JPS5945195A - Optical recording medium - Google Patents

Optical recording medium

Info

Publication number
JPS5945195A
JPS5945195A JP57156126A JP15612682A JPS5945195A JP S5945195 A JPS5945195 A JP S5945195A JP 57156126 A JP57156126 A JP 57156126A JP 15612682 A JP15612682 A JP 15612682A JP S5945195 A JPS5945195 A JP S5945195A
Authority
JP
Japan
Prior art keywords
light
dye
recording layer
polymer
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
Application number
JP57156126A
Other languages
Japanese (ja)
Inventor
Akihiko Kuroiwa
黒岩　顕彦
Noriyoshi Nanba
憲良 南波
Shigeru Asami
浅見　茂
Shiro Nakagawa
士郎 中川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDK Corp
Original Assignee
TDK Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TDK Corp filed Critical TDK Corp
Priority to JP57156126A priority Critical patent/JPS5945195A/en
Publication of JPS5945195A publication Critical patent/JPS5945195A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

PURPOSE:To obtain an optical recording medium with a better live state preservability and record preservability which provides a high recording rate, a limited deterioration in regeneration and a S/N in reading by arranging a recording layer to containing a thermoplastic vinyl based polymer with a residual pigment group as light absorbing polymer. CONSTITUTION:This recording medium has a recording layer containing a thermoplastic vinyl based polymer with a residual pigment group on a substrate. The vinyl based polymer has a residual pigment group in the side chain and the number of the average monomer composition units is below 1,000. The substrate for mounting and supporting a recording layer made up of such an light absorbing polymer shall vary in the quality, shape and dimensions to match purposes.

Description

【発明の詳細な説明】 ■　発明の背景 技技分野 本発明は光記録媒体、特に、消去および再書き込み可能
なヒートモードの光記録媒体に関する。DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Technical Field The present invention relates to optical recording media, and in particular to erasable and rewritable heat mode optical recording media.

先行技術とその問題点 光記録媒体は、媒体と書き込みないし読み出しヘッドが
非接触であるので、記録媒体が摩耗劣化しない等の特徴
をもち、このため、種々の光記録媒体の開発研究が行わ
れている。Prior art and its problems Optical recording media have the characteristics that the recording medium does not deteriorate due to wear and tear because there is no contact between the medium and the writing or reading head.For this reason, research and development of various optical recording media has been carried out. ing.

このような光記録媒体のうち、暗室による画像処理が不
要である等の点で、ヒートモード光記録媒体の開発が活
発になっている。Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing in a darkroom.

このようなヒートモードの光記録媒体は、記録光を熱と
して利用する光記録媒体であり、その）ち、レーザー記
録光で媒体の１部を融解、除去等して、ピットと称され
る***を形成ｔ２、このピットにより情報を記録し、こ
のピットの有無を読み出し光で検出するものがある。Such a heat mode optical recording medium is an optical recording medium that uses recording light as heat, and uses laser recording light to melt or remove a portion of the medium to create small holes called pits. t2, information is recorded using these pits, and the presence or absence of these pits is detected using readout light.

そして、このようなピット形成型の媒体の１例として、
熱可塑性樹脂と、光吸収体としての色素とからなる記録
層を塗設し、樹脂を融解してピットを形成するものが知
られている。As an example of such pit-forming media,
It is known that a recording layer made of a thermoplastic resin and a dye as a light absorber is coated, and the resin is melted to form pits.

そして、このような媒体は、本発明者らの研究によれば
、一旦形成したビットを消去光フ、仁いし熱により消去
して記録層表向の全体あるいは１部を平坦にし、再び書
き込みができることが確認されている。According to research conducted by the present inventors, such a medium can be used to erase bits once formed using an erasing light, an eraser, or heat to flatten the entire or part of the surface of the recording layer, and then write again. It has been confirmed that it is possible.

しかし、このよ５な従来の媒体は、熱可塑性樹脂と色素
との相溶ないしブレンド系の記録層をもつため、以下の
ような欠点がある。However, these conventional media have the following drawbacks because they have a recording layer that is compatible or blended with a thermoplastic resin and a dye.

まず、記録層中で、相分離や、色素のマイグレーション
や、ブリードや再凝集などがおこりやすい。　そして、
これらは、色素濃度が高くなるほど発生しやすくなるた
め、記録層中の色素濃度を高くすることができず、この
ため記録レートが低いという欠点がある。First, phase separation, dye migration, bleeding, and reaggregation are likely to occur in the recording layer. and,
Since these occur more easily as the dye concentration increases, it is not possible to increase the dye concentration in the recording layer, resulting in a disadvantage that the recording rate is low.

しＳ／Ｎ比の再生劣化が大きい。However, the reproduction deterioration of the S/N ratio is large.

また、再生劣化をおこしやすいことから、再生光強度を
強くできず、このために読み出しのＳ／Ｎ比が低い。Furthermore, since reproduction deterioration is likely to occur, the reproduction light intensity cannot be increased, and therefore the read S/N ratio is low.

そして、ピットの周縁部の平滑性が悪く、このためにも
Ｓ／Ｎ比が低い。Further, the smoothness of the peripheral edge of the pit is poor, and for this reason as well, the S/N ratio is low.

加えて、相分離、マイダレ−ジョン、再凝集などのため
、耐熱性などの生保存性ないし記録保存性も悪い。In addition, due to phase separation, myadalation, re-aggregation, etc., raw storage properties such as heat resistance and archival storage properties are also poor.

■　発明の目的 不発明は、このような実状に鑑みなされたものであって
、その主たる目的は、記録レートが高く、再生劣化が小
さく、読み出しのＳ／Ｎ比が高く、生保存性および記録
保存性の良好な、特に消去および再書き込み可能なヒー
トモードの媒体として好適な光記録媒体を提供すること
にある。■ Purpose of the Invention The invention was made in view of the above-mentioned circumstances, and its main purpose is to achieve a high recording rate, low playback deterioration, high readout S/N ratio, high preservation performance, and high recording performance. The object of the present invention is to provide an optical recording medium that has good storage stability and is particularly suitable as an erasable and rewritable heat mode medium.

本発明者らは、このような目的につき種々検討を行った
結果、本発明をなすに至った。The present inventors have conducted various studies for this purpose, and as a result, have completed the present invention.

すなわち、本発明は、基体上に、色素残基を有する熱可
塑性のビニル系ポリマーを含む記録層を有することを特
徴とする光記録媒体である。That is, the present invention is an optical recording medium characterized by having a recording layer containing a thermoplastic vinyl polymer having dye residues on a substrate.

■　発明の具体的構成 ９下、本発明の具体的構成について詳細に説明する。■Specific structure of the invention 9, the specific configuration of the present invention will be explained in detail.

本発明の記録層中には、光を吸ＩＸ　Ｌ、昇温する光吸
収体と昇温にともない溶融し変形する熱可塑性樹脂との
機能を併せもつ、光吸収ポリマーが含まれる。The recording layer of the present invention contains a light-absorbing polymer that has both the functions of a light absorber that absorbs light and raises its temperature and a thermoplastic resin that melts and deforms as the temperature rises.

本発明において用いる光吸収ポリマーは、色素残基な有
する熱可塑性のビニル系ポリマーである。The light-absorbing polymer used in the present invention is a thermoplastic vinyl polymer containing dye residues.

このようなポリマーは、合成が容易であり、媒体の製造
コストが安価となる。　また、結合しうる色素の種類に
関する制限が少ない。Such polymers are easy to synthesize and the manufacturing cost of the media is low. Furthermore, there are fewer restrictions on the types of dyes that can be bound.

このようなビニル系ポリマーとしては、色な種類の中か
ら、媒体の用途や、用いる記録光、読み出し光、消去方
法等に対して最適な色素を結合させることができるとい
う点では、ビニル系ポリマーを主鎖とし、側鎖に色素残
基を有するものであることが好ましい。Among these types of vinyl-based polymers, vinyl-based polymers can be bonded with the most suitable dye for the purpose of the medium, recording light, readout light, erasing method, etc. It is preferable that the main chain is , and the side chain has a dye residue.

他方、ビニル系ポリマーとしては、熱可塑性のビニル化
合物のホモポリマー、コポリマー、さらにはビニル化合
物と他のモノマーとの熱可塑性の共重合体が含まれる。On the other hand, vinyl polymers include homopolymers and copolymers of thermoplastic vinyl compounds, and thermoplastic copolymers of vinyl compounds and other monomers.

ビニル系ポリマーのモノマー構成単位としては、種々の
ビニルモノマ一単位であってよく、例えば以下のような
ものを具体例として挙げることができる。The monomer constituent unit of the vinyl polymer may be one unit of various vinyl monomers, and the following may be mentioned as specific examples.

（−ＣＨ２−ＣＨ２−）− ＋ＣＨ３−ＣＨ＋ ■ ＯＯＨ ＋ＣＨ，−ＣＨ−） ■ ＣＨ３ （−ＣＨ２−ＣＩ−（ニド Ｃ７Ｉ４゜ ＣＨ３ ■ ＋ＣＨ２−Ｃ± Ｈ３ ＋Ｃｌ−１２−Ｃ目＋ ■ Ｃ１］２−ＣＩ１（Ｃ１４，３）２ Ｎ （−ＣＨ２−Ｃｌ−１−＋ ■ ＯＮＨ２ −（−ＣＨ２−ＣＩ−ＩＣｔ　−）− ４ＣＨ２−Ｃ１１Ｆ　−）− この場合、ビニル系ポリマー中の平均モノマー構成単位
数は］　Ｑ　（１０以下であるととが好ましい。(-CH2-CH2-)- +CH3-CH+ ■ OOH +CH, -CH-) ■ CH3 (-CH2-CI-(nidoC7I4゜CH3 ■ +CH2-C± H3 +Cl-12-Cth+ ■ C1]2- CI1(C14,3)2N (-CH2-Cl-1-+ ■ONH2-(-CH2-CI-ICt-)-4CH2-C11F-)- In this case, the average number of monomer constituent units in the vinyl polymer is ] Q (preferably 10 or less.

平均モノマー構成単位数がきわめて大きくなり、重合度
が高くなると、光吸収ポリマーを用いた効果の実効が少
なくなり、書き込み感度や読み出しのＳ／Ｎ比の向上が
小さく、また、ビットが形成される光強度および温度に
明瞭なしきい値があられれず、しき℃・値のブロードニ
／グが太き（、記録レーザー光の出力変動による、読み
出しのＳ／Ｎ比の変動が太き（なる。　そして、消去性
能も小さい。When the average number of monomer constituent units becomes extremely large and the degree of polymerization becomes high, the effect of using a light-absorbing polymer becomes less effective, the improvement in writing sensitivity and reading S/N ratio is small, and bits are formed. There is no clear threshold value for light intensity and temperature, and the threshold °C/value is wide (and the reading S/N ratio is wide due to fluctuations in the output of the recording laser beam. Erasing performance is also low.

コレに対し、ビニル系ポリマー中の平均モノマー構成単
位数が１０００以下となると、このような特性がすべて
顕著に向上する。On the other hand, when the average number of monomer constituent units in the vinyl polymer is 1000 or less, all of these properties are significantly improved.

このような場合、ビニル系ポリマー中の平均モノマー構
成単位数は、特に、３００以下、より好ましくは２〜２
００であることが好ましい。In such a case, the average number of monomer constituent units in the vinyl polymer is particularly 300 or less, more preferably 2 to 2.
Preferably it is 00.

これに対し、ビニル系ポリマー中でビニルモノマー構成
単位がモノマー構成単位中にしめる比の平均は、１００
モル％であっても、それ以下の任意の値であってもよい
。On the other hand, the average ratio of vinyl monomer constituent units to monomer constituent units in a vinyl polymer is 100
It may be mol% or any value less than that.

ただ、ビニルモノマー構成単位が有する側鎖は、色素の
導入が容易である点で、後述の色素基の含有比を考慮に
入れてビニルモノマー構成単位数は５〜１００％である
ことが好ましい。However, since dyes can be easily introduced into the side chains of the vinyl monomer constituent units, the number of vinyl monomer constituent units is preferably 5 to 100%, taking into consideration the content ratio of the dye group described below.

他方、色素残基を構成する色素の種類については特に制
限はなく、用いる記録光および読み出し光の波長に応じ
、３００〜２０００ｎｍ。On the other hand, there is no particular restriction on the type of dye constituting the dye residue, and the range is from 300 to 2000 nm depending on the wavelength of the recording light and readout light used.

特に４００〜９００　ｎｍに吸収をもつ種々の色素であ
ってよい。In particular, various dyes having absorption between 400 and 900 nm may be used.

このため、アゾ系、アノトラキノン系、フタロシア二］
系、カルボニウム系、インジゴイド系、可溶性建染系、
硫化系、キノンイミン系、シアニン系、キノリン系、ニ
トロ系、ニトロソ系、スチルベン系、ピラゾロン系、チ
アゾール系、キノアニル系、アジン系、酸化系、オキザ
ジン系、アクリジン系等はいずれも使用可能である。Therefore, azo series, anothraquinone series, phthalocyanin]
type, carbonium type, indigoid type, soluble vat type,
Any of the sulfide-based, quinoneimine-based, cyanine-based, quinoline-based, nitro-based, nitroso-based, stilbene-based, pyrazolone-based, thiazole-based, quinoail-based, azine-based, oxidized-based, oxazine-based, acridine-based, etc. can be used.

ただ、色素残基の光、熱等に対する安定性を考慮に入れ
ると、特に、アゾ色素残基、アントラキノン色素残基、
フタロシアニン色素残基、シアニン色素残基、カルボニ
ウム色素残基等が好ましい。However, when considering the stability of dye residues against light, heat, etc., in particular, azo dye residues, anthraquinone dye residues,
Preferred are phthalocyanine dye residues, cyanine dye residues, carbonium dye residues, and the like.

このような色素残基は、ビニル系ボ１１マーの主鎖、通
常、ビニルモノマ一単位部分に、直接または適当な連結
基を介して結合する。Such a dye residue is bonded to the main chain of the vinyl-based 11-mer, usually one vinyl monomer unit, directly or via a suitable linking group.

好適に用いられる連結基としては、−〇−９−ｓ−、−
ｃｏ−、−ｏｏ　−、−ＣＯＯ−、−ｏｃｏ−。As the linking group suitably used, -〇-9-s-, -
co-, -oo-, -COO-, -oco-.

−５ｏ２−、−ｏｃｏｏ−、−Ｎ＋（、−（Ｒは、水素
原子、アルキル基など、以下間）、−ＣＯＮＩ（、−。-5o2-, -ocoo-, -N+(, -(R is a hydrogen atom, an alkyl group, etc.), -CONI(, -.

−ＣＯＮＩえＣｏ−、−ＮＲＣＯ−、−８ＯＮＲ−。-CONIeCo-, -NRCO-, -8ONR-.

−Ｎ　Ｒ，Ｓ　Ｏ２−すど、あるいはアルキレン基、ア
リーレン基、複素環残基なと、さらにはこれら２棟以」
二が連結したもの等がある。-N R, SO2-, alkylene groups, arylene groups, heterocyclic residues, and even more than two of these.
There are cases where the two are connected.

なお、色素残基は、任意の数にて、分子中に存在するこ
とができるが、モノマー構成単位数の、特に０．２〜１
００％存在することが好ましい。Note that the dye residue can be present in any number in the molecule, but the number of monomer constituent units is particularly 0.2 to 1.
Preferably, 00% is present.

次に、このような光吸収ポリマーの具体例を挙げるが１
本発明は、これにより限定されるものではない。Next, we will give specific examples of such light-absorbing polymers.
The present invention is not limited thereby.

なお、下記のポリマー例においては、通常の条件にて合
成した場合の分子中の色素含有量が示される。　また、
連結基は左側の連結手にて七ツマー構成単位のビニル主
鎖と連結するものである。In addition, in the following polymer examples, the dye content in the molecule is shown when synthesized under normal conditions. Also,
The linking group is one that connects to the vinyl main chain of the seven-mer structural unit at the left linking hand.

ポリマーΔ６　　　モノマー構成単位　　　　　連　結
　基１．　　　　　　　＋ＣＨ２−ＣＨ２−）−−５、
（−Ｃ１４２−ＣＩ−ＩＱ）−−−ＣＯＮＩ−１−ａυ ０　　ＮＨ（ＣＩ−１２）３ＮＨ（ＣＩ（、）３ＮＨ２
５、−（−ＣＨ２−ＣｆＬ）−−ＣＯＯ−Ｈ ７、（−ＣＨ２−ＣＨ２＋−ＣＯ− ９、〃−Ｎｌ−１−８ｏ　　− １４、　　　　　　　　　１／　　　　　　　　　Ｃ０
０Ｃ２Ｈ，−ａ３ ００１」 ＯＮ）ＩＣＨ。Polymer Δ6 Monomer structural unit Linking group 1. +CH2-CH2-)--5,
(-C142-CI-IQ)---CONI-1-aυ 0 NH(CI-12)3NH(CI(,)3NH2
5, -(-CH2-CfL)--COO-H 7, (-CH2-CH2+-CO- 9,〃-Nl-1-8o-14, 1/C0
0C2H,-a3 001”ON)ICH.

１５、　　　　　　　　　　　　＋ＣＨ２−ＣＨ２−）
−−ＣＨ−１８、Ｑ− Ｈ Ｕ２　Ｈ５０ このような光吸収ポリマーは、公知の方法に準じ、熱可
塑性ポリマーに、色素残基を結合したり、あるいは色素
残基をもつモノマーを用いて重合反応を行ったりして容
易に合成される。15, +CH2-CH2-)
--CH-18, Q-H U2 H50 Such light-absorbing polymers can be produced by bonding dye residues to thermoplastic polymers or by polymerizing them using monomers having dye residues, according to known methods. It is easily synthesized by performing

本発明における記録層は、このような光吸収ポリマーか
ら実質的に形成される。The recording layer in the present invention is substantially formed from such a light-absorbing polymer.

このような記録層を設層するには、一般に常法に従い塗
設すればよく、その厚さは、一般に、００；３〜５μｍ
程度とされる。In order to form such a recording layer, it is generally necessary to apply the coating according to a conventional method, and the thickness thereof is generally 0.3 to 5 μm.
It is considered to be a degree.

なお、このような記録層には、この他、他のポリマーな
いしオリゴマー、各種可塑剤、界面活性剤、帯電防止剤
、滑剤、難燃剤、安定剤、分散剤、レベリング剤、ブリ
ード防止剤、紫外線吸収剤、酸化防止剤、はり水剤、溶
解性向上剤、乳化剤、消泡剤、つや出し剤、ブロツキノ
グ防止剤、柔軟剤、スリップ向上剤、ピンホール防止剤
、ゆず肌等防止剤等が含有されていてもよい。In addition, such a recording layer may contain other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, leveling agents, antibleeding agents, and ultraviolet rays. Contains absorbents, antioxidants, water repellents, solubility improvers, emulsifiers, antifoaming agents, polishing agents, anti-blocking agents, softeners, slip improvers, anti-pinhole agents, anti-citrus skin etc. You can leave it there.

これに対し、このような記録層を設層支持する基体につ
いては、特に限定されるものではなく、その利質として
は種々のものを用いることができる。On the other hand, the substrate on which such a recording layer is disposed and supported is not particularly limited, and various substrates can be used depending on the characteristics.

ただ、熱伝導度、表面性、機械的強度、吸湿性、ソリな
どの点では、通常、各種ガラス、各種強化ガラス、各種
セラミクス、あるいはポリメタクリル樹脂、ポリアクリ
ル樹脂、ポリカーボネート樹脂、フェノール樹脂、エポ
キシ樹脂、ジアリルフタレート樹脂、ポリエステル樹脂
、ポリイミド樹脂、ポリエーテルケトンオン、ポリエー
テルケトン、メチルベンチンポリマー、ボリアレート樹
脂、ポリオレフィン、ポリフェニレンサルファイド、ナ
イロン、フッ素系樹脂等の各種樹脂等を用いることが好
ましい。However, in terms of thermal conductivity, surface properties, mechanical strength, hygroscopicity, warp, etc., various types of glass, various types of tempered glass, various ceramics, polymethacrylic resin, polyacrylic resin, polycarbonate resin, phenolic resin, epoxy It is preferable to use various resins such as resin, diallyl phthalate resin, polyester resin, polyimide resin, polyether ketone, polyether ketone, methylbentine polymer, polyalate resin, polyolefin, polyphenylene sulfide, nylon, and fluororesin.

また、基体の形状や寸法は、用いる用途に応じ、ディス
ク、テープ、ベルト、ドラム等種々のものとすることが
できる。Further, the shape and dimensions of the base body can be varied depending on the intended use, such as a disk, tape, belt, or drum.

この場合、本発明の媒体は、このような基体の一面上に
上記の記録層を有するものであってもよく、その両面に
記録層を有するものであってもよい。　また、基体の一
面上に記録層を塗設したものを２つ用い、それらを記録
層が向かいあうようにして、所定の間隙をもって対向さ
せ、それを密閉したりして、ホコリやギズがつかないよ
うにすることもできる。In this case, the medium of the present invention may have the above-mentioned recording layer on one surface of such a substrate, or may have recording layers on both surfaces thereof. In addition, two substrates with recording layers coated on one surface are used, and the recording layers are placed facing each other with a predetermined gap between them, and the substrate is sealed to prevent dust and scratches. You can also choose not to have one.

なお、上記した媒体には、基体上に、必要に応じ金属製
の反射層や各種樹脂ノー等の下引層な設け、この下引層
上に記録層を設層することもできる。　他の下引層とし
ては、種々の熱可塑性樹脂、熱硬化性樹脂、あるいは紫
外線ないし電子線硬化型樹脂等のコーティング層を用い
ることもできる。In addition, in the above-mentioned medium, a metal reflective layer or a subbing layer such as various resins may be provided on the substrate, if necessary, and a recording layer may be provided on the subbing layer. As other subbing layers, coating layers of various thermoplastic resins, thermosetting resins, ultraviolet rays or electron beam curable resins, etc. can also be used.

さらに、基体上に反射層、下引層、記録層の順に設層す
ることもできる。Furthermore, a reflective layer, a subbing layer, and a recording layer can be formed in this order on the substrate.

また、記録層の膜厚を、無反射設計することもできる。Furthermore, the thickness of the recording layer can be designed to be non-reflective.

加えて、基板に、案内溝を設け、この溝の凸部上におよ
び／または凹部内に、記録層を設けてもよい。In addition, a guide groove may be provided on the substrate, and a recording layer may be provided on the protrusion and/or in the recess of this groove.

さらＫ、記録層上には、必要に応じ、反射層あるいは反
透過膜層、さらには保護層などを設けることもできる。Furthermore, a reflective layer, an anti-transmissive film layer, a protective layer, etc. can be provided on the recording layer, if necessary.

■　発明の具体的作用 本発明の媒体は、一般に、走行下において、通常、所定
の如く集光した記録光をパルス状に照射する。　このと
き、記録層中の光吸収ポリマー中の色素残基の発熱によ
り、光吸収ポリマー自体が融解し、変形し、ピットが形
成される。(2) Specific Effects of the Invention In general, the medium of the present invention is generally irradiated with recording light that is focused in a predetermined manner in a pulsed manner while the medium is running. At this time, due to the heat generated by the dye residue in the light-absorbing polymer in the recording layer, the light-absorbing polymer itself melts and deforms, forming pits.

このように形成されたピットは、媒体の走行下、読み出
し光の反射光ないし透過光を検出することにより読み出
される。The pits formed in this manner are read out by detecting the reflected or transmitted light of the readout light while the medium is running.

一方、このように形成されるピットは、一旦ピットを形
成した後、これを消去し、再書き込みを行うことができ
る。On the other hand, once the pits are formed in this way, they can be erased and rewritten.

このよ５な場合、消去は、媒体の全体ないし一部を加熱
してもよく、あるいは全体ないし一部に消去光を照射し
てもよい。　また、消去光を、媒体走行下、走査して線
消去することもできる。In such a case, erasing may be performed by heating the whole or a part of the medium, or by irradiating the whole or a part of the medium with erasing light. It is also possible to perform line erasing by scanning the erasing light while the medium is running.

このような消去光の照射や加熱により、ピット形成部の
記録層は融解して・ドー坦化し、再び書き込みができる
ことになる。By such irradiation with erasing light and heating, the recording layer in the pit-forming portion is melted and flattened, making it possible to write again.

そして、このよへな消去と再書き込みは、くりかえし何
回も行うことができる。Such erasing and rewriting can be repeated many times.

■　発明の具体的効果 本発明は、所定の光吸収ポリマーから記録層を構成する
ので、相分離や、色素のマイグレーションや、ブリード
がおこらず、色素濃度を高くすることができ、書き込み
感度および記録レートが向上する。■Specific Effects of the Invention Since the recording layer of the present invention is made of a predetermined light-absorbing polymer, phase separation, dye migration, and bleeding do not occur, and the dye concentration can be increased, resulting in improved writing sensitivity and recording. Rates will improve.

また、再生劣化も少ない。Furthermore, there is little deterioration during playback.

しかも、ピットの周縁部の平滑性がよく、Ｓ／Ｎ比が高
い。Furthermore, the peripheral edges of the pits have good smoothness and a high S/N ratio.

また、色素の飛散もきわめて少ない。In addition, there is very little scattering of the dye.

さらに、生保存性や記録保存性も高い。Furthermore, it has high shelf life and archival properties.

本発明者らは、本発明の効果を確認するため種々実験を
行った。The present inventors conducted various experiments to confirm the effects of the present invention.

以下にその１例を示す。An example is shown below.

実験例１゜ 上記ポリマー洗１を下記のよへにして合成した。Experimental example 1゜ The above Polymer Wash 1 was synthesized as follows.

まず、ポリスチレンを分子量分別して、平均モノマー構
成単位数４０のポリスチレンを得た。　これをＨＮＯ３
＋Ｈ２ＳＯ４にて、２０℃で３時間かけてニトロ化した
。　次に５ｎｅｔ＋ＨＣ６にて、９０℃で１５時間かげ
て還元し、アミン化シ、さらに５℃で、ＮａＮ０．　＋
　ＨＣ／−にてジアゾニウム塩とした。　これに、５０
℃８時間β−ナフトールを反応させて、深赤色の上記ポ
リマー腐１を得た。First, polystyrene was subjected to molecular weight fractionation to obtain polystyrene having an average number of monomer constituent units of 40. This is HNO3
Nitration was performed with +H2SO4 at 20°C for 3 hours. Next, it was reduced with 5net+HC6 at 90°C for 15 hours, aminated, and further heated at 5°C with NaN0. +
It was made into a diazonium salt with HC/-. For this, 50
By reacting with β-naphthol for 8 hours at °C, the deep red polymer rot 1 was obtained.

ポリマー中の色素残基の含有量は２０モル％、収率は５
０％であった。The content of dye residue in the polymer is 20 mol%, the yield is 5
It was 0%.

このようにして得た光吸収ポリマー／１６１をトルエン
に溶解し、３０−φのアクリル基板上に０．６μ濯厚に
て塗布設層して、本発明の媒体■を得た。The thus obtained light-absorbing polymer/161 was dissolved in toluene and coated on a 30-φ acrylic substrate at a thickness of 0.6 μm to obtain a medium (2) of the present invention.

これとは別に比較のため、下記色素人を用い、また熱可
塑性樹脂として、数平均分子量２０００　（媒体■）お
よび４００００　（媒体■）のポリエチレン（ｐｓｔ）
をそれぞれ用い１色素含有量が上記媒体Ｉと同一となる
よ）にして、０．６μ雷の記録層を設層して、２種の媒
体を作製した。Separately, for comparison, the following dyes were used, and polyethylene (PST) with number average molecular weights of 2000 (medium ■) and 40000 (medium ■) were used as thermoplastic resins.
Two types of media were prepared by using a recording layer of 0.6 .mu.m thick, each having the same dye content as that of the above-mentioned medium I).

このようにして得た各媒体Ｉ〜■を回転しながら、Ｈｅ
　−Ｃｄレーザーを１μ惧φに集光しく集光部用力１ｏ
ｍＷ）パルス照射した。While rotating each of the media I to ■ obtained in this way,
-To focus the Cd laser to 1μ and φ, the power of the condenser is 1o.
mW) pulse irradiation was performed.

パルス巾を変更し、記録層表面にピットが形成されるパ
ルス巾を測定し、書き込み感度の逆数（μｓｅｃ　）と
した。　結果を下記表１に示す。The pulse width was changed, and the pulse width at which pits were formed on the surface of the recording layer was measured, and was taken as the reciprocal of the writing sensitivity (μsec). The results are shown in Table 1 below.

次に、パルス巾を１μｓｅｃに固定し、書き込みを行っ
た。Next, writing was performed with the pulse width fixed at 1 μsec.

書き込み後、Ｈｅ　−Ｃｄレーザー読み出し光を１μへ
φに集光しく集光部用力１ｍＷ）、３００ｎｓｅｃ、＜
りかえし周波数１００Ｈｚにてパルス照射した。　そし
て、この反射光をフォトダイオードで検出し、読み出し
のＳ／Ｎ比（ｄＢ）を測定した。　結果を表１に示す。After writing, the He-Cd laser readout beam was condensed to 1μ and φ, condensing force 1mW), 300nsec, <
Pulse irradiation was performed at a repeat frequency of 100 Hz. Then, this reflected light was detected with a photodiode, and the readout S/N ratio (dB) was measured. The results are shown in Table 1.

　なお、ノイズとしてはＲＭＳ値（実効値）を用いた。Note that the RMS value (effective value) was used as the noise.

さらに、書き込み後、この読み出し光を１分間照射して
、その後のＳ／Ｎ比を測定し、再生劣化を評価した。　
　１分後にＳ／Ｎ比に変化のあった場合を×、変化のな
かった場合を○にて、表１に示す。Furthermore, after writing, this readout light was irradiated for 1 minute, and the S/N ratio thereafter was measured to evaluate reproduction deterioration.
Table 1 shows cases in which there was a change in the S/N ratio after 1 minute as ×, and cases in which there was no change as ○.

また、これとは別に、書き込み後、媒体を４０℃、相対
湿度８０％にて１週間保存し、保存後のＳ／Ｎ比を測定
し、記録保存性を評価した。　全く変化のｔ【かったも
のを○、若干変化のあったものを△、大きく劣化したも
のを×にて、表１に示す。Separately, after writing, the medium was stored for one week at 40° C. and 80% relative humidity, and the S/N ratio after storage was measured to evaluate the recording stability. Table 1 shows the results as shown in Table 1, with ○ indicating no change, △ indicating a slight change, and × indicating significant deterioration.

さらに、書き込み後、赤外線ヒーターを用い、各媒体を
１２０℃、１５秒間加熱して消去を行った。　消去性能
を０、×、△で表１に示す。Furthermore, after writing, each medium was heated at 120° C. for 15 seconds using an infrared heater to perform erasing. The erasing performance is shown in Table 1 as 0, ×, and Δ.

表　　　１ 媒　　体　　　　　Ｉ　　　　　　　ｌｒ　　　　　　
　ｆｉｒ光吸収ポリマー　／ｉ６１　　　　　−　　　
　　　−ポリマー　−Ｐｓｉ（２０００）　ＰＳｔ（４
００００）色　　　素　　　　−Ａ　　　　　　　　Ａ
Ｓ／Ｎ比（ｄＢ）　　４３　　　　２２　　　　１４再
生劣化　○　　×　　　× 保　　存　　性　　○　　　　　×　　　　　　△消去
性能　○　　△　　　× 表１に示される結果から、本発明の効果があきらかであ
る。Table 1 Medium Ir
fir light absorption polymer /i61 -
- Polymer - Psi (2000) PSt (4
0000) Dye -A A
S/N ratio (dB) 43 22 14 Reproduction deterioration ○ × × Storage property ○ × Δ Erasing performance ○ Δ × From the results shown in Table 1, the effects of the present invention are clear.

実験例２゜ Ｈ 反応させて、黄色の上記ポリマー屑２を得た。Experimental example 2゜ H As a result of the reaction, yellow polymer waste 2 was obtained.

ポリマー中の色素残基含有量は２０モル％、収率は４０
％であった。The content of dye residue in the polymer is 20 mol%, the yield is 40
%Met.

このポリマー４２を用いて、実験例１と同様に媒体■を
得た。Using this polymer 42, medium (2) was obtained in the same manner as in Experimental Example 1.

また、比較のため、上記ＰＳ　ｔ　（２００（１）およ
びＰＳｔ（４００００）と、下記色素Ｂを用い、実験例
１と同様に、媒体Ｖ、■を得た。For comparison, a medium V, ■ was obtained in the same manner as in Experimental Example 1 using the above PS t (200(1) and PSt (40000)) and the following dye B.

曹き込み光および抗み出し光としてＡｒレーザーを用い
た他は、実験例１と全く同様にして、書き込み感度の逆
数、Ｓ／Ｎ比、再生劣化、保存性、消去性能を測定した
。The reciprocal of writing sensitivity, S/N ratio, reproduction deterioration, storage stability, and erasing performance were measured in exactly the same manner as in Experimental Example 1, except that Ar laser was used as the penetration light and the penetration light.

結果を下記表２に示す。The results are shown in Table 2 below.

表　　　２ 媒体　Ｗ　　　Ｖ　　　Ｖ 光吸収ポリマー　　Ａ２　　　　　−　　　　　　−樹
　　　脂　　　　−ＰＳｔ（２０００）　　ＰＳｔ（４
００００）色　　　素　　　　−Ｂ　　　　　　　　Ｂ
Ｓ／Ｎ比（ｄＢ）　　４１　　　　２５　　　　１６再
生劣化　○　　×　　　× 保　　存　　性　　○　　　　　　×　　　　　　△消
去性能　○　　△　　　× 表２に示される結果から本発明の効果があきらかである
。Table 2 Medium W V V Light absorbing polymer A2 - -Resin -PSt (2000) PSt (4
0000) Dye -B B
S/N ratio (dB) 41 25 16 Reproduction deterioration ○ × × Storage property ○ × Δ Erasing performance ○ Δ × From the results shown in Table 2, the effects of the present invention are clear.

実験例３゜ 平均モノマー構成単位数２５のα−メチルスチレンをＩ
（Ｎｏ３．５ｎＣ１２／　ＨＣｌにてアミノ化したのち
、 上記ポリマー腐３を得た。　ポリマー中の色素残基含有
量は２０モル％、収率は３０％であった。Experimental Example 3 α-methylstyrene with an average monomer constitutional unit number of 25 was
(After amination with No. 3.5nC12/HCl, the above polymer rot 3 was obtained. The content of dye residue in the polymer was 20 mol%, and the yield was 30%.

このポリマー／Ｉ６３を用い、実験例１と同様に媒体■
を得た。Using this polymer/I63, medium
I got it.

また比較のため、上記ＰＳｔ（２０ｏ０）およびＰｓｉ
（４００００）と、下記色素Ｃを用い、実験例１と同様
に、媒体■、■を得た。For comparison, the above PSt (20o0) and Psi
(40000) and the following dye C, media ① and ② were obtained in the same manner as in Experimental Example 1.

ＯＮＨ（ＣＨ２）！１ＮＨ（ＣＨ３）、ＮＨ２書き込み
光および読み出し光をＨｅ　−Ｎｅレーザーにかえた他
は、実験例１と全く同様にて各測定を行った。　結果を
表３に示す。ONH (CH2)! Each measurement was carried out in exactly the same manner as in Experimental Example 1, except that the 1NH (CH3), NH2 writing light and reading light were changed to a He-Ne laser. The results are shown in Table 3.

表　３ 媒体　■　　■　　■ 光吸収ポリマー　　Ａ３　　　　　　−　　　　　　−
樹　　　脂　　　　　　　　　ＰＳｔ（２０００）ＰＳ
ｔ（４００００）色　　　素　　　　　　　　　　　　
　ＣＣ８／Ｎ比（ｄＢ）　　　４６　　　　　２８　　
　　１９再生劣化　○　　　×　　　○ 保　　存　　性　　　○　　　　　　Ｘ　　　　　　△
消去性能　○　　　△　　　× 表３に示される結果から、本発明の効果があきらかであ
る。Table 3 Medium ■ ■ ■ Light-absorbing polymer A3 - -
Resin PSt (2000)PS
t(40000) dye
CC8/N ratio (dB) 46 28
19 Reproduction deterioration ○ × ○ Preservability ○ × △
Erasing performance ○ Δ × From the results shown in Table 3, the effect of the present invention is clear.

実験例４゜ 下記表４に示される光吸収ポリマーを用い、実験例１と
同様に媒体を作製したのち、各特性を評価した。　結果
を表４に示す。　なお、表４には、使用レーザーが併記
される。Experimental Example 4 Using the light-absorbing polymer shown in Table 4 below, a medium was prepared in the same manner as in Experimental Example 1, and then its respective properties were evaluated. The results are shown in Table 4. Note that Table 4 also lists the lasers used.

表４に示される結果から、本発明の効果があきらかであ
る。From the results shown in Table 4, the effects of the present invention are clear.

実験例５゜ 上記各実験例におけるポリマー屑の原料をかえて合成を
行い、色素残基含有量が同一で下記表５のように、平均
モノマー構成単位数の異なるものを得て、各媒体を作製
した。Experimental Example 5゜ Synthesis was carried out by changing the raw material of the polymer waste in each of the above experimental examples to obtain materials with the same dye residue content but different average numbers of monomer constituent units as shown in Table 5 below, and each medium was Created.

各媒体の特性を表５に示す。Table 5 shows the characteristics of each medium.

表５に示される結果から、モノマー構成単位数が１００
０以下となると、感度およびＳ／Ｎ比が向上し、消去性
能が向上することがわかる。From the results shown in Table 5, the number of monomer constituent units is 100
It can be seen that when the value is 0 or less, the sensitivity and S/N ratio improve, and the erasing performance improves.

出願人　東京電気化学工業株式会社 代理人　弁理士　石　井　陽　−Applicant Tokyo Denki Kagaku Kogyo Co., Ltd. Agent Patent Attorney Yo Ishii -

Claims (1)

【特許請求の範囲】 １、基体上に、色素残基な有する熱可塑性のビニル系ポ
リマーを含む記録層を有することを特徴とする光記録媒
体。 ２、　ビニル系ポリマーが、側鎖に色素残基な有する特
許請求の範囲第１項に記載の光記録媒体。 ３、　ビニル系ポリマーの平均モノマー構成単位数が１
０００以下である特許請求の範囲第１項または第２項に
記載の光記録媒体。[Scope of Claims] 1. An optical recording medium comprising a recording layer containing a thermoplastic vinyl polymer containing dye residues on a substrate. 2. The optical recording medium according to claim 1, wherein the vinyl polymer has a dye residue in its side chain. 3. The average number of monomer constituent units of the vinyl polymer is 1.
000 or less, the optical recording medium according to claim 1 or 2.
JP57156126A 1982-09-08 1982-09-08 Optical recording medium Pending JPS5945195A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP57156126A JPS5945195A (en) 1982-09-08 1982-09-08 Optical recording medium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57156126A JPS5945195A (en) 1982-09-08 1982-09-08 Optical recording medium

Publications (1)

Publication Number Publication Date
JPS5945195A true JPS5945195A (en) 1984-03-13

Family

ID=15620889

Family Applications (1)

Application Number Title Priority Date Filing Date
JP57156126A Pending JPS5945195A (en) 1982-09-08 1982-09-08 Optical recording medium

Country Status (1)

Country Link
JP (1) JPS5945195A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0153736A2 (en) * 1984-03-01 1985-09-04 E.I. Du Pont De Nemours And Company Optical recording element
WO1986001460A1 (en) * 1984-09-03 1986-03-13 Mitsubishi Chemical Industries Limited Optical recording medium
JPS61232447A (en) * 1985-04-08 1986-10-16 ヘキスト・セラニーズ・コーポレーション Optical data memory medium having color forming block/polymer information layer
US4619990A (en) * 1985-03-11 1986-10-28 Minnesota Mining And Manufacturing Company Polymeric dyes with pendent chromophore groups capable of undergoing thermoplastic deformation
US4666819A (en) * 1985-03-11 1987-05-19 Minnesota Mining And Manufacturing Company Optical information storage based on polymeric dyes
JPS646949A (en) * 1987-02-23 1989-01-11 Agency Ind Science Techn Cross-linked porphine-based optical recording medium
US5059510A (en) * 1985-02-04 1991-10-22 Hoechst Celanese Corp. Media for optical information storage comprising an organic macrocyclic chromophore substituted with a film conferring organic substituent
US5362812A (en) * 1993-04-23 1994-11-08 Minnesota Mining And Manufacturing Company Reactive polymeric dyes
US6475589B1 (en) 2001-12-17 2002-11-05 General Electric Company Colored optical discs and methods for making the same
US6475588B1 (en) 2001-08-07 2002-11-05 General Electric Company Colored digital versatile disks

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0153736A2 (en) * 1984-03-01 1985-09-04 E.I. Du Pont De Nemours And Company Optical recording element
WO1986001460A1 (en) * 1984-09-03 1986-03-13 Mitsubishi Chemical Industries Limited Optical recording medium
EP0192778A1 (en) * 1984-09-03 1986-09-03 Mitsubishi Kasei Corporation Optical recording medium
US4737443A (en) * 1984-09-03 1988-04-12 Mitsubishi Chemical Industries Limited Optical recording medium
US5059510A (en) * 1985-02-04 1991-10-22 Hoechst Celanese Corp. Media for optical information storage comprising an organic macrocyclic chromophore substituted with a film conferring organic substituent
US4619990A (en) * 1985-03-11 1986-10-28 Minnesota Mining And Manufacturing Company Polymeric dyes with pendent chromophore groups capable of undergoing thermoplastic deformation
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US6475588B1 (en) 2001-08-07 2002-11-05 General Electric Company Colored digital versatile disks
US6623827B2 (en) 2001-08-07 2003-09-23 General Electric Company Colored digital versatile disks
US6475589B1 (en) 2001-12-17 2002-11-05 General Electric Company Colored optical discs and methods for making the same

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