JPS62121939A - Optical information recording medium - Google Patents

Abstract

PURPOSE:To obtain a recording medium which permits recording and reproduction by the use of an inexpensive light source such as semiconductor laser and has a good shelf life by depositing a thin film contg. the metallic napthalocyanine expressed by the specific formula or the deriv. thereof on a base material. CONSTITUTION:The thin film contg. the metallic napthalocyanine expressed by the formula or the deriv. thereof is deposited on the base material. Since the metallic napthalocyanine has a low m.p., the vapor deposition temp. can be made lower. This medium permits recording and reproduction by using the compact and relatively inexpensive light source such as semiconductor laser or He-Ne laser, has excellent long-term shelf stability, obviates the photodeterioration by reproducing light, has high sensitivity, is safe and can be discarded as it is. The higher reflectivity is obtd. and the S/N ratio is improved by laminating the above-mentioned thin film and thin film contg. a dye having metallic brightness on the base material in optional order.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、光学的情報記録媒体に関し、特に高密度光エ
ネルギービームによって状態変化を生ぜしめることによ
り記録再生を行なう光学的情報記録媒体に係る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an optical information recording medium, and particularly to an optical information recording medium in which recording and reproduction are performed by causing a state change with a high-density light energy beam. .

１　　〔従来の技術及び問題点〕 従来、回転しているディスク状の光学的情報記録媒体に
レーザー光を照射して情報の記録再生を行う情報記録装
置が知られている。その１つに記録層がレーザー光を吸
収してその照射部分が局部的に加熱され融解、蒸発、あ
るいは凝集等の物理的変化を起こし、非照射部分との間
に光学的差異を生じさせて情報が記録されるものがある
。その中に、収束させたレーザー光によって金属薄膜を
局部的に加熱蒸発させ情報を記録するものがある。こう
した金属としては、Ｐｂ　、　Ｂｌ　、　Ｔｅ　、　Ｓ
ｅ　、　Ｔｉ等及びこれらの合金が用いられる。これら
は、真空蒸着法等により容易に大面積の均一な薄膜が得
られ、近赤外域でも光吸収を有するため半導体レーザー
が使用できるという長所があるが、反面反射率が大きく
熱伝導率が犬きく、比熱も大きいという欠点がある。特
に、反射率が大きいということは、レーザー光のエネル
ギーｆ：有効に利用できないので、記録に要する光エネ
ルギーが大きくなシ、大出力レーザー光源を必要とする
ために記録装置が大型かつ高価になる欠点がある。又、
Ｔｅ。1 [Prior Art and Problems] Conventionally, an information recording device is known that records and reproduces information by irradiating a rotating disk-shaped optical information recording medium with a laser beam. One of these is when the recording layer absorbs the laser beam, and the irradiated area is locally heated, causing physical changes such as melting, evaporation, or aggregation, and creating an optical difference between it and the non-irradiated area. Some information is recorded. Among them, there is one that records information by locally heating and evaporating a thin metal film using a focused laser beam. These metals include Pb, Bl, Te, S
E, Ti, etc. and alloys thereof are used. These have the advantage that a uniform thin film over a large area can be easily obtained by vacuum evaporation, and semiconductor lasers can be used because they absorb light even in the near-infrared region, but on the other hand, they have a high reflectance and a low thermal conductivity. It also has the disadvantage of having a large specific heat. In particular, a high reflectance means that the energy f of the laser beam cannot be used effectively, so the optical energy required for recording is large, and a high-output laser light source is required, making the recording device large and expensive. There are drawbacks. or,
Te.

Ｂｉ　、　Ｓｅ等は毒性を有するという欠点もある。Bi, Se, etc. also have the disadvantage of being toxic.

一方、有機色素薄膜をスピンナー塗布、ディ゛ツピング
法、真空蒸着法により基板上に形成した情報記録媒体が
知られている。代表的な有機色素（染料）としては、ア
ントラキノン染料（！！＃開昭５８−２２４４４８　）
、ナフトキノン染料（％開昭５８−２２４７９３　）、
シアニン染料（特開昭５８−１１２７９０　）が用いら
れている。しかしながら、これらはいずれも長期保存性
、近赤外域における光吸収強度、読み出し光に対する安
定性に問題がある。On the other hand, information recording media are known in which a thin organic dye film is formed on a substrate by spinner coating, dipping, or vacuum evaporation. A typical organic pigment (dye) is anthraquinone dye (!! #Kaisho 58-224448)
, naphthoquinone dye (%Kasho 58-224793),
Cyanine dye (Japanese Unexamined Patent Publication No. 58-112790) is used. However, all of these have problems in long-term storage, light absorption intensity in the near-infrared region, and stability against readout light.

このようなことから、上述した問題については種々の改
良案が出されている。例えば記録感度を改良するために
反射防止層を設けること（ｔ！！ｆ開昭５０−１５１１
５１　）や、記録層上に保護膜を設けること（特開昭５
５−２２９６１、特開昭５７−６６５４１）酸素による
退色防止物質を混合すること（特開昭５９−５５７９５
）が提案されているが問題点を解消するには至っていな
い。For this reason, various improvement proposals have been proposed regarding the above-mentioned problems. For example, providing an antireflection layer to improve recording sensitivity (t!!f
51) or providing a protective film on the recording layer (Japanese Patent Application Laid-open No. 5
5-22961, JP-A-57-66541) Mixing a substance that prevents fading due to oxygen (JP-A-59-55795)
) has been proposed, but it has not yet solved the problem.

本発明は、半導体レーザー、Ｈｅ−Ｎｅレーザー等のコ
ン／４’クトで比較的安価々光源を用いて記録再生が可
能で、長期間に亘って保存ができ、再生光による光劣化
のない感度の高い光学的情報記録媒体を提供しようとす
るものである。The present invention enables recording and reproduction using a relatively inexpensive light source such as a semiconductor laser or He-Ne laser, can be stored for a long period of time, and has sensitivity that does not deteriorate due to reproduction light. The objective is to provide an optical information recording medium with high performance.

〔問題点を解決するための手段及び作用〕本発明は、基
材上に一般式 〔但し、式中のＭはＨｒ　Ｃｕ　、　Ｆｅ　、　Ｎｉ　
、　Ｃｏ　。[Means and effects for solving the problems] The present invention provides a method for dissolving the general formula [where M is Hr Cu, Fe, Ni] on a base material.
, Co.

Ｃｒ　、　Ｚｎ　、　Ｓｎ　＊　Ｐｂ　＊　Ａｔ、　Ｉ
ｎ　、　Ｇａ　、　Ｖ　、　Ｍｇ。Cr, Zn, Sn*Pb*At, I
n, Ga, V, Mg.

Ｃｄ　　、Ｐｄ　　、Ｔｉ　　、Ｍｎ　　、Ｌｉ　　、
Ｃａ　　、Ｃｅ　　、Ｐｒ　　、Ｎｄ。Cd, Pd, Ti, Mn, Li,
Ca, Ce, Pr, Nd.

Ｐｍ　、　Ｓｍ　、　Ｅｕ　、　Ｇｄ　＋　Ｔｂを示し
、ＸはハＯ）ｆン基、アルキル基、カルボキシル基、ア
ルコキシ基、ヒドロキシル基、アリル基、アルキルカル
ボキシ基、ｍは０〜４の整数を示すＩＫで表わされる金
属ナフタロシアニン又はその誘導体を含む薄膜を担持さ
せたことを特徴とする光学的情報記録媒体である。Pm, Sm, Eu, Gd + Tb; This is an optical information recording medium characterized by supporting a thin film containing a metal naphthalocyanine or a derivative thereof represented by:

上記一般式にて表わされる金属ナフタロシアニンは無金
属のナフタロシアニンと金属塩を反応させることにより
、金属ナフタロシアニン誘導体は無金属のナフタロシア
ニン誘導体と金属塩を反応させることにより、夫々得ら
れる。こうした金属ナフタロシアニン及びその誘導体は
、中心金属として上記一般式の如（Ｈｅ　Ｃｕ　＋　Ｎ
ｌ　ｌＴｉ　ｔ　Ｚｎ　、Ｃｒ　＊　Ｆｅ　＋　Ａｔ＋
　Ｃｏ　＋　Ｓｎ　１Ｍｇ　＋　Ｍｎ等が配位できるた
め、レーザー波長や膜形成等の条件により適宜選択可能
である。なお、前記一般式中の４つのナフタリンの内の
１つ乃至３つをベンゼン環に置き換えてもよい。こうし
た金属ナフタロシアニンは融点が低いために、蒸着温度
を低減できる。The metal naphthalocyanine represented by the above general formula can be obtained by reacting a metal-free naphthalocyanine with a metal salt, and the metal naphthalocyanine derivative can be obtained by reacting a metal-free naphthalocyanine derivative with a metal salt. These metal naphthalocyanines and their derivatives have the central metal as shown in the above general formula (He Cu + N
l lTi t Zn, Cr * Fe + At+
Since Co + Sn 1Mg + Mn etc. can be coordinated, it can be selected as appropriate depending on conditions such as laser wavelength and film formation. Note that one to three of the four naphthalenes in the general formula may be replaced with benzene rings. Since these metal naphthalocyanines have a low melting point, the deposition temperature can be reduced.

上記金属ナフタロシアニン又はその誘導体は、真空蒸着
法、スパッタ法、イオングレート法、プラズマ重合法、
スピンナー塗布法、ディッピング法等の膜形成手段によ
り基材上に薄膜（記録層）を形成できる。特に、真空蒸
着法が適しており、金属ナフタロシアニン又はその誘導
体を単体で薄膜を形成できる。なお、塗布法だより薄膜
を形成する場合にはバインダとしてニトロセルロース、
／＋Ｊビニルアルコール、塩化ビニル、メチルメタクリ
レート、ポリエステル、ポリアミド、ポリカーゴネート
、エポキシ樹脂等の樹脂を用いる。こうした薄膜（記録
層）の厚さは５０〜５００　ｎｍの範囲にすることが望
ましい。この理由は、記録層の厚さを５０　ｎｍ未満に
すると、反射率の変化が小さ過ぎて信号Ｓ／Ｎ比が劣化
し易くなり、かといってその厚さが５００ｎｍを越える
と膜厚当シの光エネルギーが小さくなり感度低下を招く
恐れがある。The above metal naphthalocyanine or its derivative can be produced by vacuum evaporation method, sputtering method, ion grating method, plasma polymerization method,
A thin film (recording layer) can be formed on the substrate by a film forming method such as a spinner coating method or a dipping method. In particular, a vacuum deposition method is suitable, and a thin film can be formed using a single metal naphthalocyanine or a derivative thereof. In addition, when forming a thin film using the coating method, nitrocellulose or nitrocellulose is used as a binder.
/+J A resin such as vinyl alcohol, vinyl chloride, methyl methacrylate, polyester, polyamide, polycargonate, or epoxy resin is used. The thickness of such a thin film (recording layer) is preferably in the range of 50 to 500 nm. The reason for this is that when the thickness of the recording layer is less than 50 nm, the change in reflectance is too small and the signal S/N ratio tends to deteriorate, whereas when the thickness exceeds 500 nm, the film thickness There is a risk that the light energy will decrease, leading to a decrease in sensitivity.

上記基材としては、基材裏面側から記録再生を行なう場
合には収束光に対して透明なものが用いられ、例えばガ
ラス、アクリル樹脂、ポリカーゴネート、ポリオレフィ
ン等を挙げることができる。記録層側から書き込み、読
み出しを行なう場合には、前記材料の他にアルミニウム
、銅等の金属や紙もしくは顔料を分散させた樹脂等を用
いることができる。As the base material, a material transparent to convergent light is used when recording and reproduction is performed from the back side of the base material, and examples thereof include glass, acrylic resin, polycargonate, polyolefin, and the like. When writing and reading are performed from the recording layer side, metals such as aluminum and copper, paper, resin in which pigments are dispersed, etc. can be used in addition to the above-mentioned materials.

なお、上記金属ナフタロシアニン又はその誘導体は化学
的に安定な物質であるため、その記録層上に保護層を設
けなくともよいが、必要に応じて５ＩＯ２、ＳｉＯ、ｋ
１２０５　、　ＭｇＦ２等の無機化合物の保護層、又は
アクリル樹脂、ポリカーゴネート、ポリエステル、工Ｉ
キシ樹脂、ポリブチラール、ポリスチレン等の有機化合
物の保護層を設けてもよい。Note that since the metal naphthalocyanine or its derivative is a chemically stable substance, it is not necessary to provide a protective layer on the recording layer, but if necessary, 5IO2, SiO, k
1205, protective layer of inorganic compound such as MgF2, or acrylic resin, polycargonate, polyester,
A protective layer of an organic compound such as xylene resin, polybutyral, polystyrene, etc. may be provided.

また、金属ナフタロシアニン又はその誘導体とＴｏ　、
　Ｂｉ　＊　Ａｔ　＋　Ａｇ　、　Ｓｓ　、　Ａｓ　、
　Ｓｂ　、　Ｃｒ　。Moreover, metal naphthalocyanine or its derivative and To,
Bi * At + Ag, Ss, As,
Sb, Cr.

Ｎ１等の金属全共蒸着させることによって高反射性の記
録層を基材上に形成できる。A highly reflective recording layer can be formed on the base material by fully codepositing a metal such as N1.

更に、上記一般式にて表わされる金属ナフタロシアニン
又はその誘導体を含む薄膜を光吸収層とし、これと金属
光沢性を有する色素を含む薄膜（光反射層）とを任意の
順序で基材上に積層して記録媒体を構成してもよい。こ
の場合、光反射層の膜厚により反射率を制御することが
できる。Furthermore, a thin film containing metal naphthalocyanine or its derivative represented by the above general formula is used as a light absorption layer, and this and a thin film containing a pigment having metallic luster (light reflection layer) are formed on the substrate in any order. A recording medium may be constructed by laminating them. In this case, the reflectance can be controlled by the thickness of the light reflective layer.

上記色素としては、例えばシアニン色素、メロシアニン
色素、トリフェニルメタン系色素、アントラキノン、ナ
フトキノン、フタロシアニン等を用いることができ、こ
うした色素を含む薄膜は光反射層として作用する。かか
る薄膜は、真空蒸着法、スピンナー法により形成される
。As the dye, for example, cyanine dye, merocyanine dye, triphenylmethane dye, anthraquinone, naphthoquinone, phthalocyanine, etc. can be used, and a thin film containing such a dye acts as a light reflecting layer. Such a thin film is formed by a vacuum evaporation method or a spinner method.

なお、前記色素は夫々の種類の波長域で反射率の極大を
有し、かつ光吸収力も波長により異なるため、使用する
装置の光源波長により適宜選択され用いられる。Note that the dye has a maximum reflectance in each type of wavelength range, and its light absorption power also differs depending on the wavelength, so it is appropriately selected and used depending on the light source wavelength of the device used.

上記光吸収層、光反射層としての各薄膜の他に必要に応
じて中間層、保護層を設けることが〒もスー山間層は一
培豊袢の向Ｎ２共に酸素、水分からの保護の目的で設け
られ、主に樹脂又は無機化合物から形成される。樹脂と
しては、前述した金属ナフタロシアニン又はその誘導体
の混合物として用いられるものが適し、必要に応じて、
記録再生以外の不要光をカットするための光吸収剤や酸
化防止剤等を混入する。これらは、スピンナー法、ディ
ップ法により薄膜として形成される。無機化合物として
は、５ｉ０２　。In addition to the above-mentioned thin films as the light-absorbing layer and the light-reflecting layer, intermediate layers and protective layers may be provided as necessary. It is mainly made of resin or inorganic compounds. As the resin, those used as a mixture of the above-mentioned metal naphthalocyanine or its derivatives are suitable, and if necessary,
Light absorbers, antioxidants, etc. are mixed in to cut out unnecessary light for purposes other than recording and reproduction. These are formed as thin films by a spinner method or a dip method. As an inorganic compound, 5i02.

８１０　、　ＡｔＯ、ＳｎＯ、ＭｇＦ２等が用いられ、
イオンビーム、電子ビーム、ス・臂ツタ法により薄膜が
形成される。保護層も中間層と同様の構成をとり、光、
酸素、水分からの記録層の保護、傷、ホコリからの保藤
のために用いられる。810, AtO, SnO, MgF2, etc. are used,
Thin films are formed using ion beams, electron beams, and the armpit method. The protective layer has the same structure as the intermediate layer, and has the same structure as the intermediate layer.
It is used to protect the recording layer from oxygen and moisture, and protect it from scratches and dust.

更に、上記金属光沢性を有する色素の代りにアルミニウ
ム、銀、銅、テルル等の金属蒸着膜を光反射膜として用
いてもよい。Further, instead of the pigment having metallic luster, a vapor-deposited film of a metal such as aluminum, silver, copper, or tellurium may be used as the light-reflecting film.

次に、本発明の光学的情報記録媒体の構成と記録再生方
法について説明する。Next, the structure and recording/reproduction method of the optical information recording medium of the present invention will be explained.

第１図は、光学的情報記録媒体を示すもので、この記録
媒体１は基本的には基材２上に金属すフタロシアニン又
はその誘導体を含む薄膜（記録層）３を設けた構成にな
っている。記録再生は、レーデ光を集光レンズにより記
録層３上に０．８〜１．５μｍの大きさのスポットに集
光して行なわれる。記録再生光は、記録層３側から照射
してもよいが、透明な基材を用いる場合には基材２側か
ら照射する方が一般的に汚れやゴミの影響が生じにくく
なる。FIG. 1 shows an optical information recording medium. This recording medium 1 basically has a structure in which a thin film (recording layer) 3 containing metal phthalocyanine or its derivative is provided on a base material 2. There is. Recording and reproduction are performed by condensing Radhe light onto a spot with a size of 0.8 to 1.5 μm on the recording layer 3 using a condensing lens. The recording/reproducing light may be irradiated from the recording layer 3 side, but when a transparent base material is used, irradiation from the base material 2 side is generally less likely to be affected by dirt or dust.

第２図は、同一構成の２枚の記録媒体１′ｔ−記録層３
側が互に対向するようにスペーサ４を介して配置させた
ものである。なお、第２図中の５はエアーギャップ、６
はスピンドル穴ヲ夫々示す。このような構成では、記録
再生光を基材２側から入射させるため、前述したのと同
様、汚れやゴミの影響を生じにくくなる。FIG. 2 shows two recording media 1't-recording layer 3 having the same configuration.
They are arranged with spacers 4 in between so that their sides face each other. In addition, 5 in Fig. 2 is an air gap, and 6 is an air gap.
indicates each spindle hole. In such a configuration, since the recording and reproducing light is incident from the base material 2 side, the effects of dirt and dust are less likely to occur, as described above.

第３図は、記録層３表面を樹脂層２で保護した記録媒体
１を示す。FIG. 3 shows a recording medium 1 in which the surface of the recording layer 3 is protected by a resin layer 2.

第４図は、基板２上にアンダーコート層８を介して有機
色素の光反射層９と金属ナフタロシアニン又はその誘導
体の光吸収層１０を順次積層した記録媒体１である。か
かる記録媒体１では、集束レーザー光は基板２側、記録
層側いずれからでも入射可能であるが、感度の点から基
原２側から入射させることが望ましい。FIG. 4 shows a recording medium 1 in which a light-reflecting layer 9 made of an organic dye and a light-absorbing layer 10 made of metal naphthalocyanine or a derivative thereof are sequentially laminated on a substrate 2 with an undercoat layer 8 interposed therebetween. In such a recording medium 1, the focused laser beam can enter from either the substrate 2 side or the recording layer side, but from the viewpoint of sensitivity, it is preferable to enter it from the base 2 side.

第５図は、第４図と光反射層９．光吸収層１０の積層順
序を入れ替えた構造の記録媒体１を示す。この場合は、
記録層側よりレーザー光を入射させることが望ましい。FIG. 5 shows FIG. 4 and the light reflecting layer 9. A recording medium 1 having a structure in which the order of stacking the light absorption layers 10 is changed is shown. in this case,
It is desirable that the laser beam be incident on the recording layer side.

第６図は、基、ｔ２上にアンダーコート層８を介して光
吸収層１０、中間層１１、光反射層９、保護層７を順次
積層して記録層を形成した記録媒体１である。レーザー
光は、第４図と同様、基板２側から入射させることが望
ましい。また、この場合、保護層、中間層は特に設ける
必要がない場合、省略できる。FIG. 6 shows a recording medium 1 in which a recording layer is formed by sequentially laminating a light absorbing layer 10, an intermediate layer 11, a light reflecting layer 9, and a protective layer 7 on a substrate t2 with an undercoat layer 8 interposed therebetween. It is desirable that the laser beam be incident from the substrate 2 side as in FIG. 4. Further, in this case, the protective layer and the intermediate layer can be omitted if there is no particular need to provide them.

なお、第４図〜第６図の記録媒体においてアンダーコー
ト層を省略してもよい。Note that the undercoat layer may be omitted in the recording media shown in FIGS. 4 to 6.

第７図は、光反射層９及び光吸収層１０を有する同一構
成の２枚の記録媒体を記録層側が互に対向するようにス
ペーサ４を介して配置させたエアーサンドインチ構造の
ものである。なお、第７図中の５はエアーギャップ、６
はスピンドル穴である。このような構成によれば、記録
層をホコリや傷から保護し易くなるという利点を有する
。FIG. 7 shows an air sandwich structure in which two recording media having the same structure, each having a light reflection layer 9 and a light absorption layer 10, are arranged with a spacer 4 in between so that the recording layers face each other. . In addition, 5 in Fig. 7 is an air gap, and 6 is an air gap.
is the spindle hole. Such a configuration has the advantage that the recording layer can be easily protected from dust and scratches.

〔発明の実施例〕[Embodiments of the invention]

以下、本発明の実施例を詳細に説明する。 Examples of the present invention will be described in detail below.

実施例１ 厚さ１．２ｆｉのアクリル基板上に、下記構造式（１）
に示すアルミニラ、＜◇タロシアニンを真空度１．　Ｑ
　Ｘ　１０−５ｔｏｒｒで真空蒸着して膜厚１１００ｎ
の記録層を形成することにより記録媒体を得た。Example 1 The following structural formula (1) was formed on an acrylic substrate with a thickness of 1.2 fi.
Aluminum oxide shown in <◇Talocyanine was prepared at a vacuum degree of 1. Q
Vacuum evaporated at X 10-5 torr, film thickness 1100n
A recording medium was obtained by forming a recording layer of.

・・・（１） 得られた記録媒体の記録層の反射率を分光光度計で測定
したところ、波長８３０ｎｍにおいて基板側で２７チで
あった。また、前記記録媒体上に波長８３０ｎｍの半導
体レーザの出力光を直径１．２μｍのスポット径に集光
し、線速６　ｍ　／ｓｅｃ、出カフｍＷで記録層側から
Ｉ　ＭＨｚの信号の書込みを行なったところ、記録感度
は３．ＯｎＪ／スポット、再生ＣＮ値は５２　ｄＢであ
った。(1) When the reflectance of the recording layer of the obtained recording medium was measured with a spectrophotometer, it was 27 cm on the substrate side at a wavelength of 830 nm. Further, the output light of a semiconductor laser with a wavelength of 830 nm was focused on the recording medium to a spot diameter of 1.2 μm, and a signal of I MHz was written from the recording layer side at a linear velocity of 6 m/sec and an output power of mW. When I did this, the recording sensitivity was 3. OnJ/spot, reproduction CN value was 52 dB.

実施例２ 厚さ１．２−のガラス基板（コーニング社規）に、前記
構造式（１）のＡｔの代わりにＣｕを導入した銅ナフタ
ロシアニンを実施例１と同様な条件で真空蒸着して厚さ
９５　ｎｍの薄膜を形成した後、この薄膜上に真空度１
．ＯＸ　１０　　ｔｏｒｒの条件でアルミニウムを真空
蒸着して膜厚１１００ｎのＡｔ反射層を形成して前記薄
膜と反射層からなる記録層を有する記録媒体を得た。Example 2 Copper naphthalocyanine in which Cu was introduced in place of At in the structural formula (1) was vacuum-deposited on a 1.2-thick glass substrate (Corning company regulations) under the same conditions as in Example 1. After forming a thin film with a thickness of 95 nm, a vacuum degree of 1 was applied on this thin film.
．． Aluminum was vacuum-deposited under conditions of OX 10 torr to form an At reflective layer with a thickness of 1100 nm, thereby obtaining a recording medium having a recording layer composed of the thin film and the reflective layer.

得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において記録層側で３８俤であった。The reflectance of the recording layer of the obtained recording medium was at a wavelength of 830 nm.
In this case, the distance on the recording layer side was 38 yen.

また、前記記録媒体に実施例１と同様、半導体レーザに
より書込み再生を行なったところ、記録感度は４．０ｎ
Ｊ／スポツト、再生ＣＮ値は４９ｄＢであった。Further, when writing and reproducing were performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 4.0 nm.
J/Spot, the reproduced CN value was 49 dB.

実施例３ 厚さ１．２　ｍのアクリル基板上に、前記構造式（１）
のＡｔの代わｂにＣｏ　ｆ導入し、かつ４つのナフタリ
ンのうちの１つ又は２つのベンゼン環に塩素を導入した
塩素化コバルトナフタロシアニンを実施例１と同様な条
件で真空蒸着して厚さ９５ｎｍの記録層を形成すること
により記録媒体を得た。Example 3 The structural formula (1) was formed on an acrylic substrate with a thickness of 1.2 m.
Chlorinated cobalt naphthalocyanine, in which Cof was introduced in place of At in b and chlorine was introduced into one or two benzene rings of the four naphthalenes, was vacuum deposited under the same conditions as in Example 1 to obtain a thickness. A recording medium was obtained by forming a 95 nm recording layer.

得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で２２俤であった。また、前記記録媒体
に実施例１と同様、半導体レーザによシ書込み再生を行
なったところ、記録感度は３．８ｎＪ／スポツト、再生
ＣＮ値は４８ｄＢであった。The reflectance of the recording layer of the obtained recording medium was at a wavelength of 830 nm.
It was 22 yen on the board side. Further, when writing and reproduction were performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 3.8 nJ/spot, and the reproduction CN value was 48 dB.

実施例４ 厚さ１．２　ｔｍのアクリル基板上に、前記構造式（Ｉ
）のＡｔの代わりにＴｉを導入し、かつ該Ｔｉに酸素を
結合させた酸化チタンナフタロシアニンを実施例１と同
様な条件で真空蒸着して厚ざ８０ｎｍの記録層を形成す
ることにより記録媒体を得た。Example 4 The above structural formula (I
) by introducing Ti in place of At and bonding oxygen to the Ti, titanium oxide naphthalocyanine, was vacuum-deposited under the same conditions as in Example 1 to form a recording layer with a thickness of 80 nm, thereby producing a recording medium. I got it.

得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で２９１であった。また、前記記録媒体
に実施例１と同様、半導体レーデによシ書込み再生を行
なったところ、記録感度は３．５ｎＪ／スポツト、再生
ＣＮ値は４９　ｄＢであった。The reflectance of the recording layer of the obtained recording medium was at a wavelength of 830 nm.
It was 291 on the substrate side. Further, when writing and reproduction were performed on the recording medium using a semiconductor radar in the same manner as in Example 1, the recording sensitivity was 3.5 nJ/spot, and the reproduction CN value was 49 dB.

実施例５ 厚さ１．２　ｍのアクリル基板上に、前記構造式（１）
のＡｔの代わりに水素（Ｈ）を導入した無金属ナフタロ
シアニンを実施例１と同様な条件で真空蒸着して厚さ１
１０５ｎの記録層を形成することにより記録媒体を得た
・ 得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で２８憾であった。また、前記記録媒体
に実施例１と同様、半導体レーザにより書込み再生を行
なったところ、記録感度は３．３ｎＪ／スポツト、再生
ＣＮ値は５１ｄＢであっ△ 実施例６ 厚さ１．２　ｍのアクリル基板上に、金属テルル及び前
記構造式（１）のＡｔの代わりにｐｂを導入した鉛ナフ
タロシアニンを実施例１と同様な条件で真空蒸着して厚
さ５５　ｎｍの記録層を形成することにより記録媒体を
得た。Example 5 The above structural formula (1) was formed on an acrylic substrate with a thickness of 1.2 m.
A metal-free naphthalocyanine in which hydrogen (H) was introduced instead of At was vacuum-deposited under the same conditions as in Example 1 to a thickness of 1.
A recording medium was obtained by forming a recording layer of 105 nm. The reflectance of the recording layer of the obtained recording medium was at a wavelength of 830 nm.
It was 28% on the board side. Further, when writing and reproducing was performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 3.3 nJ/spot, and the reproducing CN value was 51 dB. On the substrate, metallic tellurium and lead naphthalocyanine in which PB was introduced in place of At in the structural formula (1) were vacuum-deposited under the same conditions as in Example 1 to form a recording layer with a thickness of 55 nm. Obtained a recording medium.

得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で４３１であった。また、前記記録媒体
に実施例１と同様、半導体レーザにより書込み再生を行
なったところ、記録感度は３．９ｎＪ／スポツト、再生
ＣＮ値は４９　ｄＢであった。The reflectance of the recording layer of the obtained recording medium was at a wavelength of 830 nm.
It was 431 on the substrate side. Further, when writing and reproducing were performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 3.9 nJ/spot, and the reproducing CN value was 49 dB.

実施例７ 厚さ１．２瓢のアクリル基板上に、前記構造式（１）の
アルミニウ７◇タロシアニン及び前記構造式（１）のＡ
ｔの代わりにＴｉを導入したチタンナフタロシアニンを
実施例１と同様な条件で真空蒸着、共着して厚さ８０　
ｎｍの記録層を形成することにより記録媒体、を得た。Example 7 Aluminum 7◇talocyanine of the structural formula (1) and A of the structural formula (1) were placed on an acrylic substrate with a thickness of 1.2 mm.
Titanium naphthalocyanine, in which Ti was introduced instead of T, was vacuum-deposited and co-deposited under the same conditions as in Example 1 to a thickness of 80 mm.
A recording medium was obtained by forming a recording layer with a thickness of 1 nm.

得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で３１％であった。また、前記記録媒体
に実施例１と同様、半導体レーザによシ書込み再生を行
なったところ、記録感度は３．１ｎＪ／スポツト、再生
ＣＮ値は５３　ｄＢであった。The reflectance of the recording layer of the obtained recording medium was at a wavelength of 830 nm.
It was 31% on the substrate side. Further, when writing and reproducing was performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 3.1 nJ/spot, and the reproducing CN value was 53 dB.

実施例８ 厚さ１．２−のガラス基板上に下記構造式（Ｉｆ）に示
す色素（日本感光色素研究所＜ｍｍ商品名；ＮＫ−１２
５）をジクロルメタンに溶解してスピンナー塗布して厚
さ７０　ｎｍの薄膜を形成した。Example 8 A dye represented by the following structural formula (If) (Japan Photosensitive Dye Research Institute <mm, trade name: NK-12) was deposited on a 1.2-thick glass substrate.
5) was dissolved in dichloromethane and coated with a spinner to form a thin film with a thickness of 70 nm.

つづいて、この薄膜上に前記構造式（１）のＡｔの代わ
りにＺｎを導入し九亜鉛ナフタロシアニンを真空度１．
ＯＸ　１０　　ｔｏｒｒの条件で加熱蒸着して厚さ３０
　ｎｍの薄膜を積層して記録層を形成することにより記
録媒体を得た。Subsequently, Zn was introduced onto this thin film in place of At in the structural formula (1), and nine zinc naphthalocyanine was applied to the film at a vacuum degree of 1.
Deposited by heating under the conditions of OX 10 torr to a thickness of 30
A recording medium was obtained by laminating thin films of nm thickness to form a recording layer.

・・・（ＩＩ） 得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で３６１であった。また、前記記録媒体
に実施例１と同様、半導体レーザにより書込み再生を行
なったところ、記録感度は２．５ｎＪ／スポツト、再生
ＣＮ値は５０　ｄＢであった。...(II) The reflectance of the recording layer of the obtained recording medium is at a wavelength of 830 nm.
It was 361 on the substrate side. Further, when writing and reproducing were performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 2.5 nJ/spot, and the reproducing CN value was 50 dB.

実施例９ 下記構造式（Ｉ［）に示す色素（日本感光色素研究所■
梨商品名：ＮＫ−２０１４）と１．２ニツケルジチオレ
一ト錯体（三井東圧ファイン社製商品名；　ＰＡ１００
６）とを４：１の割合にて混合し、更にアクリル樹脂（
三菱レーヨン社製商品名；ダイヤナールＢＲ−６０）を
バインダ樹脂として１０重量係添加した。つづいて、こ
の混合物をメチルエチルケトンで溶解して２％濃度の溶
液を調製した後、この溶液を紫外線硬化型レジンで下地
処理された厚さ１．２瓢のアクリル板の該下地レジン上
にスピンナーコータで塗布し、乾燥して厚さ６０　ｎｍ
の薄膜を形成し次。ひきつづき、この薄膜上に前記構造
式（Ｉ）のＡ２０代わりＫＣｏを導入したコバルトナフ
タロシアニン’ｔＸ空度１．Ｑ　Ｘ　Ｉ　Ｑ　　ｔｏｒ
ｒの条件で加熱蒸着して厚さ４０　ｎｍの薄膜を積層し
て記録層を形成することにより記録媒体を得た。Example 9 Dye represented by the following structural formula (I[) (Japan Photosensitive Color Research Institute ■
pear (trade name: NK-2014) and 1.2 nickel dithiolet complex (trade name, manufactured by Mitsui Toatsu Fine Co., Ltd.; PA100)
6) in a ratio of 4:1, and then add acrylic resin (
10% of DIANAL BR-60 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) was added as a binder resin. Next, this mixture was dissolved in methyl ethyl ketone to prepare a 2% solution, and this solution was coated with a spinner onto the base resin of a 1.2-inch thick acrylic board that had been base-treated with an ultraviolet curable resin. and dried to a thickness of 60 nm.
Next, form a thin film of Subsequently, on this thin film, cobalt naphthalocyanine 'tX vacancy 1. Q X I Q tor
A recording medium was obtained by forming a recording layer by laminating thin films with a thickness of 40 nm by heating and vapor deposition under conditions of r.

得られ念記碌媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で３８％であった。また、前記記録媒体
に実施例１と同様、半導体レーザにより書込み再生を行
なったところ、記録感度は２．６ｎＪ／スポツト、再生
ＣＮ値は５０　ｄＢであった〇 比較例１ 厚さ１．２　ｔｍのガラス基板上に、金属テルルを真空
度１．ＯＸ　１０−５ｔｏｒｒの条件で真空蒸着して厚
さ３５　ｎｍの記録層を形成することによ少記録媒体を
得た。The reflectance of the recording layer of the obtained commemorative medium is at a wavelength of 830 nm.
It was 38% on the substrate side. Further, when writing and reproducing was performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 2.6 nJ/spot, and the reproduction CN value was 50 dB. Comparative Example 1 Thickness: 1.2 tm Metal tellurium was placed on a glass substrate at a vacuum level of 1. A small recording medium was obtained by forming a recording layer with a thickness of 35 nm by vacuum deposition under the condition of OX 10-5 torr.

得られた記録媒体に実施例１と同様、半導体レーデによ
り書込み再生を行なったところ、記録感度は５．５ｎＪ
／ス／ｙト、再生ＣＮ値は５０ｄＢであった。When writing and reproducing was performed on the obtained recording medium using a semiconductor radar in the same manner as in Example 1, the recording sensitivity was 5.5 nJ.
/st/y, the reproduced CN value was 50 dB.

比較例２ 前記構造式（ｎ）に示す色素（日本感光色素研究所■実
高品名；ＮＫ−１２５）を塩化メチレンで溶解して２俤
溶液とした後、この溶液を厚さ１、２　ｍのガラス板上
にスピンナーコータで塗布し、乾燥して厚さ８０　ｎｍ
の記録層を形成することＫよ少記録媒体を得た。Comparative Example 2 A dye represented by the above structural formula (n) (Japan Photosensitive Color Research Institute ■Jitaka product name; NK-125) was dissolved in methylene chloride to form a 2-layer solution, and this solution was dissolved in a 1-2 m thick solution. Coated onto a glass plate using a spinner coater and dried to a thickness of 80 nm.
A recording medium with a recording layer of less than K was obtained.

得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で４５俤であった。また、前記記録媒体
に実施例１と同様、半導体レーザにより書込み再生を行
なったところ、記録感度は３．１ｎＪ／スポツト、再生
ＣＮ値は５０　ｄＢであった。The reflectance of the recording layer of the obtained recording medium was at a wavelength of 830 nm.
It was 45 yen on the board side. Furthermore, when writing and reproducing were performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 3.1 nJ/spot, and the reproducing CN value was 50 dB.

比較例３ 前記構造式＜ＩＩＩ）に示す色素（日本感光色素研究所
■梨商品名：ＮＫ−２０１４）と１．２ニツケルジチオ
レ一ト錯体（三井東圧ファイン社製商品名：　ＰＡ１０
０６　）とを４：１の割合にて混合し、更にアクリル樹
脂（三菱レーヨン社製商品名；ダイヤナールＢＲ−６０
）をバインダ樹脂として１５重重量部加した。つづいて
、この混合物をテトラヒドロフランで溶解して２％濃度
の溶液を調製した後、この溶液を紫外線硬化型レジンで
下地処理された厚さ１．２　ｍのアクリル板の該下地レ
ジン上にスピンナーコータで塗布し、乾燥して厚さ７５
ｎｍの記録層を形成することにより記録媒体を得た。Comparative Example 3 A dye shown in the above structural formula <III) (Japan Photosensitive Color Research Institute ■Nashi product name: NK-2014) and a 1.2 nickel dithioleto complex (Mitsui Toatsu Fine Co., Ltd. product name: PA10)
06) at a ratio of 4:1, and further acrylic resin (product name: Dianal BR-60 manufactured by Mitsubishi Rayon Co., Ltd.)
) was added as a binder resin in an amount of 15 parts by weight. Next, this mixture was dissolved in tetrahydrofuran to prepare a 2% solution, and then this solution was coated with a spinner coater onto the base resin of a 1.2 m thick acrylic board that had been base-treated with an ultraviolet curable resin. Coat with and dry to a thickness of 75
A recording medium was obtained by forming a recording layer of nm thickness.

得られた記録媒体の記録層の反射率は、波長８３０ｎｍ
において基板側で２８％であった。また、前記記録媒体
に実施例１と同様、半導体レーザにより書込み再生を行
なったところ、記録感度は３．８ｎＪ／スポツト、再生
ＣＮ値は４７　ｄＢであった。The reflectance of the recording layer of the obtained recording medium was at a wavelength of 830 nm.
It was 28% on the substrate side. Further, when writing and reproduction were performed on the recording medium using a semiconductor laser in the same manner as in Example 1, the recording sensitivity was 3.8 nJ/spot, and the reproduction CN value was 47 dB.

上述した本実施例１〜９及び比較例２．３によシ得られ
た記録媒体を５０℃、相対湿度９５チの雰囲気下に５０
０時間放置し、放置前後の反射率低下率を測定する耐熱
・湿性試験を行なった。また、各記録媒体に２５℃、６
０優の雰囲気で５００Ｗのタングステン光を５０備隔て
て１００時間照射し、同様忙反射率低下高を測定する耐
光試験を行なった。更に、各記録媒体の再生劣化につい
て、促進テストとしてレーザ出力０．７ｍＷの連続光を
３０分間照射した後のＣＮ値の変化を測定した。以上の
結果を下記表に示す。The recording media obtained in Examples 1 to 9 and Comparative Example 2.3 described above were heated for 50 minutes in an atmosphere of 50°C and relative humidity of 95°C.
A heat resistance/humidity test was conducted by allowing the sample to stand for 0 hours and measuring the rate of decrease in reflectance before and after leaving it. In addition, each recording medium was heated at 25°C and 6°C.
A light fastness test was conducted in which 500W tungsten light was irradiated at 50 intervals for 100 hours in a zero-light atmosphere, and the decrease in reflectance was similarly measured. Furthermore, regarding reproduction deterioration of each recording medium, as an accelerated test, changes in CN value were measured after irradiating continuous light with a laser output of 0.7 mW for 30 minutes. The above results are shown in the table below.

・反射率の低下のために測定不能 〔発明の効果〕 以上詳述した如く、本発明によれば半導体レーザー、）
（ｅ−Ｎｅレーザー等のコンノ母りトテ比較的安価な光
源を用いて記録再生が可能で、かつ長期保存安定性に優
れ、再生光による光劣化がなく、高感度で、更に安全で
そのまま廃棄が可能な光学的情報記録媒体を提供できる
。更に、一般式に示す金属ナフタロシアニン又はその誘
導体を含む薄膜と金属光沢性を有する色素を含む薄膜と
を任意の順序で基材上に積層することにより、前記特性
の他に高い反射率を有し、Ｓ／Ｎ比を向上して光学的情
報記録媒体を提供できる。・Unmeasurable due to decrease in reflectance [Effects of the invention] As detailed above, according to the present invention, semiconductor lasers,
(Recording and reproduction is possible using a relatively inexpensive light source such as an e-Ne laser, and it has excellent long-term storage stability. There is no optical deterioration due to reproduction light, and it is highly sensitive. Furthermore, it is safe and can be disposed of as is. Furthermore, a thin film containing a metal naphthalocyanine or a derivative thereof represented by the general formula and a thin film containing a dye having metallic luster can be laminated on a base material in any order. Therefore, in addition to the above characteristics, it has a high reflectance and an improved S/N ratio, making it possible to provide an optical information recording medium.

【図面の簡単な説明】[Brief explanation of drawings]

第１図〜第７図は、夫々本発明の光学的情報記録媒体を
示す概略図である。 １・・・記録媒体、２・・・基材、３・・・薄膜（記録
層）５・・・エアーギャップ、７・・・樹脂層、８・・
・アンダーコート層、９・・・光反射層、１０・・・光
吸収層、１１・・・中間層。 を 第１図 第２図 を 第３図 嘗 第６囚 第７図1 to 7 are schematic diagrams showing optical information recording media of the present invention, respectively. DESCRIPTION OF SYMBOLS 1... Recording medium, 2... Base material, 3... Thin film (recording layer) 5... Air gap, 7... Resin layer, 8...
- Undercoat layer, 9... Light reflecting layer, 10... Light absorbing layer, 11... Intermediate layer. Figure 1 Figure 2 Figure 3 Figure 6 Prisoner Figure 7

Claims (2)

【特許請求の範囲】[Claims] （１）基材上に、一般式 ▲数式、化学式、表等があります▼ 〔但し、式中のＭはＨ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｏ、Ｃｒ
、Ｚｎ、Ｓｎ、Ｐｂ、Ａｌ、Ｉｎ、Ｇａ、Ｖ、Ｍｇ、Ｃ
ｄ、Ｐｄ、Ｔｉ、Ｍｎ、Ｌｉ、Ｃａ、Ｃｅ、Ｐｒ、Ｎｄ
、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂを示し、Ｘはハロゲン
基、アルキル基、カルボキシル基、アルコキシ基、ヒド
ロキシル基、アリル基、アルキルカルボキシ基、ｍは０
〜４の整数を示す〕にて表わされる金属ナフタロシアニ
ン又はその誘導体を含む薄膜を担持させたことを特徴と
する光学的情報記録媒体。(1) On the base material, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [However, M in the formula is H, Cu, Fe, Ni, Co, Cr
, Zn, Sn, Pb, Al, In, Ga, V, Mg, C
d, Pd, Ti, Mn, Li, Ca, Ce, Pr, Nd
, Pm, Sm, Eu, Gd, Tb, X is a halogen group, alkyl group, carboxyl group, alkoxy group, hydroxyl group, allyl group, alkylcarboxy group, m is 0
1. An optical information recording medium comprising a thin film containing a metal naphthalocyanine or a derivative thereof represented by [indicating an integer of ~4]. （２）前記一般式にて表わされる金属ナフタロシアニン
又はその誘導体を含む薄膜と金属光沢を有する色素を含
む色素とを任意の順序で基材上に積層したことを特徴と
する特許請求の範囲第１項記載の光学的情報記録媒体。(2) A thin film containing a metal naphthalocyanine represented by the above general formula or a derivative thereof and a dye containing a dye having metallic luster are laminated on a base material in any order. The optical information recording medium according to item 1.