JP2005267670A - Two-layer type optical recording medium and its manufacturing method - Google Patents

Two-layer type optical recording medium and its manufacturing method Download PDF

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JP2005267670A
JP2005267670A JP2004073841A JP2004073841A JP2005267670A JP 2005267670 A JP2005267670 A JP 2005267670A JP 2004073841 A JP2004073841 A JP 2004073841A JP 2004073841 A JP2004073841 A JP 2004073841A JP 2005267670 A JP2005267670 A JP 2005267670A
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layer
outer peripheral
peripheral side
recording medium
side end
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Tatsuo Kenjo
竜雄 見上
Toru Yashiro
徹 八代
Yuki Nakamura
有希 中村
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Ricoh Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-layer type optical recording medium having satisfactory durability and to provide its manufacturing method. <P>SOLUTION: (1) In the two-layer type optical recording medium wherein a reflection layer consisting of silver or a silver alloy, a recording layer containing an organic dye and a protective layer containing a sulfur element are successively formed on a guide groove side surface of a substrate having a holding hole at its center part and the guide groove on its surface, the reflection layer and the protective layer does not come in contact with each other. (2) In the two-layer type optical recording medium described in (1), the outer peripheral side end part of the reflection layer is positioned on the inner side of the outer peripheral side end part of the substrate and the outer peripheral side end part of the recording layer is superposed on or positioned on the outer side of the outer peripheral side end part of the reflection layer. (3) In the two-layer type optical recording medium described in (1), the outer peripheral side end part of the reflection layer is positioned on the inner side of the outer peripheral side end part of the substrate, the outer peripheral side end part of the recording layer is positioned on the inner side of the outer peripheral side end part of the reflection layer and the outer peripheral side end part of the protective layer is superposed on or positioned on the inner side of the outer peripheral side end part of the recording layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、有機色素を含む記録層を有する2層型光記録媒体及びその製造方法に関する。   The present invention relates to a two-layer optical recording medium having a recording layer containing an organic dye and a method for producing the same.

読み出し専用のDVD(デジタルバーサタイルディスク)などの光記録媒体に加えて、記録可能なDVD(DVD+RW、DVD+R、DVD−R、DVD−RW、DVD−RAMなど)が実用化されている。
このDVD+R、DVD+RWなどは、従来の記録可能なCD−R、CD−RW(記録型コンパクトディスク)技術の延長上に位置するもので、再生専用DVDとの再生互換性を確保するために、記録密度(トラックピッチ、信号マーク長)と基板厚さがCD条件からDVD条件に合うように設計されている。
例えば、DVD+Rでは、CD−Rと同様に、基板上に色素をスピンコーティングして光記録層を設け、その背後に金属反射層を設けた情報記録用基板を、貼り合せ材を介して同形状の基板と貼り合せるという構成が採用されている。
In addition to optical recording media such as a read-only DVD (digital versatile disk), recordable DVDs (DVD + RW, DVD + R, DVD-R, DVD-RW, DVD-RAM, etc.) have been put into practical use.
These DVD + R, DVD + RW, etc. are positioned on the extension of conventional recordable CD-R, CD-RW (recordable compact disc) technology, and are recorded to ensure playback compatibility with playback-only DVDs. The density (track pitch, signal mark length) and substrate thickness are designed to meet the DVD conditions from the CD conditions.
For example, in DVD + R, as in CD-R, an information recording substrate in which an optical recording layer is provided by spin-coating a dye on a substrate and a metal reflective layer is provided behind it is formed in the same shape via a bonding material. The structure of being bonded to the substrate is used.

ところで、読み出し専用DVDでは、記録容量を増大させるために、2層の記録層を有するものが提案されている。図1は、このような2層の記録層を有するDVDの構造を示す断面図である。第1基板と第2基板は、紫外線硬化樹脂から形成された接着層を挟むことにより貼り合わされている。第1基板の内側の面には第1記録層が形成されており、第2基板の内側の面には第2記録層が形成されている。第1記録層は、金属薄膜等を用いた半透明膜として形成されている。第2記録層は反射膜として形成されており、金属膜などから形成されている。第1及び第2記録層には凸凹状の記録マークが形成され、再生レーザー光を反射・干渉する効果にて記録信号を読み取る。2つの記録層から信号を読み取るため、最大8.5GB程度の記憶容量が得られる。
また、第1及び第2基板の厚みはそれぞれ約0.6mmであり、接着層の厚みは約50μmである。第1記録層となる半透明膜は、その反射率が30%程度となるように形成されており、第2記録層を再生するために照射されるレーザー光は第1記録層で全光量の約30%が反射して減衰したのち、第2記録層の反射膜で反射し、更に第1記録層で減衰を受けた後、ディスクから出ていく。再生光であるレーザー光をそれぞれ第1記録層又は第2記録層上に焦点が位置するように絞り、反射光を検出することによりそれぞれの記録層の信号を再生することができる。なお、DVDの場合記録再生に用いるレーザー光波長は約650nmである。
By the way, a read-only DVD has been proposed which has two recording layers in order to increase the recording capacity. FIG. 1 is a cross-sectional view showing the structure of a DVD having such two recording layers. The first substrate and the second substrate are bonded together by sandwiching an adhesive layer formed from an ultraviolet curable resin. A first recording layer is formed on the inner surface of the first substrate, and a second recording layer is formed on the inner surface of the second substrate. The first recording layer is formed as a translucent film using a metal thin film or the like. The second recording layer is formed as a reflective film, and is formed from a metal film or the like. Uneven recording marks are formed on the first and second recording layers, and the recording signal is read by the effect of reflecting / interfering the reproduction laser beam. Since signals are read from the two recording layers, a maximum storage capacity of about 8.5 GB can be obtained.
The thickness of the first and second substrates is about 0.6 mm, and the thickness of the adhesive layer is about 50 μm. The translucent film serving as the first recording layer is formed so that the reflectance thereof is about 30%, and the laser beam irradiated for reproducing the second recording layer is the total amount of light in the first recording layer. After about 30% is reflected and attenuated, it is reflected by the reflective film of the second recording layer, further attenuated by the first recording layer, and then exits the disk. The signal of each recording layer can be reproduced by detecting the reflected light by narrowing the laser light as the reproduction light so that the focal point is located on the first recording layer or the second recording layer, respectively. In the case of DVD, the laser beam wavelength used for recording / reproduction is about 650 nm.

DVD−ROM作成時に、量産前の段階でのデータ内容の確認や客先承認用などの用途において、スタンパを作成してディスク化したものを用いる代りに、容易に作成できDVD−ROMと互換性のあるDVD±Rを用いることが多い。しかしながら記録型DVDは現在1層タイプのものしかないため、2層DVD−ROMの場合にはDVD±Rを用いてサンプルを作成することができず、量産時と同じくスタンパを作成してDVD−ROMを作成する場合がある。このときにデータ内容の間違いなどがあった場合には内容を修正して再度マスタリングする必要があるため、コストと時間がかかってしまう。また、2層DVD−ROMのバックアップが行えないDVD±R/RWをPCデータのバックアップに使用すると、記録容量が不足することがある。そこで、2層DVD−ROM互換性を有する光記録媒体の開発が望まれている。
従来の2層型光記録媒体としては、例えば特許文献1に、図2に示すような第1基板上に有機色素からなる第1記録層と第1反射層を順に設けたディスクと、第2基板上に第2反射層と第2記録層を順に設けたディスクを記録層を内側にして接着層で貼り合わせた構成のものが開示されている。しかしながら上記構成においては、第2記録層と接着層が接しているため経時的に色素が接着剤により侵されるといった現象が生じ、耐久性に問題がある。
When creating a DVD-ROM, it can be easily created and compatible with a DVD-ROM instead of using a stamper created as a disk for purposes such as confirmation of data contents before mass production and customer approval. Often, DVD ± R is used. However, since recordable DVDs are currently only of a single layer type, in the case of a dual layer DVD-ROM, it is not possible to create a sample using DVD ± R. A ROM may be created. If there is an error in the data contents at this time, it is necessary to correct the contents and perform mastering again, which increases costs and time. Also, if DVD ± R / RW, which cannot back up a dual layer DVD-ROM, is used for PC data backup, the recording capacity may be insufficient. Therefore, development of an optical recording medium having double-layer DVD-ROM compatibility is desired.
As a conventional two-layer type optical recording medium, for example, Patent Document 1 discloses a disc in which a first recording layer made of an organic dye and a first reflective layer are sequentially provided on a first substrate as shown in FIG. A disc having a second reflective layer and a second recording layer in order on a substrate and having a recording layer inside is bonded with an adhesive layer is disclosed. However, in the above configuration, since the second recording layer and the adhesive layer are in contact with each other, a phenomenon occurs in which the dye is eroded by the adhesive over time, and there is a problem in durability.

特開平11−06622号公報Japanese Patent Laid-Open No. 11-06622

本発明者らは、上記従来技術の問題点を解決するため、図3に示すように接着層と第2記録層の間に保護層を設けることにより接着剤による色素の侵食を防ぐ方法を見出した。また、第2反射層に銀又は銀合金を用いることにより高い反射率が得られ、保護層に硫黄元素を含む材料を用いることにより良好な特性が得られることを見出した。しかしながら、銀又は銀合金からなる反射層と硫黄元素を含む保護層が接触した場合には、銀と硫黄が反応して硫化銀が形成され反射層が侵食されるという問題がある。
本発明は、この問題を解決した良好な耐久性を有する2層型光記録媒体及びその製造方法の提供を目的とする。
In order to solve the above-described problems of the prior art, the present inventors have found a method for preventing dye erosion by an adhesive by providing a protective layer between the adhesive layer and the second recording layer as shown in FIG. It was. Moreover, it discovered that a high reflectance was obtained by using silver or a silver alloy for the second reflective layer, and good characteristics were obtained by using a material containing sulfur element for the protective layer. However, when a reflective layer made of silver or a silver alloy and a protective layer containing a sulfur element come into contact, there is a problem that silver and sulfur react to form silver sulfide and the reflective layer is eroded.
An object of the present invention is to provide a two-layered optical recording medium having good durability that solves this problem and a method for producing the same.

上記課題は、次の1)〜8)の発明によって解決される。
1) 中央に保持用の穴を有し表面に案内溝を有する基板の案内溝側の面に銀又は銀合金からなる反射層、有機色素を含む記録層、硫黄元素を含む保護層を順に形成してなる光記録媒体において、反射層と保護層が接していないことを特徴とする光記録媒体。
2) 反射層の外周側端部が基板の外周側端部よりも内側にあり、記録層の外周側端部が反射層の外周側端部に対し同一もしくは外側にあることを特徴とする1)記載の2層型光記録媒体。
3) 反射層の外周側端部が基板の外周側端部よりも内側にあり、記録層の外周側端部が反射層の外周側端部よりも内側にあり、保護層の外周側端部が記録層の外周側端部に対し同一もしくは内側にあることを特徴とする1)記載の2層型光記録媒体。
4) 反射層の内周側端部が基板の内周側端部よりも外側にあり、記録層の内周側端部が反射層の内周側端部に対し同一もしくは内側にあることを特徴とする1)〜3)の何れかに記載の2層型光記録媒体。
5) 反射層の内周側端部が基板の内周側端部よりも外側にあり、記録層の内周側端部が反射層の内周側端部に対し外側にあり、保護層の内周側端部が記録層の内周側端部に対し同一もしくは外側にあることを特徴とする1)〜3)の何れかに記載の光記録媒体。
6) 基板上に反射層、記録層を形成した後、又は保護層を形成した後に、外周端部の記録層を除去することを特徴とする2)又は3)記載の2層型光記録媒体の製造方法。
7) 基板上に反射層を形成した後、色素溶液を吐出してスピンコート法により反射層の内周側端部よりも内側に記録層の内周側端部を形成し、記録層内周側端部よりも保護層の内周側端部が内側になるように保護層を形成することを特徴とする4)記載の2層型光記録媒体の製造方法。
8) 請求項7記載の製造方法により、保護層の内周側端部が反射層の内周側端部よりも1mm以上内周側になるように作製されたことを特徴とする4)記載の2層型光記録媒体。
The above problems are solved by the following inventions 1) to 8).
1) A reflective layer made of silver or a silver alloy, a recording layer containing an organic dye, and a protective layer containing a sulfur element are sequentially formed on the surface of the guide groove side of the substrate having a holding hole in the center and having a guide groove on the surface. An optical recording medium, wherein the reflective layer and the protective layer are not in contact with each other.
2) The outer peripheral side end of the reflective layer is inside the outer peripheral side end of the substrate, and the outer peripheral side end of the recording layer is the same as or outside the outer peripheral side end of the reflective layer. 2 layer type optical recording medium.
3) The outer peripheral end of the reflective layer is on the inner side of the outer peripheral end of the substrate, the outer peripheral end of the recording layer is on the inner side of the outer peripheral end of the reflective layer, and the outer peripheral end of the protective layer Are the same or inside with respect to the outer peripheral end of the recording layer. 2. The two-layer type optical recording medium according to 1), wherein
4) The inner peripheral side end of the reflective layer is outside the inner peripheral side end of the substrate, and the inner peripheral side end of the recording layer is the same or inside the inner peripheral side end of the reflective layer. The two-layer optical recording medium according to any one of 1) to 3), which is characterized in that
5) The inner peripheral end of the reflective layer is outside the inner peripheral end of the substrate, the inner peripheral end of the recording layer is outside the inner peripheral end of the reflective layer, and the protective layer The optical recording medium according to any one of 1) to 3), wherein the inner peripheral side end is the same as or outside the inner peripheral side end of the recording layer.
6) The two-layer type optical recording medium according to 2) or 3), wherein the recording layer at the outer peripheral edge is removed after forming the reflective layer, the recording layer on the substrate, or after forming the protective layer. Manufacturing method.
7) After forming the reflective layer on the substrate, the dye solution is discharged, and the inner peripheral side end of the recording layer is formed inside the inner peripheral side end of the reflective layer by spin coating. 4. The method for producing a two-layer type optical recording medium according to 4), wherein the protective layer is formed so that the inner peripheral side end of the protective layer is on the inner side than the side end.
8) The manufacturing method according to claim 7, wherein the inner peripheral side end portion of the protective layer is manufactured to be 1 mm or more inner peripheral side than the inner peripheral side end portion of the reflective layer. A two-layer optical recording medium.

以下、上記本発明について詳細に説明する。
本発明の光記録媒体は、通常、次のようにして作成する。
まず、中心に保持用の孔を有し表面に案内溝を有する第二基板上に、蒸着、スパッタリング又はイオンプレーティング法により第二反射層を形成する。反射層材料としてはレーザー光波長に対する反射率が高いAg又はAg合金を用いる。
続いて第二反射層の上に有機色素からなる第二記録層を形成する。第二記録層に用いる色素材料としては、例えば、シアニン系色素、フタロシアニン系色素、ピリリウム系・チオピリリウム系色素、アズレニウム系色素、スクアリリウム系色素、アゾ系色素、ホルマザンキレート系色素、Ni,Crなどの金属錯塩系色素、ナフトキノン系・アントラキノン系色素、インドフェノール系色素、インドアニリン系色素、トリフェニルメタン系色素、トリアリルメタン系色素、アミニウム系・ジインモニウム系色素及びニトロソ化合物を挙げることができる。これらは単独で用いても混合して用いても構わない。また、バインダー、安定剤等を含有させることも可能である。第二記録層の形成手段としては、上記色素材料をしかるべき溶媒に溶解しスピンコート法により塗布する手段が一般的である。
続いて第二記録層の上に保護層を形成して第二の光記録媒体とする。保護層は色素を侵食しないことを考慮して、蒸着、スパッタリング又はイオンプレーティング法により形成する。保護層材料としては光透過性が高い無機物質、特に記録特性が良好であることから硫黄元素を含有するZnS・SiO、ZnS・SiC、ZnS等を含むものを用いる。
次に、第一基板上に第一記録層、第一反射層を順に設けた第一の光記録媒体と貼り合わせることにより2層型光記録媒体とすることができる。貼り合わせにはアクリレート系、エポキシ系、ウレタン系の紫外線硬化型又は熱硬化型接着剤等が使用できるが、透明シートにより貼り合わせる方法でも良い。
Hereinafter, the present invention will be described in detail.
The optical recording medium of the present invention is usually prepared as follows.
First, a second reflective layer is formed by vapor deposition, sputtering, or ion plating on a second substrate having a holding hole at the center and a guide groove on the surface. As the reflective layer material, Ag or an Ag alloy having a high reflectance with respect to the wavelength of the laser beam is used.
Subsequently, a second recording layer made of an organic dye is formed on the second reflective layer. Examples of the dye material used for the second recording layer include cyanine dyes, phthalocyanine dyes, pyrylium / thiopyrylium dyes, azurenium dyes, squarylium dyes, azo dyes, formazan chelate dyes, and Ni and Cr. Examples thereof include metal complex dyes, naphthoquinone dyes / anthraquinone dyes, indophenol dyes, indoaniline dyes, triphenylmethane dyes, triallylmethane dyes, aminium dyes / diimmonium dyes, and nitroso compounds. These may be used alone or in combination. It is also possible to contain a binder, a stabilizer and the like. As a means for forming the second recording layer, a means for dissolving the dye material in an appropriate solvent and applying it by spin coating is common.
Subsequently, a protective layer is formed on the second recording layer to obtain a second optical recording medium. The protective layer is formed by vapor deposition, sputtering or ion plating in consideration of not eroding the dye. As the protective layer material, an inorganic substance having a high light transmission property, particularly a material containing ZnS.SiO 2 , ZnS.SiC, ZnS or the like containing a sulfur element because of good recording characteristics is used.
Next, a two-layer optical recording medium can be obtained by laminating with a first optical recording medium in which a first recording layer and a first reflective layer are provided in this order on a first substrate. An acrylate-based, epoxy-based, or urethane-based ultraviolet curable adhesive or thermosetting adhesive can be used for bonding, but a method of bonding with a transparent sheet may be used.

以上の構成の光記録媒体において、銀又は銀合金からなる第二反射層と硫黄元素を含有する保護層が接触すると硫化銀を形成し第二反射層の腐食がおき耐久性に問題が生じる。これを解消する方法としては、光記録媒体の外周側端部の形状を、図4に示すように第二記録層の外周側端部が第二反射層の外周側端部に対し同一もしくは外側にあるようにするとよい。この場合には保護層の外周端部が何れの位置にあっても第二反射層と接触することはない。図4の(2)では、第二反射層の端部と保護層とが接しているように見えるが、実際の第二反射層は極めて薄い薄膜であり、端部における接触面積は僅少であるから、端部において実用上問題が生じる程に第二反射層が侵食されることはない。
或いは図5に示すように第二記録層の外周側端部が第二反射層の外周側端部よりも内側にあり、保護層の外周側端部が第二記録層の外周側端部に対し同一もしくは内側にあるようにしてもよい。
この際に第二反射層の外周側端部を第二基板の外周側端部よりも内側に形成することが望ましい。何故ならば、第一の光記録媒体と貼り合わせるときに、接着剤との密着性の高い第二基板と接着剤を接触させることにより接着性を向上させるが、第二反射層が基板外縁部まであると第二反射層の外縁が外気と接触することとなり、腐食が生じ易いためである。
In the optical recording medium having the above configuration, when the second reflective layer made of silver or a silver alloy and the protective layer containing sulfur element come into contact with each other, silver sulfide is formed and the second reflective layer is corroded, resulting in a problem in durability. As a method of solving this, the shape of the outer peripheral side end of the optical recording medium is the same as or outside the outer peripheral side end of the second reflective layer as shown in FIG. It is good to be in. In this case, the outer peripheral end of the protective layer is not in contact with the second reflective layer regardless of the position. In FIG. 4 (2), the end of the second reflective layer seems to be in contact with the protective layer, but the actual second reflective layer is a very thin thin film, and the contact area at the end is very small. Therefore, the second reflective layer is not eroded to such an extent that a practical problem occurs at the end.
Alternatively, as shown in FIG. 5, the outer peripheral end of the second recording layer is on the inner side of the outer peripheral end of the second reflective layer, and the outer peripheral end of the protective layer is on the outer peripheral end of the second recording layer. However, they may be the same or inside.
At this time, it is desirable to form the outer peripheral end of the second reflective layer inside the outer peripheral end of the second substrate. The reason is that when the second optical recording medium is bonded to the first optical recording medium, the adhesive is improved by bringing the second substrate and the adhesive into contact with each other. This is because the outer edge of the second reflective layer comes into contact with the outside air and corrosion tends to occur.

また、図6に示すように第二記録層の内周側端部が第二反射層の内周側端部に対し同一もしくは内側にあることが望ましい。この場合には保護層の内周端部が何れの位置にあっても第二反射層と接触することはない。図6の(2)では、図4の(2)の場合と同様に第二反射層の端部と保護層とが接しているように見えるが、実際の第二反射層は極めて薄い薄膜であり、端部における接触面積は僅少であるから、端部において実用上問題が生じる程に第二反射層が侵食されることはない。
或いは図7に示すように第二記録層の内周側端部が第二反射層の内周側端部に対し外側にあり、保護層の内周側端部が第二記録層の内周側端部に対し同一もしくは外側にあることが望ましい。
この際に第二反射層の内周側端部を第二基板の内周側端部よりも外側に形成することが望ましい。何故ならば、第一の光記録媒体と貼り合わせるときに、接着剤との密着性の高い第二基板と接着剤を接触させて接着性を向上させるが、第二反射層が基板内縁部まであると第二反射層の内縁が外気と接触することとなり、腐食が生じ易いためである。
更に、もう一方の光記録媒体と貼り合わせる時に接着層と第二記録層が接すると記録層中の色素材料が溶出する恐れがある。よって保護層が第二記録層を覆う形状が望ましく、光記録媒体の外周側端部については図4の(2)、(4)又は図5の(2)の形状、内周側端部については図6の(2)、(4)又は図7の(2)の形状が望ましい。
Further, as shown in FIG. 6, it is desirable that the inner peripheral side end portion of the second recording layer be the same or inside the inner peripheral side end portion of the second reflective layer. In this case, the inner peripheral end of the protective layer does not come into contact with the second reflective layer regardless of the position. 6 (2), the end of the second reflective layer seems to be in contact with the protective layer as in FIG. 4 (2), but the actual second reflective layer is a very thin thin film. In addition, since the contact area at the end is very small, the second reflective layer is not eroded to such an extent that a practical problem occurs at the end.
Alternatively, as shown in FIG. 7, the inner peripheral end of the second recording layer is outside the inner peripheral end of the second reflective layer, and the inner peripheral end of the protective layer is the inner periphery of the second recording layer. It is desirable to be the same or outside the side end.
At this time, it is desirable to form the inner peripheral end of the second reflective layer outside the inner peripheral end of the second substrate. This is because, when bonding to the first optical recording medium, the adhesive is improved by contacting the adhesive with the second substrate having high adhesion to the adhesive, but the second reflective layer extends to the inner edge of the substrate. This is because the inner edge of the second reflective layer comes into contact with the outside air, and corrosion is likely to occur.
Further, if the adhesive layer and the second recording layer are in contact with each other when the other optical recording medium is bonded, the dye material in the recording layer may be eluted. Therefore, the shape in which the protective layer covers the second recording layer is desirable, and the outer peripheral side end of the optical recording medium is the shape of (2), (4) or FIG. 5 (2) in FIG. 4, and the inner peripheral side end. The shape of (2), (4) in FIG. 6 or (2) in FIG. 7 is desirable.

スピンコート法によって上記の形状を実現するため、外周端部においては第二反射層上に第二記録層を形成した後、又は第二記録層上に保護層を形成した後で外周側端部の記録層を除去する方法が好ましい。除去方法としては記録層を溶解する溶媒を用いて洗い流す方法が好適である。また内周端部においては、第二反射層を形成した後に第二反射層の内周側端部よりも内側から色素を塗布し、形成した第二記録層の内周側端部よりも内側に保護層の内周側端部を形成する方法が好ましい。このとき第二反射層の内周側端部よりも保護層の内周側端部が1mm以上内周にあることが望ましい。この間隔が1mmよりも小さい場合にはスピンコートにより第二記録層を形成する際に、その内周側端部が変動やバラツキのため保護層の内周側端部よりも内側になったり、第二反射層の内周側端部よりも外側になったりするため問題となることがある。   In order to realize the above-described shape by the spin coating method, the outer peripheral end portion is formed on the outer peripheral end portion after forming the second recording layer on the second reflective layer or after forming the protective layer on the second recording layer. A method of removing the recording layer is preferable. As a removal method, a method of washing away using a solvent that dissolves the recording layer is suitable. Also, at the inner peripheral edge, after the second reflective layer is formed, the dye is applied from the inner side of the inner peripheral side end of the second reflective layer, and inside the inner peripheral side end of the formed second recording layer. The method of forming the inner peripheral side end of the protective layer is preferred. At this time, it is desirable that the inner peripheral side end of the protective layer is 1 mm or more inner peripheral than the inner peripheral side end of the second reflective layer. When this interval is smaller than 1 mm, when the second recording layer is formed by spin coating, the inner peripheral end thereof is on the inner side than the inner peripheral end of the protective layer due to fluctuations and variations, This may be a problem because it may be outside the inner peripheral side end of the second reflective layer.

本発明によれば、硫黄元素を含む保護層による銀又は銀合金からなる反射層の侵食を防ぐことができる良好な耐久性を有する2層型光記録媒体及びその製造方法を提供できる。   ADVANTAGE OF THE INVENTION According to this invention, the two-layer type optical recording medium which has the favorable durability which can prevent the corrosion of the reflection layer which consists of silver or a silver alloy by the protective layer containing a sulfur element, and its manufacturing method can be provided.

以下、実施例により本発明を更に具体的に説明するが、本発明はこれらの実施例により限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.

<実施例1>
中心穴及びトラックピッチ0.74μmの案内溝を有する厚さ0.6mm、直径120mmの円盤状ポリカーボネート基板上に、半径20mm〜59.6mmの範囲において、スパッタリングにより厚さ1300ÅのAg反射層を形成した。
続いて、スクアリリウム色素を2,2,3,3−テトラフルオルプロプロパノール中に濃度1.5重量%で溶解した溶液を、半径19mmから外側の部分にスピンコート法により塗布して記録層を形成した。
続いて、ZnS・SiOをスパッタリングにより半径18mm〜59.5mmの範囲に厚さ1200Åで形成し保護層とした。
続いて、スピンコーターで1−メトキシ−2−プロパノールを半径59.2mmの位置に吐出し、保護層の外縁部よりも外周部の色素を除去して第二の光記録媒体を作成した。
次いで、この第二の光記録媒体の保護層上に日本化薬製DVD−003(紫外線硬化型接着剤)を塗布した後、第一の光記録媒体(厚さ0.57mm、直径120mmの案内溝を有する円盤状ポリカーボネート基板上にスクアリリウム色素を2,2,3,3−テトラフルオルプロパノール中に濃度1.0重量%で溶解した溶液をスピンコート法により塗布して記録層を形成し、その上に銀合金膜を厚さ120Å形成したもの)を重ねて回転させることにより接着剤を均一に延展し、続いて紫外線を照射して接着剤を硬化させ2層光記録媒体を得た。
この2層型光記録媒体に対し、波長657nm、NA0.65の光学系を有する記録装置を用いて線速度9.2m/s、記録パワー21mWの条件で記録を行い、線速度3.8m/s、再生パワー0.7mWの条件でタイムインターバルアナライザを用いてジッタの測定を行ったところ、半径23mmにおいて7.3%、半径58.5mmにおいて7.6%であった。
更に、この2層型光記録媒体を80℃85%の条件下で300時間放置した後、ジッタを測定したところ、半径23mmにおいて7.6%、半径58.5mmにおいて7.7%であり耐久性は良好であった。
<Example 1>
An Ag reflective layer having a thickness of 1300 mm is formed by sputtering in a radius range of 20 mm to 59.6 mm on a disk-shaped polycarbonate substrate having a thickness of 120 mm and a diameter of 0.6 mm having a center hole and a guide groove having a track pitch of 0.74 μm. did.
Subsequently, a solution in which squarylium dye was dissolved in 2,2,3,3-tetrafluoropropropanol at a concentration of 1.5% by weight was applied to the outer portion from a radius of 19 mm by a spin coating method to form a recording layer. Formed.
Subsequently, ZnS · SiO 2 was formed in a radius of 18 mm to 59.5 mm by sputtering to a thickness of 1200 mm to form a protective layer.
Subsequently, 1-methoxy-2-propanol was ejected to a position having a radius of 59.2 mm with a spin coater, and the dye on the outer peripheral portion than the outer peripheral portion of the protective layer was removed to prepare a second optical recording medium.
Next, after applying Nippon Kayaku DVD-003 (ultraviolet curable adhesive) on the protective layer of the second optical recording medium, the first optical recording medium (thickness 0.57 mm, diameter 120 mm guide) A recording layer is formed by applying a solution prepared by dissolving squarylium dye in 2,2,3,3-tetrafluoropropanol at a concentration of 1.0% by weight on a disc-shaped polycarbonate substrate having grooves by a spin coating method, The adhesive was uniformly spread by rotating a silver alloy film having a thickness of 120 mm thereon and rotated, and subsequently the adhesive was cured by irradiating ultraviolet rays to obtain a two-layer optical recording medium.
This two-layer optical recording medium was recorded under the conditions of a linear velocity of 9.2 m / s and a recording power of 21 mW using a recording apparatus having an optical system with a wavelength of 657 nm and NA of 0.65, and a linear velocity of 3.8 m / s. The jitter was measured using a time interval analyzer under the conditions of s and reproduction power of 0.7 mW, and found to be 7.3% at a radius of 23 mm and 7.6% at a radius of 58.5 mm.
Further, this two-layer optical recording medium was allowed to stand for 300 hours at 80 ° C. and 85%, and then the jitter was measured. As a result, it was 7.6% at a radius of 23 mm and 7.7% at a radius of 58.5 mm. The property was good.

<実施例2>
中心穴及びトラックピッチ0.74μmの案内溝を有する厚さ0.6mm、直径120mmの円盤状ポリカーボネート基板上に、半径20mm〜59.4mmの範囲において、スパッタリングにより厚さ1300ÅのAg反射層を形成した。
続いて、スクアリリウム色素を2,2,3,3−テトラフルオルプロパノール中に濃度1.5wt%で溶解した溶液を、半径19mmから外側の部分にスピンコート法により塗布して記録層を形成した。
続いて、ZnS・SiOをスパッタリングにより半径18mm〜59.3mmの範囲に厚さ1200Åで形成し保護層とした。
続いて、スピンコーターで1−メトキシ−2−プロパノールを半径59.2mmの位置に吐出し、保護層の外縁部よりも外周部の色素を除去して第二の光記録媒体を作成した。
次いで、この第二の光記録媒体の保護層上に日本化薬製DVD−003(紫外線硬化型接着剤)を塗布した後、第一の光記録媒体(厚さ0.57mm、直径120mmの案内溝を有する円盤状ポリカーボネート基板上にスクアリリウム色素を2,2,3,3−テトラフルオルプロパノール中に濃度1.0重量%で溶解した溶液をスピンコート法により塗布して記録層を形成し、その上に銀合金膜を厚さ120Å形成したもの)を重ねて回転させることにより接着剤を均一に延展し、続いて紫外線を照射して接着剤を硬化させ2層型光記録媒体を得た。
この2層型光記録媒体に対し、波長657nm、NA0.65の光学系を有する記録装置を用いて線速度9.2m/s、記録パワー21mWの条件で記録を行い、線速度3.8m/s、再生パワー0.7mWの条件でタイムインターバルアナライザを用いてジッタの測定を行ったところ、半径23mmにおいて7.4%、半径58.5mmにおいて7.7%であった。
更に、この光記録媒体を80℃85%の条件下で300時間放置した後、ジッタを測定したところ、半径23mmにおいて7.5%、半径58.5mmにおいて7.8%であり耐久性は良好であった。
<Example 2>
An Ag reflective layer having a thickness of 1300 mm is formed by sputtering in a radius range of 20 mm to 59.4 mm on a disk-like polycarbonate substrate having a thickness of 120 mm and a diameter of 0.6 mm having a center hole and a guide groove having a track pitch of 0.74 μm. did.
Subsequently, a solution in which squarylium dye was dissolved in 2,2,3,3-tetrafluoropropanol at a concentration of 1.5 wt% was applied to the outer portion from a radius of 19 mm by a spin coating method to form a recording layer. .
Subsequently, ZnS · SiO 2 was formed in a radius of 18 mm to 59.3 mm by sputtering to a thickness of 1200 mm to form a protective layer.
Subsequently, 1-methoxy-2-propanol was ejected to a position having a radius of 59.2 mm with a spin coater, and the dye on the outer peripheral portion than the outer peripheral portion of the protective layer was removed to prepare a second optical recording medium.
Next, after applying Nippon Kayaku DVD-003 (ultraviolet curable adhesive) on the protective layer of the second optical recording medium, the first optical recording medium (thickness 0.57 mm, diameter 120 mm guide) A recording layer is formed by applying a solution prepared by dissolving squarylium dye in 2,2,3,3-tetrafluoropropanol at a concentration of 1.0% by weight on a disc-shaped polycarbonate substrate having grooves by a spin coating method, The adhesive was uniformly spread by rotating and rotating a silver alloy film having a thickness of 120 mm thereon, and then the adhesive was cured by irradiating ultraviolet rays to obtain a two-layer optical recording medium. .
This two-layer optical recording medium was recorded under the conditions of a linear velocity of 9.2 m / s and a recording power of 21 mW using a recording apparatus having an optical system with a wavelength of 657 nm and NA of 0.65, and a linear velocity of 3.8 m / s. The jitter was measured using a time interval analyzer under the conditions of s and reproduction power of 0.7 mW, and found to be 7.4% at a radius of 23 mm and 7.7% at a radius of 58.5 mm.
Further, the optical recording medium was allowed to stand for 300 hours at 80 ° C. and 85%, and the jitter was measured. As a result, the durability was 7.5% at a radius of 23 mm and 7.8% at a radius of 58.5 mm. Met.

<比較例1>
中心穴及びトラックピッチ0.74μmの案内溝を有する厚さ0.6mm、直径120mmの円盤状ポリカーボネート基板上に、半径20mm〜59.4mmの範囲において、スパッタリングにより厚さ1300ÅのAg反射層を形成した。
続いて、スクアリリウム色素を2,2,3,3−テトラフルオルプロパノール中に濃度1.5重量%で溶解した溶液を、半径21mmから外側の部分にスピンコート法により塗布して記録層を形成した。
続いて、ZnS・SiOをスパッタリングにより半径18mm〜59.3mmの範囲に厚さ1200Åで形成し保護層とした。
続いて、スピンコーターで1−メトキシ−2−プロパノールを半径59.2mmの位置に吐出し、保護層の外縁部よりも外周部の色素を除去して第二の光記録媒体を作成した。
次いで、この第二の光記録媒体の保護層上に日本化薬製DVD−003(紫外線硬化型接着剤)を塗布した後、第一の光記録媒体(厚さ0.57mm、直径120mmの案内溝を有する円盤状ポリカーボネート基板上にスクアリリウム色素を2,2,3,3−テトラフルオルプロパノール中に濃度1.0重量%で溶解した溶液をスピンコート法により塗布して記録層を形成し、その上に銀合金膜を厚さ120Å形成したもの)を重ねて回転させることにより接着剤を均一に延展し、続いて紫外線を照射して接着剤を硬化させ2層型光記録媒体を得た。
この2層型光記録媒体に対し、波長657nm、NA0.65の光学系を有する記録装置を用いて線速度9.2m/s、記録パワー21mWの条件で記録を行い、線速度3.8m/s、再生パワー0.7mWの条件でタイムインターバルアナライザを用いてジッタの測定を行ったところ、半径23mmにおいて7.5%、半径58.5mmにおいて7.6%であった。
更に、この光記録媒体を80℃85%の条件下で300時間放置した後、ジッタを測定したところ、半径23mmにおいて10.5%、半径58.5mmにおいて7.8%であり、光記録媒体内周部において銀反射膜の腐食による特性の悪化が生じた。
<Comparative Example 1>
An Ag reflective layer having a thickness of 1300 mm is formed by sputtering in a radius range of 20 mm to 59.4 mm on a disk-like polycarbonate substrate having a thickness of 120 mm and a diameter of 0.6 mm having a center hole and a guide groove having a track pitch of 0.74 μm. did.
Subsequently, a solution in which squarylium dye is dissolved in 2,2,3,3-tetrafluoropropanol at a concentration of 1.5% by weight is applied to the outer portion from a radius of 21 mm by a spin coating method to form a recording layer. did.
Subsequently, ZnS · SiO 2 was formed in a radius of 18 mm to 59.3 mm by sputtering to a thickness of 1200 mm to form a protective layer.
Subsequently, 1-methoxy-2-propanol was ejected to a position having a radius of 59.2 mm with a spin coater, and the dye on the outer peripheral portion than the outer peripheral portion of the protective layer was removed to prepare a second optical recording medium.
Next, after applying Nippon Kayaku DVD-003 (ultraviolet curable adhesive) on the protective layer of the second optical recording medium, the first optical recording medium (thickness 0.57 mm, diameter 120 mm guide) A recording layer is formed by applying a solution prepared by dissolving squarylium dye in 2,2,3,3-tetrafluoropropanol at a concentration of 1.0% by weight on a disc-shaped polycarbonate substrate having grooves by a spin coating method, The adhesive was uniformly spread by rotating and rotating a silver alloy film having a thickness of 120 mm thereon, and then the adhesive was cured by irradiating ultraviolet rays to obtain a two-layer optical recording medium. .
Recording was performed on the two-layer optical recording medium under the conditions of a linear velocity of 9.2 m / s and a recording power of 21 mW using a recording apparatus having an optical system with a wavelength of 657 nm and NA of 0.65. The jitter was measured using a time interval analyzer under the conditions of s and reproduction power of 0.7 mW, and it was 7.5% at a radius of 23 mm and 7.6% at a radius of 58.5 mm.
Further, this optical recording medium was allowed to stand for 300 hours at 80 ° C. and 85%, and then jitter was measured. As a result, it was 10.5% at a radius of 23 mm and 7.8% at a radius of 58.5 mm. The deterioration of the characteristics due to the corrosion of the silver reflecting film occurred in the inner periphery.

従来の2層の記録層を有するDVDの構造を示す断面図。Sectional drawing which shows the structure of DVD which has the conventional two recording layers. 特許文献1に記載された光記録媒体の構造を示す断面図。Sectional drawing which shows the structure of the optical recording medium described in patent document 1. FIG. 本発明者等が見出した接着層と第2記録層の間に保護層を設けることにより接着剤による色素の侵食を防ぐ方法を示す図。The figure which shows the method of preventing the erosion of the pigment | dye by an adhesive agent by providing a protective layer between the contact bonding layer which the present inventors etc. discovered, and the 2nd recording layer. 第二記録層の外周側端部が第二反射層の外周側端部に対し同一もしくは外側にあるようにした例を示す図。(1)第二記録層と第二反射層の外周側端部が同一の例。(2)保護層が外周側端部を覆う例。(3)第二記録層が第二反射層の外周側端部を覆う例。(4)第二記録層が第二反射層の外周側端部を覆い、保護層が第二記録層の外周側端部を覆う例。The figure which shows the example which made it the outer peripheral side edge part of a 2nd recording layer be the same or the outer side with respect to the outer peripheral side edge part of a 2nd reflective layer. (1) An example in which the outer peripheral side ends of the second recording layer and the second reflective layer are the same. (2) An example in which the protective layer covers the outer peripheral end. (3) An example in which the second recording layer covers the outer peripheral side end of the second reflective layer. (4) An example in which the second recording layer covers the outer peripheral end of the second reflective layer, and the protective layer covers the outer peripheral end of the second recording layer. 第二記録層の外周側端部が第二反射層の外周側端部よりも内側にあり、保護層の外周側端部が第二記録層の外周側端部に対し同一もしくは内側にあるようにした例を示す図。(1)保護層の外周側端部が第二記録層の外周側端部よりも内側になる例。(2)保護層と第二記録層の外周側端部が同一の例。The outer peripheral end of the second recording layer is on the inner side of the outer peripheral end of the second reflective layer, and the outer peripheral end of the protective layer is the same or on the inner side of the outer peripheral end of the second recording layer The figure which shows the example made. (1) An example in which the outer peripheral side end of the protective layer is inside the outer peripheral side end of the second recording layer. (2) An example in which the outer peripheral side ends of the protective layer and the second recording layer are the same. 第二記録層の内周側端部が第二反射層の内周側端部に対し同一もしくは内側にある例を示す図。(1)第二記録層と第二反射層の内周側端部が同一の例。(2)保護層が内周側端部を覆う例。(3)第二記録層が第二反射層の内周側端部を覆う例。(4)第二記録層が第二反射層の内周側端部を覆い、保護層が第二記録層の内周側端部を覆う例。The figure which shows the example in which the inner peripheral side edge part of a 2nd recording layer is the same or inside with respect to the inner peripheral side edge part of a 2nd reflective layer. (1) An example in which the inner peripheral side ends of the second recording layer and the second reflective layer are the same. (2) An example in which the protective layer covers the inner peripheral side end. (3) An example in which the second recording layer covers the inner peripheral side end of the second reflective layer. (4) An example in which the second recording layer covers the inner peripheral end of the second reflective layer and the protective layer covers the inner peripheral end of the second recording layer. 第二記録層の内周側端部が第二反射層の内周側端部に対し外側にあり、保護層の内周側端部が第二記録層の内周側端部に対し同一もしくは外側にある例を示す図。(1)保護層の内周側端部が第二記録層の内周側端部よりも外側になる例。(2)保護層と第二記録層の内周側端部が同一の例。The inner peripheral end of the second recording layer is outside the inner peripheral end of the second reflective layer, and the inner peripheral end of the protective layer is the same as the inner peripheral end of the second recording layer or The figure which shows the example which exists in the outer side. (1) An example in which the inner peripheral end of the protective layer is outside the inner peripheral end of the second recording layer. (2) An example in which the inner peripheral side ends of the protective layer and the second recording layer are the same.

Claims (8)

中央に保持用の穴を有し表面に案内溝を有する基板の案内溝側の面に銀又は銀合金からなる反射層、有機色素を含む記録層、硫黄元素を含む保護層を順に形成してなる光記録媒体において、反射層と保護層が接していないことを特徴とする2層型光記録媒体。   A reflective layer made of silver or a silver alloy, a recording layer containing an organic dye, and a protective layer containing sulfur element are formed in this order on the guide groove side surface of the substrate having a holding hole in the center and a guide groove on the surface. A two-layer optical recording medium, wherein the reflective layer and the protective layer are not in contact with each other. 反射層の外周側端部が基板の外周側端部よりも内側にあり、記録層の外周側端部が反射層の外周側端部に対し同一もしくは外側にあることを特徴とする請求項1記載の2層型光記録媒体。   2. The outer peripheral side end of the reflective layer is inside the outer peripheral side end of the substrate, and the outer peripheral side end of the recording layer is the same as or outside the outer peripheral side end of the reflective layer. The two-layer optical recording medium described. 反射層の外周側端部が基板の外周側端部よりも内側にあり、記録層の外周側端部が反射層の外周側端部よりも内側にあり、保護層の外周側端部が記録層の外周側端部に対し同一もしくは内側にあることを特徴とする請求項1記載の2層型光記録媒体。   The outer peripheral end of the reflective layer is on the inner side of the outer peripheral end of the substrate, the outer peripheral end of the recording layer is on the inner side of the outer peripheral end of the reflective layer, and the outer peripheral end of the protective layer is the recording end. 2. The two-layer type optical recording medium according to claim 1, wherein the two-layer optical recording medium is the same or inward of the outer peripheral side end of the layer. 反射層の内周側端部が基板の内周側端部よりも外側にあり、記録層の内周側端部が反射層の内周側端部に対し同一もしくは内側にあることを特徴とする請求項1〜3の何れかに記載の2層型光記録媒体。   The inner edge of the reflective layer is outside the inner edge of the substrate, and the inner edge of the recording layer is the same or inside the inner edge of the reflective layer. The two-layer optical recording medium according to claim 1. 反射層の内周側端部が基板の内周側端部よりも外側にあり、記録層の内周側端部が反射層の内周側端部に対し外側にあり、保護層の内周側端部が記録層の内周側端部に対し同一もしくは外側にあることを特徴とする請求項1〜3の何れかに記載の2層型光記録媒体。   The inner edge of the reflective layer is outside the inner edge of the substrate, the inner edge of the recording layer is outside the inner edge of the reflective layer, and the inner circumference of the protective layer. The two-layered optical recording medium according to any one of claims 1 to 3, wherein the side end portion is the same as or outside the inner peripheral side end portion of the recording layer. 基板上に反射層、記録層を形成した後、又は保護層を形成した後に、外周端部の記録層を除去することを特徴とする請求項2又は3記載の2層型光記録媒体の製造方法。   4. The two-layer optical recording medium according to claim 2, wherein the recording layer at the outer peripheral edge is removed after forming the reflective layer, the recording layer on the substrate, or after forming the protective layer. Method. 基板上に反射層を形成した後、色素溶液を吐出してスピンコート法により反射層の内周側端部よりも内側に記録層の内周側端部を形成し、記録層内周側端部よりも保護層の内周側端部が内側になるように保護層を形成することを特徴とする請求項4記載の2層型光記録媒体の製造方法。   After forming the reflective layer on the substrate, the dye solution is discharged, and the inner peripheral end of the recording layer is formed inside the inner peripheral end of the reflective layer by spin coating, and the inner peripheral end of the recording layer is formed. 5. The method for producing a two-layer optical recording medium according to claim 4, wherein the protective layer is formed so that the inner peripheral side end of the protective layer is on the inner side than the portion. 請求項7記載の製造方法により、保護層の内周側端部が反射層の内周側端部よりも1mm以上内周側になるように作製されたことを特徴とする請求項4記載の2層型光記録媒体。
The manufacturing method according to claim 7, wherein the inner peripheral side end portion of the protective layer is made to be 1 mm or more inner peripheral side than the inner peripheral side end portion of the reflective layer. Two-layer optical recording medium.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2008059676A1 (en) * 2006-11-14 2008-05-22 Panasonic Corporation Multilayer information recording medium and method for manufacturing the same
EP2071570A1 (en) 2007-12-12 2009-06-17 Taiyoyuden Co., Ltd. Optical information recording medium and manufacturing method thereof
US8075972B2 (en) 2005-04-07 2011-12-13 Mitsubishi Kagaku Media Co., Ltd. Optical recording medium

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8075972B2 (en) 2005-04-07 2011-12-13 Mitsubishi Kagaku Media Co., Ltd. Optical recording medium
WO2008059676A1 (en) * 2006-11-14 2008-05-22 Panasonic Corporation Multilayer information recording medium and method for manufacturing the same
JP2008287854A (en) * 2006-11-14 2008-11-27 Panasonic Corp Multilayer information recording medium and method for manufacturing the same
US8017210B2 (en) 2006-11-14 2011-09-13 Panasonic Corporation Multilayer information recording medium and method for manufacturing the same
EP2071570A1 (en) 2007-12-12 2009-06-17 Taiyoyuden Co., Ltd. Optical information recording medium and manufacturing method thereof
US8119216B2 (en) 2007-12-12 2012-02-21 Taiyo Yuden Co., Ltd. Optical information recording medium and manufacturing method thereof

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