を有
するＡ層（記録層）とアズレニウム塩化合物を有するＢ
層（輻射線吸収層）の積層体からなる光記録媒体を得る
ことができる。In this way, the A layer (recording layer) having the diacetylene derivative compound and the B layer having the azulenium salt compound are formed on the substrate.
An optical recording medium consisting of a stack of layers (radiation absorbing layer) can be obtained.
斯る記録媒体は、半導体レーザーによる高密度、高解像
度記録を可能とするものである。Such a recording medium enables high-density, high-resolution recording using a semiconductor laser.
以下、図示例（第１図）に従って１本発明の記録媒体を
説明する。Hereinafter, one recording medium of the present invention will be explained according to an illustrated example (FIG. 1).
前述の如くして形成された記録媒体は、光や熱により吸
収波長が変化して見かけの色が変わる。The recording medium formed as described above changes its absorption wavelength due to light or heat, and its apparent color changes.
まず、無色透明な記録層に紫外線を照射すると、ジアセ
チレン誘導体化合物が重合してポリジアセチレン誘導体
化合物となり、その結果、最大吸収波長が６２０〜６６
０ｎｍの青色に変化する。First, when a colorless and transparent recording layer is irradiated with ultraviolet rays, diacetylene derivative compounds polymerize to form polydiacetylene derivative compounds, resulting in a maximum absorption wavelength of 620 to 66
The color changes to 0 nm blue.
この変化は、紫外線を照射することによって起こり、熱
や溶剤によっては起こらない。This change is caused by UV irradiation and not by heat or solvents.
また、この変化は不可逆であるので、一度青色になった
膜は、無色透明膜には戻らない。Furthermore, since this change is irreversible, once the film turns blue, it will not return to its colorless and transparent state.
次に、半導体レーザ（波長８００〜８５０ｎｍ）を用い
て、記録媒体の所定の箇所をレーザビーム照射すると、
３層２（第１図）の被照射部位４は、レーザビーム５を
吸収して自身は加熱される（第１図（ａ））。Next, when a predetermined location on the recording medium is irradiated with a laser beam using a semiconductor laser (wavelength: 800 to 850 nm),
The irradiated region 4 of the three layers 2 (FIG. 1) absorbs the laser beam 5 and is heated (FIG. 1(a)).
しかして、３層２の加熱部位４と接触ないしは近接する
Ａ層（記録層）３の対応部位６も熱伝導により５０℃以
上に加熱され、最大吸収波長が５４０ｎｍの赤色に変化
する（第１図（ｂ）’）、この変化も不可逆である。As a result, the corresponding region 6 of the A layer (recording layer) 3 that is in contact with or close to the heated region 4 of the third layer 2 is also heated to 50° C. or higher due to thermal conduction, and changes to a red color with a maximum absorption wavelength of 540 nm (the first (b)'), this change is also irreversible.
本発明は、斯かるジアセチレン及びアズレニウム塩化合
物の特性を記録媒体に利用したものである。The present invention utilizes the properties of such diacetylene and azulenium salt compounds in a recording medium.
尚、必要に応じて記録層（Ａ層）上又は輻射線吸収層（
Ｂ層）上に不図示の保護膜を設けてもよい。In addition, if necessary, a layer may be added on the recording layer (layer A) or on the radiation absorbing layer (
A protective film (not shown) may be provided on layer B).
基板ないし単体としては、ガラス、プラスチック、紙、
金属等の種々の固体材料が用いられるが、必要に応じて
特定波長の輻射線を通すものに限定される。As a substrate or a single unit, glass, plastic, paper,
Various solid materials can be used, such as metals, but are limited to those that are transparent to specific wavelengths of radiation, if desired.
斯くして、入力情報に応じ、記録層上の所定の部位に色
変化による記録を行うことができる。In this way, it is possible to perform color change recording at a predetermined location on the recording layer according to the input information.
本発明を更に詳細に説明するために、以下に実施例を挙
げる。Examples are given below to explain the present invention in more detail.
実施例１
（１１）式に示したアズレニウムｌ！Ｉ化合物１部を塩
化メチレン１０部に充分溶かしたものを塗布液Ｂ１とし
て用意した。Example 1 Azulenium l! shown in formula (11)! Coating liquid B1 was prepared by sufficiently dissolving 1 part of Compound I in 10 parts of methylene chloride.
次に、ガラス基板ないし担体をスピンナー塗布機に装着
し、前記塗布液Ｂ１を前記ガラス基板上の中央部に少量
滴下した後、所定時間、所定回転数で所定の膜厚になる
ように回転塗布した。Next, the glass substrate or carrier is mounted on a spinner coater, and after dropping a small amount of the coating liquid B1 onto the center of the glass substrate, the coating liquid B1 is applied by rotation at a predetermined number of revolutions for a predetermined period of time to obtain a predetermined film thickness. did.
このようにして、ガラス基板りのアズレニウム塩化合物
の膜厚が、各々１００，２００゜１０００．３０００．
６０００人のものを多数準備した。In this way, the film thickness of the azulenium salt compound on the glass substrate was adjusted to 100°, 200°, 1000°, and 3000°, respectively.
We prepared many things for 6,000 people.
次に、下式に示したジアセチレン誘導体化合物１部を
Ｃ１４Ｈ２９−Ｃ＝Ｃ−Ｃ＝Ｃ−Ｃ１０Ｈ２０−ＣＯＯ
Ｎ ａベンゼン１０部に十分溶かした溶液（塗布液Ａｌ
）を用意した。Next, 1 part of the diacetylene derivative compound shown in the following formula was added to C14H29-C=C-C=C-C10H20-COO
A solution sufficiently dissolved in 10 parts of Na benzene (coating liquid Al
) was prepared.
次に、アズレニウム塩化合物が塗膜されたガラス基板を
スピンナー塗布機に装着し、前記塗布液Ａ１を前記アズ
レニウム塩化合物の膜の表面中央部に少量滴下した後、
所定の時間内、所定の回転数でスピンナーを回転させ、
所定の膜厚に塗膜した。Next, the glass substrate coated with the azulenium salt compound was mounted on a spinner coater, and a small amount of the coating liquid A1 was dropped onto the center of the surface of the azulenium salt compound film.
Rotate the spinner at a predetermined number of rotations within a predetermined time,
A film was coated to a predetermined thickness.
このようにして１表−１に示すようにガラス基板上にア
ズレニウム塩化合物を有する層とジアセチレン誘導体化
合物を有する層を積層した２５種の記録媒体を作製した
。In this way, 25 types of recording media were produced in which a layer containing an azulenium salt compound and a layer containing a diacetylene derivative compound were laminated on a glass substrate as shown in Table 1-1.
記録実験１
実施例１で製造された各記録媒体に、２５４１ｍの紫外
線を均一、且つ十分に照射し、記録層を青色膜とした。Recording Experiment 1 Each recording medium manufactured in Example 1 was uniformly and sufficiently irradiated with ultraviolet rays of 2541 m to form a blue film in the recording layer.
次に、出力３ ｍ Ｗ 、波長８３０ｎｍの半導体レー
ザビーム（ビーム径４ＪＬｍ）を入力情報に従って各々
の記録媒体に照射した。その結果を第１表に示す。Next, a semiconductor laser beam (beam diameter: 4 JLm) with an output of 3 mW and a wavelength of 830 nm was irradiated onto each recording medium according to the input information. The results are shown in Table 1.
但し、記録評価として記録の可否と品質を判断し、特に
良好な記録を行なえたものをＯ１良好なものをＯ１記録
が劣悪なものを×とした。However, as a recording evaluation, the availability and quality of recording were judged, and those with particularly good recording were given a good O1, and those with poor O1 recording were given a ×.
実施例２
ジアセチレン誘導体化合物として下記
Ｃｌ０Ｈ２１−Ｃ＝Ｃ−Ｃ＝Ｃ−Ｃ２Ｈ４−ＣＯＯＨで
表わされるものを使用したことを除き、実施例１と全く
同様にして記録媒体を製造した（表−２）。Example 2 A recording medium was produced in exactly the same manner as in Example 1, except that the diacetylene derivative compound represented by the following Cl0H21-C=C-C=C-C2H4-COOH was used (Table 2 ).
記録実験２
実施例２の記録媒体を用いたことを除き、記録実験ｌと
同様にして記録を行なった。Recording Experiment 2 Recording was carried out in the same manner as Recording Experiment 1, except that the recording medium of Example 2 was used.
その結果を表−２に示す。The results are shown in Table-2.
実施例３
アズレニウム塩化合物として（ｍ）式で表わされるもの
を使用したことを除き、実施例１と全く同様にして記録
媒体を製造した。Example 3 A recording medium was produced in exactly the same manner as in Example 1, except that the azulenium salt compound represented by formula (m) was used.
記録実験３ 実施例３の記録媒体を用いたことを除き。Recording experiment 3 Except that the recording medium of Example 3 was used.
記録実験ｌと同様にして記録を行なった。Recording was performed in the same manner as in Recording Experiment 1.
その結果は、表−１９表−２と全く同様であった。The results were exactly the same as Table-19 and Table-2.
表−１膜厚条件の異なる記録媒体と記録結果表−２膜厚
条件の異なる記録媒体と記録結果なる累積膜を介在させ
ることも行われる。Table 1 Recording media with different film thickness conditions and recording results Table 2 Recording media with different film thickness conditions and recording results A cumulative film may be interposed.
本発明の効果を以下に列挙する。 The effects of the present invention are listed below.
（１）ジアセチレン誘導体化合物の薄膜を記録層とし、
アズレニウム塩化合物を有する輻射線吸収層とを併用し
たことにより、軽量、低出力で且つ安価な半導体レーザ
記録が実施可能である。(1) A thin film of a diacetylene derivative compound is used as a recording layer,
By using a radiation absorbing layer containing an azulenium salt compound in combination, light-weight, low-output, and inexpensive semiconductor laser recording can be performed.
（２）大面積の指体上に、均質な光記録媒体を得ること
が可能である。(2) It is possible to obtain a homogeneous optical recording medium on a large-area finger body.
第１図（ａ） （ｂ）は本発明の光記Ｑ １Ｍ体の概略
構成図であると同時に、本発明に係る光記録プロセスを
説明するための模式的構成図である。FIGS. 1(a) and 1(b) are schematic configuration diagrams of the optical recording Q 1M body of the present invention, and are also schematic configuration diagrams for explaining the optical recording process according to the present invention.
Claims (1)
塩化合物を有するＢ層とを積層して成ることを特徴とす
る光記録媒体。An optical recording medium comprising a layer A having a diacetylene derivative compound and a layer B having an azulenium salt compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60187738A JPS6246685A (en) | 1985-08-27 | 1985-08-27 | Optical recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60187738A JPS6246685A (en) | 1985-08-27 | 1985-08-27 | Optical recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6246685A true JPS6246685A (en) | 1987-02-28 |
Family
ID=16211326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60187738A Pending JPS6246685A (en) | 1985-08-27 | 1985-08-27 | Optical recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6246685A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02305334A (en) * | 1989-05-18 | 1990-12-18 | Kubota Corp | Electronic governor device |
| WO2000020130A1 (en) * | 1998-10-01 | 2000-04-13 | The Secretary Of State For Defence | Surface coatings |
-
1985
- 1985-08-27 JP JP60187738A patent/JPS6246685A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02305334A (en) * | 1989-05-18 | 1990-12-18 | Kubota Corp | Electronic governor device |
| WO2000020130A1 (en) * | 1998-10-01 | 2000-04-13 | The Secretary Of State For Defence | Surface coatings |
| GB2365437A (en) * | 1998-10-01 | 2002-02-20 | Secr Defence | Surface coatings |
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