JP2008181601A - Optical recording medium and visible information recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical recording medium in which visible information excellent in contrast and visibility can be recorded and a recorded image can be clearly maintained for a long period of time and which is compatible with multi-color image formation, particularly the optical recording medium in which the visible information having high contrast and visibility can be recorded by the same laser beam for use in recording information on an information recording layer and the recorded image can be clearly maintained for a long period of time. <P>SOLUTION: The optical recording medium 10 includes a visible information recording layer 14 above/on substrates 16, 26. The visible information recording layer includes at least two kinds of dyes including a prescribed dye. The optical recording medium may further include the recording layer 18 in which information can be recorded or reproduced by irradiation with the laser beam 12. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical recording medium, and more particularly to an optical recording medium having a recording layer for recording digital data or the like and a visible information recording layer for recording visible information for identifying the recorded data. Furthermore, the present invention relates to a visible information recording method on the optical recording medium.

  Conventionally, an optical information recording medium (optical disk) capable of recording information only once by laser light is known. As this optical disc, there are a write-once type CD (so-called CD-R) and a write-once type digital vasatile disc (so-called DVD-R).

  By the way, the optical disc has a music title of music data recorded on the recording surface, a title for identifying the recorded data, etc. on the surface opposite to the recording surface on which digital data such as music data is recorded. A label with a label printed with visible information is known. Such an optical disk is manufactured by printing a title or the like on a circular label sheet in advance by a printer or the like, and sticking the label sheet on a surface opposite to the recording surface of the optical disk.

  However, when producing an optical disc in which a desired visible image such as a title is recorded on the label surface as described above, a printer is required separately from the optical disc drive. Therefore, it is necessary to perform complicated operations such as recording on the recording surface of a certain optical disk using the optical disk drive, and then taking out the optical disk from the optical disk drive and attaching a label sheet printed by a separately prepared printer. There is.

On the other hand, Patent Documents 1 and 2 disclose that an image is formed with a laser beam on a label surface provided on a surface opposite to an information (digital information) recording surface. By using such a method, a desired image can be recorded on the label surface of the optical disc by the optical disc drive without separately preparing a printer or the like. In particular, if the laser light source used for recording or reproducing information (digital information) and the laser light source used for image recording can be shared as in the method described in Patent Document 2, the hardware resources of the recording apparatus are reduced. You can also
JP-A-11-66617 Japanese Patent Laid-Open No. 2002-203321

However, a visible image formed by a high-power gas laser such as a carbon dioxide laser used in the method described in Patent Document 1 has low contrast and poor visibility.
On the other hand, in the image recording method described in Patent Document 2, since the laser beam is irradiated on the label surface with a trajectory different from that of normal digital data recording, it is conventionally used for the information (digital information) recording surface of an optical disc. It was difficult to form a high-contrast visible image with the above dye. In addition, cyan dyes that are currently proposed as dyes that can be used in the image recording method are mainly used, but in recent years, it has been required to form a visible image with a desired color tone (so-called multicolor). It has been. Further, the dye is required to have high light resistance capable of maintaining a clear image over a long period of time.

  Under such circumstances, the present invention can record visible information with high contrast and excellent visibility, can maintain a recorded image clearly over a long period of time, and can further support multicolorization. Visible information with high contrast and excellent visibility can be recorded with the same laser beam used for recording information on the recording medium, especially the information recording layer, and the recorded image can be clearly recorded over a long period of time. The present invention has been made for the purpose of providing an optical recording medium that can be maintained at the same time.

［一般式（Ｉ）中、Ｚａ²¹およびＺａ²²は、各々独立に、酸性核を形成する原子群を表し、Ｍａ²¹、Ｍａ²²およびＭａ²³は、各々独立に、置換または無置換のメチン基を表し、Ｋａ²¹は、０〜３の範囲の整数を表し、Ｑ¹は、一価の陽イオンを表す。但し、Ｋａ²¹が２または３を表すとき、Ｚａ²²が形成する酸性核は、Ｚａ²¹が形成する酸性核の互変異性体とは異なる酸性核であり、複数存在するＭａ²¹、Ｍａ²²は、それぞれ同じでも異なっていてもよく、Ｋａ²¹が０または１であるとき、Ｚａ²²が形成する酸性核は、Ｚａ²¹が形成する酸性核の互変異性体であっても、該互変異性体とは異なる酸性核であってもよい。］

［一般式（ＩＩＩ）中、Ｚａ³¹およびＺａ³²は、各々独立に、酸性核を形成する原子群を表し、Ｍａ³¹、Ｍａ³²およびＭａ³³は、各々独立に、置換または無置換のメチン基を表し、Ｌは、２つの結合とともにπ共役系を形成しない２価の連結基を表し、Ｋａ³¹は、０〜３の範囲の整数を表し、Ｑ³は、一価の陽イオンを表すか、または２Ｑ³で、２価の陽イオンを表し、Ｋａ³¹が２または３であるとき、複数存在するＭａ³¹、Ｍａ³²は、それぞれ同じでも異なっていてもよい。］
[２]一般式（Ｉ）中、Ｚａ²¹が形成する酸性核は、下記一般式（Ａ−１）〜（Ａ−１２）のいずれかで表される酸性核であり、Ｚａ²²が形成する酸性核は、下記一般式（Ｂ−１）〜（Ｂ−１２）のいずれかで表される酸性核である[１]に記載の光記録媒体。

[一般式（Ａ−１）〜（Ａ−１２）、（Ｂ−１）〜（Ｂ−１２）中、＊印は、上記酸性核がＭａ²¹またはＭａ²³と連結する位置を表し、Ｒ^a1、Ｒ^a2、Ｒ^b1、Ｒ^b2、Ｒ^c1、Ｒ^c2、Ｒ^d1、Ｒ^d2、Ｒ^e1、Ｒ^e2、Ｒ^k、Ｒ^f1、Ｒ^g1、Ｒ^h1、Ｒ^j1、Ｒ^j2、Ｒ^k1、Ｒ^k2、Ｒ^k3、Ｒ^k4、Ｒ^m1、Ｒ^m2、Ｒ^m3、Ｒ^m4、Ｒⁿ¹およびＲⁿ²は、各々独立に、水素原子または置換基であり、Ｚａ²¹が形成する酸性核とＺａ²²が形成する酸性核の主骨格が同一であるとき、複数存在する酸性核置換基は、それぞれ同じでも異なっていてもよい。］
[３]一般式（ＩＩＩ）中、Ｚａ³¹が形成する酸性核は、下記一般式（Ａ−１）〜（Ａ−１２）のいずれかで表される酸性核であり、Ｚａ³²が形成する酸性核は、下記一般式（Ｂ−１）〜（Ｂ−１２）のいずれかで表される酸性核である[１]または[２]に記載の光記録媒体。

[一般式（Ａ−１）〜（Ａ−１２）、（Ｂ−１）〜（Ｂ−１２）中、＊印は、上記酸性核がＭａ³¹またはＭａ³³と連結する位置を表し、Ｒ^a1、Ｒ^a2、Ｒ^b1、Ｒ^b2、Ｒ^c1、Ｒ^c2、Ｒ^d1、Ｒ^d2、Ｒ^e1、Ｒ^e2、Ｒ^k、Ｒ^f1、Ｒ^g1、Ｒ^h1、Ｒ^j1、Ｒ^j2、Ｒ^k1、Ｒ^k2、Ｒ^k3、Ｒ^k4、Ｒ^m1、Ｒ^m2、Ｒ^m3、Ｒ^m4、Ｒⁿ¹およびＲⁿ²は、各々独立に、水素原子または置換基であり、Ｚａ³¹が形成する酸性核とＺａ³²が形成する酸性核の主骨格が同一であるとき、複数存在する酸性核置換基は、それぞれ同じでも異なっていてもよい。］
[４]一般式（Ｉ）で表される色素は、下記一般式（ＩＶ）、（Ｖ）、（ＶＩ）、（ＶＩＩ）、（ＶＩＩＩ）、（ＩＸ）、（Ｘ）、（ＸＩ）または（ＸＩＩ）で表される色素である[１]〜[３]のいずれか１項に記載の光記録媒体。

［一般式（ＩＶ）、（Ｖ）、（ＶＩ）、（ＶＩＩ）、（ＶＩＩＩ）、（ＩＸ）、（Ｘ）、（ＸＩ）、（ＸＩＩ）中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷、Ｒ²⁸、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁷、Ｒ⁴⁸、Ｒ⁴⁹、Ｒ⁵⁰、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³、Ｒ⁵⁴、Ｒ⁵⁵、Ｒ⁵⁶、Ｒ⁵⁷、Ｒ⁵⁸、Ｒ⁵⁹、Ｒ⁶⁰、Ｒ⁶¹、Ｒ⁶²およびＲ⁶³は、各々独立に、水素原子または置換基を表し、Ｍａ²⁷、Ｍａ²⁸およびＭａ²⁹は、各々独立に、置換または無置換のメチン基を表し、Ｋａ²³は、０または１を表し、Ｋａ²⁴は、０〜２の範囲の整数を表し、Ｘ¹は、酸素原子またはＣＨ₂を表し、Ｙ¹は酸素原子または硫黄原子を表し、Ｑは、一価の陽イオンを表す。］
[５]前記可視情報記録層は、下記一般式（ＩＩ）で表される色素を少なくとも１種含有する[１]〜[４]のいずれかに記載の光記録媒体。

［一般式（ＩＩ）中、Ｚａ²³は酸性核を形成する原子群を表し、Ｚａ^23'はＺａ²³が形成する酸性核の互変異性体である酸性核を形成する原子群を表し、Ｍａ²⁴、Ｍａ²⁵およびＭａ²⁶は、各々独立に、置換または無置換のメチン基を表し、Ｋａ²²は、２または３を表し、複数存在するＭａ²⁵、Ｍａ²⁶は、それぞれ同じでも異なっていてもよく、Ｑ²は、一価の陽イオンを表す。］
[６]一般式（ＩＩ）中のＺａ²³が形成する酸性核は、下記一般式（Ａ−１）〜（Ａ−１２）のいずれかで表される酸性核である[５]に記載の光記録媒体。

［一般式（Ａ−１）〜（Ａ−１２）中、＊印は、上記酸性核がＭａ²⁶と連結する位置を表し、Ｒ^a1、Ｒ^a2、Ｒ^b1、Ｒ^b2、Ｒ^c1、Ｒ^c2、Ｒ^d1、Ｒ^d2、Ｒ^e1、Ｒ^e2、Ｒ^f1、Ｒ^g1、Ｒ^h1、Ｒ^j1、Ｒ^j2、Ｒ^k1、Ｒ^k2、Ｒ^k3、Ｒ^k4、Ｒ^m1、Ｒ^m2、Ｒ^m3、Ｒ^m4、Ｒⁿ¹およびＲⁿ²は、各々独立に、水素原子または置換基である。］
[７]一般式（Ｉ）中のＫａ²¹は、０〜２の範囲の整数を表し、
一般式（ＩＩ）中のＫａ²²はＫａ²¹とは異なる０〜２の範囲の整数を表す[５]または[６]に記載の光記録媒体。
[８]一般式（ＩＩ）で表される色素は、下記一般式（ＸＶＩＩＩ）で表される色素である[５]に記載の光記録媒体。

[一般式（ＸＶＩＩＩ）中、Ｒ¹⁵¹、Ｒ¹⁵²、Ｒ¹⁵³、Ｒ¹⁵⁴、Ｒ¹⁵⁵、Ｒ¹⁵⁶、Ｒ¹⁵⁷、Ｒ¹⁵⁸、Ｒ¹⁵⁹およびＲ¹⁶⁰は、各々独立に、水素原子または、置換基を表し、Ｒ¹⁶¹およびＲ¹⁶⁷は、各々独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、シアノ基、置換もしくは無置換のカルバモイル基、置換もしくは無置換のアルコシキシ基、置換もしくは無置換のアルコキシカルボニル基、置換もしくは無置換のアリールオキシカルボニル基、または置換もしくは無置換のアシルアミノ基を表し、Ｒ¹⁶²、Ｒ¹⁶³、Ｒ¹⁶⁴、Ｒ¹⁶⁵およびＲ¹⁶⁶は、各々独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアシルアミノ基、または置換もしくは無置換のヘテロ環基を表し、Ｒ⁷¹、Ｒ⁷²、Ｒ⁷³、Ｒ⁷⁴、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、Ｒ⁷⁸、Ｒ⁷⁹、Ｒ⁸⁰、Ｒ⁸¹、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴、Ｒ⁸⁵、Ｒ⁸⁶、Ｒ⁸⁷およびＲ⁸⁸は、各々独立に、水素原子または置換基を表す。]
[９]前記可視情報記録層は、一般式（Ｉ）および／または一般式（ＩＩＩ）で表される色素と一般式（ＩＩ）で表される色素とを含有する[５]〜[８]のいずれかに記載の光記録媒体。
[１０]前記可視情報記録層は、一般式（Ｉ）で表される色素および一般式（ＩＩＩ）で表される色素を含有する[１]〜[９]のいずれかに記載の光記録媒体。
[１１]前記可視情報記録層は、一般式（ＩＩＩ）で表される色素、一般式（ＩＶ）〜（ＸＩＩ）で表される色素からなる群から選ばれる少なくとも一種の色素、および一般式（ＩＩ）で表される色素を含有する[５]〜[１０]のいずれかに記載の光記録媒体。
[１２]レーザー光を照射して情報の記録および／または再生が可能な記録層を更に有する、[１]〜[１１]のいずれかに記載の光記録媒体。
[１３]第一基板、前記記録層、反射層、前記可視情報記録層、および第二基板をこの順に有する、[１２]に記載の光記録媒体。
[１４]前記光記録媒体はディスク状である[１]〜[１３]のいずれかに記載の光記録媒体。
[１５][１２]〜[１４]のいずれかに記載の光記録媒体の前記可視情報記録層への可視情報記録方法であって、
前記可視情報を、前記記録層への情報の記録に用いるレーザー光と同じレーザー光を用いて記録することを特徴とする可視情報記録方法。
[１６][１４]に記載の光記録媒体の前記可視情報記録層への可視情報記録方法であって、
前記可視情報を、前記光記録媒体の半径方向に遥動し且つ略同一の軌跡に複数回照射されるレーザー光を用いて記録することを特徴とする可視情報記録方法。 Means for achieving the object is as follows.
[1] An optical recording medium having a visible information recording layer on a substrate,
The visible information recording layer contains at least two dyes, and at least one dye selected from the group consisting of dyes represented by the following general formula (I) and dyes represented by the general formula (III) An optical recording medium comprising:

[In the general formula (I), Za ²¹ and Za ²² each independently represent an atomic group forming an acidic nucleus, and Ma ²¹ , Ma ²² and Ma ²³ each independently represent a substituted or unsubstituted methine group. Ka ²¹ represents an integer in the range of 0 to 3, and Q ¹ represents a monovalent cation. However, when Ka ²¹ represents 2 or 3, the acidic nucleus formed by Za ²² is an acidic nucleus different from the tautomer of the acidic nucleus formed by Za ²¹ , and a plurality of Ma ²¹ and Ma ²² are Each of them may be the same or different, and when Ka ²¹ is 0 or 1, the acidic nucleus formed by Za ²² may be a tautomer of the acidic nucleus formed by Za ²¹ . It may be an acidic nucleus different from the body. ]

[In the general formula (III), Za ³¹ and Za ³² each independently represent an atomic group forming an acidic nucleus, and Ma ³¹ , Ma ³² and Ma ³³ each independently represent a substituted or unsubstituted methine group. L represents a divalent linking group that does not form a π-conjugated system with two bonds, Ka ³¹ represents an integer in the range of 0 to 3, and Q ³ represents a monovalent cation. Or 2Q ³ represents a divalent cation, and when Ka ³¹ is 2 or 3, a plurality of Ma ³¹ and Ma ³² may be the same or different from each other. ]
[2] In the general formula (I), an acidic nucleus formed by Za ²¹ is an acidic nucleus represented by any one of the following general formulas (A-1) to (A-12), and Za ²² is formed. The optical recording medium according to [1], wherein the acidic nucleus is an acidic nucleus represented by any one of the following general formulas (B-1) to (B-12).

[In General Formulas (A-1) to (A-12) and (B-1) to (B-12), * represents the position at which the acidic nucleus is linked to Ma ²¹ or Ma ^23, and R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^k , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k1 , R ^{k2, R k3, R k4,} R m1, R m2, R m3, R m4, R n1 and R ⁿ² are each independently a hydrogen atom or a substituent, an acidic nucleus and Za ²² which Za ²¹ is formed When the main skeletons of the acidic nuclei formed are the same, the plurality of acidic nuclei substituents may be the same or different. ]
[3] In the general formula (III), an acidic nucleus formed by Za ³¹ is an acidic nucleus represented by any one of the following general formulas (A-1) to (A-12), and Za ³² is formed. The acidic recording medium according to [1] or [2], wherein the acidic nucleus is an acidic nucleus represented by any one of the following general formulas (B-1) to (B-12).

[In General Formulas (A-1) to (A-12) and (B-1) to (B-12), * represents a position where the acidic nucleus is linked to Ma ³¹ or Ma ^33, and R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^k , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k1 , R ^{k2, R k3, R k4,} R m1, R m2, R m3, R m4, R n1 and R ⁿ² are each independently a hydrogen atom or a substituent, an acidic nucleus and Za ³² which Za ³¹ is formed When the main skeletons of the acidic nuclei formed are the same, the plurality of acidic nuclei substituents may be the same or different. ]
[4] The dye represented by the general formula (I) is represented by the following general formula (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) or The optical recording medium according to any one of [1] to [3], which is a dye represented by (XII).

[In formulas (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³¹ , R ³² , R ³³ , R ³⁴ , ^{R 41, R 42, R 43} , R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54, R 55, R 56, R 57 , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² and R ⁶³ each independently represents a hydrogen atom or a substituent, and Ma ²⁷ , Ma ²⁸ and Ma ²⁹ are each independently substituted or unsubstituted. Ka ²³ represents 0 or 1, Ka ²⁴ represents an integer in the range of 0 to 2, X ¹ represents an oxygen atom or CH ₂ , and Y ¹ represents an oxygen atom or a sulfur atom. Q is a monovalent cation Represent. ]
[5] The optical recording medium according to any one of [1] to [4], wherein the visible information recording layer contains at least one dye represented by the following general formula (II).

[In the general formula (II), Za ²³ represents an atomic group forming an acidic nucleus, Za ^{23 ′} represents an atomic group forming an acidic nucleus that is a tautomer of the acidic nucleus formed by Za ²³ , and Ma ²⁴ , Ma ²⁵ and Ma ²⁶ each independently represent a substituted or unsubstituted methine group, Ka ²² represents 2 or 3, and a plurality of Ma ²⁵ and Ma ²⁶ may be the same or different. Often, Q ² represents a monovalent cation. ]
[6] The acidic nucleus formed by Za ²³ in the general formula (II) is an acidic nucleus represented by any one of the following general formulas (A-1) to (A-12) [5] Optical recording medium.

[In General Formulas (A-1) to (A-12), * represents a position where the acidic nucleus is linked to Ma ^26, and R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k1 , R ^k2 , R ^k3 , R ^k4 , R ^m1 , R ^m2 , R ^m3 , R ^m4 , ^Rn1 and ^Rn2 are each independently a hydrogen atom or a substituent. ]
[7] Ka ²¹ in the general formula (I) represents an integer in the range of 0 to 2,
The optical recording medium according to [5] or [6], wherein Ka ²² in the general formula (II) represents an integer in the range of 0 to 2 different from Ka ²¹ .
[8] The optical recording medium according to [5], wherein the dye represented by the general formula (II) is a dye represented by the following general formula (XVIII).

[In the general formula (XVIII), R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ , R ¹⁵⁸ , R ¹⁵⁹ and R ¹⁶⁰ each independently represents a hydrogen atom or a substituent. R ¹⁶¹ and R ¹⁶⁷ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted alkoxy group Represents a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted acylamino group, and R ¹⁶² , R ¹⁶³ , R ¹⁶⁴ , R ¹⁶⁵ and R ¹⁶⁶ are each independently Hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted acylamino group, or substituted or unsubstituted hete It represents a cyclic ^{group, R 71, R 72, R} 73, R 74, R 75, R 76, R 77, R 78, R 79, R 80, R 81, R 82, R 83, R 84, R 85, R ⁸⁶ , R ⁸⁷ and R ⁸⁸ each independently represents a hydrogen atom or a substituent. ]
[9] The visible information recording layer contains a dye represented by the general formula (I) and / or the general formula (III) and a dye represented by the general formula (II) [5] to [8]. The optical recording medium according to any one of the above.
[10] The optical recording medium according to any one of [1] to [9], wherein the visible information recording layer contains a dye represented by the general formula (I) and a dye represented by the general formula (III) .
[11] The visible information recording layer includes at least one dye selected from the group consisting of a dye represented by the general formula (III), a dye represented by the general formulas (IV) to (XII), and a general formula ( The optical recording medium according to any one of [5] to [10], which contains a dye represented by II).
[12] The optical recording medium according to any one of [1] to [11], further including a recording layer capable of recording and / or reproducing information by irradiating a laser beam.
[13] The optical recording medium according to [12], comprising a first substrate, the recording layer, a reflective layer, the visible information recording layer, and a second substrate in this order.
[14] The optical recording medium according to any one of [1] to [13], wherein the optical recording medium has a disk shape.
[15] A visible information recording method on the visible information recording layer of the optical recording medium according to any one of [12] to [14],
The visible information recording method, wherein the visible information is recorded using the same laser beam as that used for recording information on the recording layer.
[16] A visible information recording method on the visible information recording layer of the optical recording medium according to [14],
The visible information recording method, wherein the visible information is recorded by using laser light which is oscillated in a radial direction of the optical recording medium and irradiated a plurality of times on substantially the same locus.

  ADVANTAGE OF THE INVENTION According to this invention, it is an optical recording medium which can record visible information with high contrast and excellent visibility, Comprising: It can provide the optical recording medium which can respond to multi-coloring. The dye is suitable for a system for forming an image by a new recording method different from normal digital data recording. In the system, the dye forms visible information with high contrast and high light resistance. be able to.

[Optical recording medium]
The optical recording medium of the present invention is an optical recording medium having a visible information recording layer on a substrate, and the visible information recording layer contains at least two dyes and is represented by the following general formula (I): And at least one dye selected from the group consisting of dyes represented by formula (III).
The optical recording medium of the present invention contains at least two dyes in the visible information recording layer. In this way, by using two or more kinds of pigments in combination, a desired color tone can be realized by color mixing, and multicolorization can be supported.
In addition, the dye represented by the following general formula (I) and the dye represented by the general formula (III) absorb laser light, convert light-to-heat, and decompose (discolor) when decomposed by generated heat. Therefore, visible information having high contrast and excellent visibility can be formed. Furthermore, the visible information formed by the dye has excellent light resistance.
As described above, according to the present invention, an optical recording medium capable of recording visible information with high contrast and excellent visibility, and capable of maintaining a recorded image clearly over a long period of time. Can be provided.
Below, the detail of the pigment | dye contained in the said visible information recording layer is demonstrated.

Dye represented by general formula (I)

In the general formula (I), Za ²¹ and Za ²² each independently represent an atomic group forming an acidic nucleus. Examples include those described in James, The Theory of the Photographic Process, 4th edition, McMillan, 1977, p. 198. Specifically, each optionally substituted pyrazol-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4- ON, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, thiophen-3-one, thiophen-3-one-1,1-dioxide, 3,3-dioxo [1 , 3] oxathiolane-5-one, indoline-2-one, indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione (for example, Meldrum's acid, etc.), barbituric acid, 2-thio Barbituric acid, coumarin-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone, 5 or 6 member Nuclei such as hexane-1,3-dione, pentane-1,3-dione, indan-1,3-dione, and the like, preferably pyrazol-5-one, pyrazolidine-3, Mention may be made of 5-dione, barbituric acid, 2-thiobarbituric acid, 1,3-dioxane-4,6-dione, or 3,3-dioxo [1,3] oxathiolane-5-one.

The acidic nucleus formed by Za ²¹ is preferably an acidic nucleus represented by any one of the following general formulas (A-1) to (A-12).

In the above general formula, * represents the position at which the acidic nucleus is connected to Ma ^21, and the acidic nucleus substituents R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k1 , R ^k2 , R ^k3 , R ^k4 , R ^m1 , R ^m2 , R ^m3 and R ^m4 , R ⁿ¹ and R ⁿ² is each independently a hydrogen atom or a substituent.

The acidic nucleus formed by Za ²² is preferably the following general formula (B-1) to tautomer of the acidic nucleus represented by the general formulas (A-1) to (A-12). It is an acidic nucleus represented by any of (B-12).

In the above general formula, * represents the position where the acidic nucleus is linked to Ma ^23, and the definition and details of each substituent of the acidic nucleus are the same as described above. When the acidic nuclei formed by Za ²¹ and the acidic skeleton formed by Za ²² are the same, a plurality of acidic nucleus substituents may be the same or different.

Substituents for substituting the acidic nucleus are halogen atoms, alkyl groups (including cycloalkyl groups and bicycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group) ), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group Heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imido group, phosphino group Examples include phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group. Among these, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms is preferable.
The acidic nucleus is preferably unsubstituted, substituted with a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or substituted with a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

Ma ²¹ , Ma ²² and Ma ²³ each independently represent a substituted or unsubstituted methine group. Preferably, the substituent is preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, isopropyl group), a halogen atom (for example, chlorine, bromine, iodine, fluorine), an alkoxy group having 1 to 20 carbon atoms ( For example, methoxy group, ethoxy group, isopropyl group), aryl group having 6 to 26 carbon atoms (for example, phenyl group, 2-naphthyl group), heterocyclic group having 0 to 20 carbon atoms (for example, 2-pyridyl group, 3 -Pyridyl group), an aryloxy group having 6 to 20 carbon atoms (for example, phenoxy group, 1-naphthoxy group, 2-naphthoxy group), an acylamino group having 1 to 20 carbon atoms (for example, acetylamino group, benzoylamino group), A carbamoyl group having 1 to 20 carbon atoms (for example, N, N-dimethylcarbamoyl group), sulfo group, hydroxy group, carboxy group, Kiruchio group (such as methylthio), a cyano group. Further, it may be bonded to other methine groups to form a ring structure, or may be bonded to an atomic group represented by Za ²¹ or Za ²² to form a ring structure.
Ma ²¹ , Ma ²² and Ma ²³ are each independently preferably a methine group which is unsubstituted or substituted with an ethyl group, a methyl group or a phenyl group. Most preferred is an unsubstituted methine group.

Ka ²¹ represents an integer in the range of 0 to 3. When Ka ²¹ represents 2 or 3, the acidic nucleus formed by Za ²² is an acidic nucleus different from the tautomer of the acidic nucleus formed by Za ²¹ , and a plurality of Ma ²¹ and Ma ²² are respectively They may be the same or different, and when Ka ²¹ is 0 or 1, the acidic nucleus formed by Za ²² may be a tautomer of the acidic nucleus formed by Za ²¹ , May be different acidic nuclei. Ka ²¹ is preferably 1 to 2.

Q ¹ represents a monovalent cation. The ion represented by Q ¹ is not particularly limited, and may be an ion composed of an inorganic compound or an ion composed of an organic compound. Examples of the monovalent cation represented as Q ¹ include metal ions such as sodium ion and potassium ion, onium such as quaternary ammonium ion, oxonium ion, sulfonium ion, phosphonium ion, selenonium ion and iodonium ion. Ions.

The cation represented by Q ¹ is preferably an onium ion, and more preferably a quaternary ammonium ion. Of the quaternary ammonium ions, 4,4′-bipyridinium cation represented by general formula (I-4) in JP-A No. 2000-52658 and JP-A No. 2002-59652 are particularly preferable. 4,4′-bipyridinium cation. In the case of a dicationic compound such as 4,4′-bipyridinium cation, Q ¹ corresponds to 1/2 (the dicationic compound).

  The dye represented by the general formula (I) is preferably a dye represented by the following general formula (IV) to general formula (XII). Below, the detail of the said pigment | dye is demonstrated.

In the general formulas (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), R ¹¹ , R ¹² , R ¹³ , R ^{14 , R 15, R 16, R} 17, R 18, R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 31, R 32, R 33, R 34, R ^{41, R 42, R 43,} R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54, R 55, R 56, R 57, R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² and R ⁶³ (sometimes referred to as “R”) each independently represents a hydrogen atom or a substituent. The substituent is a halogen atom, a substituted or unsubstituted alkyl group (including a cycloalkyl group and a bicycloalkyl group), a substituted or unsubstituted alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), substituted or unsubstituted Alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, Substituted or unsubstituted silyloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted carbamoyloxy group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted Aryloxycarbonyloxy group Substituted or unsubstituted amino group (including anilino group), substituted or unsubstituted acylamino group, substituted or unsubstituted aminocarbonylamino group, substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted aryloxycarbonyl An amino group, a substituted or unsubstituted sulfamoylamino group, a substituted or unsubstituted alkyl and arylsulfonylamino group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, Substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted sulfamoyl group, sulfo group, substituted or unsubstituted alkyl and arylsulfinyl group, substituted or unsubstituted alkyl and arylsulfonyl group, substituted or unsubstituted An acyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted aryl and heterocyclic azo group, a substituted or unsubstituted imide group, Examples include substituted or unsubstituted phosphino groups, substituted or unsubstituted phosphinyl groups, substituted or unsubstituted phosphinyloxy groups, substituted or unsubstituted phosphinylamino groups, or substituted or unsubstituted silyl groups. It is done.

  More specifically, R can be a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom) or an alkyl group (a linear, branched or cyclic substituted or unsubstituted alkyl group). The alkyl group is an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group). Group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group) ), A bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, Bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), and Structure often tricyclo structure is intended to encompass such. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents the alkyl group of the above concept.

  Furthermore, R represents an alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They include alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl group, allyl group, prenyl group, geranyl group, oleyl group), cycloalkenyl groups (preferably having 3 carbon atoms). A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as a 2-cyclopenten-1-yl group and 2-cyclohexene -1-yl group), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a hydrogen atom of a bicycloalkene having one double bond. A monovalent group, for example, bicyclo [2,2,1] hept-2-en-1-yl, It is intended to include cyclo [2,2,2] oct-2-en-4-yl). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, or a trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms) Aryl group such as phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group), heterocyclic group (preferably 5- or 6-membered substituted or unsubstituted, aromatic Alternatively, it is a monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and more preferably a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. -Furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl Group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group) Group), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, a 2-methylphenoxy group, a 4-t-butylphenoxy group, a 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group, t-butyldimethylsilyloxy group), heterocyclic oxy group (preferably carbon number) 2-30 substituted or unsubstituted heterocyclic oxy groups, 1-phenyltetrazole-5- Xyl group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms) Oxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyl Oxy group), Arco A xoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryl An oxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy Group), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, such as an amino group or a methylamino group) , Dimethyla Group, anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, 6 to 30 carbon atoms) Substituted or unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), amino Carbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonyl Amino group), alkoxy A rubonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, an N- Methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m -N-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino group, N, N-dimethylamino group) Sulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted groups having 6 to 30 carbon atoms) Arylsulfonylamino group of, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group ( Preferably, it is a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, or an n-hexadecylthio group, an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as The Nylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl Group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group ( Preferably, a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, C6-C30 substituted or unsubstituted arylsulfinyl group, for example, methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably having 1 to carbon atoms) 30 substituted or unsubstituted alkylsulfonyl groups, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl groups (Preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms. Hetero bonded to carbonyl group Carbonyl group, for example, acetyl group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group), aryloxycarbonyl group (Preferably, a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group), An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, or an n-octadecyloxycarbonyl group), a carbamoyl group Preferably, the substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (Methylsulfonyl) carbamoyl group), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo Group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide, N-phthalimide group), phosphino group (preferably carbon number) 2 to 30 substituted or unsubstituted phosphino groups such as dimethylphosphino group, diphenylphospho Sulfino group, methylphenoxyphosphino group), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group), Phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group), phosphinylamino group (Preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group) or a silyl group (preferably having 3 to 3 carbon atoms) 30 substituted or unsubstituted silyl groups such as trimethylsilyl group, t-butyldi It is also possible Chirushiriru group, a phenyl dimethylsilyl group).

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are hydrogen Atoms are most preferred.
R ³¹ , R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Of these, a substituted or unsubstituted aryl group is more preferable.
^{R 45, R 46, R 47} , R 48, R 49, R 50, R 51, R 52, R 53, R 54, R 55, R 56, R 57, R 58, R 59, R 60, R 61 R ⁶² and R ⁶³ are preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a hydrogen atom, and a substituted or unsubstituted group having 1 to 20 carbon atoms. A substituted alkyl group is more preferred.

Ma ²⁷ , Ma ²⁸ and Ma ²⁹ each independently represent a substituted or unsubstituted methine group. Details thereof are as described for Ma ²¹ , Ma ²² and Ma ²³ in the general formula (I), and specific examples and preferred examples thereof are also the same.

Ka ²³ represents 0 or 1, preferably 1. Ka ²⁴ represents an integer in the range of 0 to 2, and is preferably 1 or 2.

X ¹ represents an oxygen atom or CH ₂ , preferably an oxygen atom. Y ¹ represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

Q represents a monovalent cation. The details are as described above for Q ¹ in formula (I), and specific examples and preferred examples are also the same.

  Specific examples of the dye represented by formula (I) are shown below, but the present invention is not limited to the following specific examples.

Dye represented by general formula (III)

In the general formula (III), Za ³¹ represents Za ³¹ and Za ³² each independently represents an atomic group forming an acidic nucleus. The details of the acidic nucleus formed by Za ³¹ and Za ³² are as described for Za ²¹ and Za ²² in the general formula (I), and specific examples and preferred examples are also the same. That is, the acidic nucleus Za ³¹ in the general formula (III) is formed is preferably an acidic nucleus represented by any one of the following formulas (A-1) ~ (A -12), Za 32 is The acidic nucleus to be formed is preferably an acidic nucleus represented by any one of the following general formulas (B-1) to (B-12) which are tautomers thereof.

In the above formula, * represents a position where the acidic nucleus is linked to Ma ³¹ or Ma ³³ . Substituents R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k , R ^k1 , R ^k2 , R ^k3 , R ^k4 , R ^m1 , R ^m2 , R ^m3 , R ^m4 , R ⁿ¹ and R ⁿ² are each independently a hydrogen atom or a substituent, As described above. When the acidic skeleton formed by Za ³¹ and the acidic skeleton formed by Za ³² are the same, the plurality of acidic nucleus substituents may be the same or different.

Ma ³¹ , Ma ³² and Ma ³³ each independently represent a substituted or unsubstituted methine group. The substituent is preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, isopropyl group), a halogen atom (for example, chlorine, bromine, iodine, fluorine), or an alkoxy group having 1 to 20 carbon atoms. (For example, methoxy group, ethoxy group, isopropoxy group), aryl group having 6 to 26 carbon atoms (for example, phenyl group, 2-naphthyl group), heterocyclic group having 0 to 20 carbon atoms (for example, 2-pyridyl group) , 3-pyridyl group), aryloxy group having 6 to 20 carbon atoms (for example, phenoxy group, 1-naphthoxy group, 2-naphthoxy group), acylamino group having 1 to 20 carbon atoms (for example, acetylamino group, benzoylamino group) ), A carbamoyl group having 1 to 20 carbon atoms (for example, N, N-dimethylcarbamoyl group), a sulfo group, a hydroxy group, a carboxy group, or 1 to 2 carbon atoms. An alkylthio group (e.g. methylthio group), a cyano group. Further, it may be bonded to other methine groups to form a ring structure, or may be bonded to an atomic group represented by Za ³¹ or Za ³² to form a ring structure.

Ma ³¹ , Ma ³² and Ma ³³ are each independently any one of unsubstituted, methine groups substituted with an ethyl group, a methyl group and a phenyl group. Most preferred is an unsubstituted methine group.

L represents a divalent linking group that does not form a π-conjugated system with two bonds. The divalent linking group is not particularly limited except that it does not form a π-conjugated system between chromophores to which they are bonded, but is preferably an alkylene group (preferably having 1 to 20 carbon atoms, for example, a methylene group, an ethylene group, propylene). Group, butylene group, pentylene group), arylene group (preferably having 6 to 26 carbon atoms such as phenylene group or naphthylene group), alkenylene group (preferably having 2 to 20 carbon atoms such as ethenylene group or propenylene group), alkynylene group ( Preferably it has 2 to 20 carbon atoms, such as ethynylene group, propynylene group), —CO—N (R ¹⁰¹ ) —, —CO—O—, —SO ₂ —N (R ¹⁰² ) —, —SO ₂ —O—, -N (R ¹⁰³ ) -CO-N (R ¹⁰⁴ )-, -SO _2- , -SO-, -S-, -O-, -CO-, -N (R ¹⁰⁵ )-, a heterylene group (preferably Charcoal 1 to 26, for example, 6-chloro-1,3,5-triazyl-2,4-diyl group, pyrimidine-2,4-diyl group) or a combination of one or more and 0 to 100 carbon atoms Hereinafter, it preferably represents 1 to 20 linking groups. R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , and R ¹⁰⁵ each independently represent any of a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. In addition, one or more linking groups represented by L may exist between two chromophores to which they are linked, and a plurality (preferably two) may be bonded to form a ring. Good.
L is preferably one in which two alkylene groups (preferably an ethylene group) are bonded to form a ring. Among them, the case where a 5- or 6-membered ring (preferably a cyclohexyl ring) is formed is more preferable.

In the general formula (III), Ka ³¹ represents an integer in the range of 0 to 3. When Ka ³¹ is 2 or 3, a plurality of Ma ³¹ and Ma ³² may be the same or different. Ka ³¹ is preferably 2.

Q ³ represents a monovalent cation or 2Q ³ represents a divalent cation. The cation represented by Q ³ is not particularly limited, and may be an ion made of an inorganic compound or an ion made of an organic compound. The details of the cation represented as Q ^{3 are} as described above for Q ¹ in formula (I), and specific examples and preferred examples are also the same.

In general formula (III), preferably, the acidic nuclei formed by Za ³¹ and Za ³² are each independently substituted with an unsubstituted or substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or carbon. Pyrazol-5-one, pyrazolidine-3,5-dione, barbituric acid, 2-thiobarbituric acid, 1,3-dioxane-4,6 substituted with a substituted or unsubstituted aryl group of formula 6-20 -Dione, 3,3-dioxo [1,3] oxathiolane-5-one, wherein Ma ³¹ , Ma ³² and Ma ³³ are each independently unsubstituted or ethyl, methyl or phenyl Any one of substituted methine groups, L is a group in which two alkylene groups (preferably an ethylene group) are bonded to form a 5- or 6-membered ring, Ka ³¹ is 2, and 2Q ³ Represented by 4,4′-bipyridinium cation represented by the general formula (I-4) of JP-A-2000-52658 or 4,4 ′-disclosed in JP-A-2002-59652. In this embodiment, it is a bipyridinium cation. As a more preferable embodiment of the dye represented by the general formula (III), a dye represented by the following general formula (XVIV) can be mentioned.

In general formula (XVIV), R ¹ and R ² each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent. R ¹ and R ² may be bonded to each other to form a ring structure. R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and two R ⁶ may be bonded to form a divalent linking group. L ¹ represents a divalent linking group. n represents an integer in the range of 0-2. Q ⁴ represents a monovalent cation or 2Q ⁴ represents a divalent cation. When n is 2, a plurality of R ³ and R ⁴ may be the same or different.

Hereinafter, the general formula (XVIV) will be described in detail.
R ¹ and R ² each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ¹ and R ² may be bonded to each other to form a ring structure. R ¹ and R ² are preferably each independently a substituted or unsubstituted alkyl group. Further preferably, R ^1, R ² is individually an unsubstituted alkyl group having 1 to 6 carbon atoms.
R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a substituent. R ³ , R ⁴ and R ⁵ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. More preferably, they are a hydrogen atom, an ethyl group, a methyl group, or a phenyl group. Most preferably, R ³ , R ⁴ and R ⁵ are all hydrogen atoms.
R ⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Among them, those in which two R ⁶ are bonded to form a divalent linking group are preferable.
L ¹ is a divalent linking group. Preferably, L ¹ is a substituted or unsubstituted alkylene group. L ¹ and R ⁶ are most preferably those in which L ¹ and two R ⁶ form a ring structure. In this case, the ring structure is preferably a 5- or 6-membered ring (more preferably a 6-membered ring).
n represents an integer in the range of 0-2. n is preferably 2. Q ⁴ represents a monovalent cation or 2Q ⁴ represents a divalent cation. When n is 2, a plurality of R ³ and R ⁴ may be the same or different.

  Although the preferable specific example of the pigment | dye represented by general formula (III) or (XVIV) is given to the following, this invention is not limited to the following specific example. In addition, the tautomer of the exemplary compound shown below is also contained in the pigment | dye represented by general formula (III) or general formula (XVIV).

The optical recording medium of the present invention contains at least two dyes in the visible information recording layer, and contains at least a dye represented by formula (I) or (III), preferably represented by formula (I). And a dye represented by the general formula (III). The visible information recording layer may contain one kind of each of the dyes represented by the general formula (I) and the general formula (III), and each of the dyes represented by the general formula (I) and the general formula (III). Two or more types can also be included. Further, the dye contained in the visible information recording layer may be only the dye represented by the general formula (I) and / or the general formula (III), but the general formula (I) and / or the general formula (III). ) And other dyes may be used in combination. In this case, the dyes used in combination are cyanine dyes, imidazoquinoxaline dyes, pyrylium / thiopyrylium dyes, azurenium dyes, squarylium dyes, azo dyes, metal complex dyes such as Ni and Cr (phthalocyanine dyes, azo dyes) Metal chelate dyes, pyromethene metal chelate dyes), naphthoquinone dyes, anthraquinone dyes, indophenol dyes, indoaniline dyes, triphenylmethane dyes, merocyanine dyes, oxonol dyes, aminium dyes, UV absorbers Among these, cyanine dyes, phthalocyanine dyes, azo dyes (including metal chelate dyes), merocyanine dyes, oxonol dyes, and ultraviolet absorbers are particularly preferably used. Among these, a preferable dye as the dye used in combination is an oxonol dye represented by the general formula (II).
Below, the pigment | dye represented by general formula (II) is demonstrated.

Dye represented by general formula (II)

In the general formula (II), Za ²³ represents an atomic group that forms an acidic nucleus, and Za ^{23 ′} represents an atomic group that forms an acidic nucleus that is a tautomer of the acidic nucleus formed by Za ²³ . The details of the acidic nucleus formed by Za ²³ and Za ^{23 ′} in the general formula (II) are as described for Za ²¹ and Za ²² in the general formula (I), and specific examples and preferred examples are also the same. It is. That is, the acidic nucleus formed by Za ²³ in the general formula (II) is an acidic nucleus represented by any of the following general formulas (A-1) to (A-12), and Za ^{23 ′} is formed. The acidic nucleus is an acidic nucleus represented by any one of the following general formulas (B-1) to (B-12), which are tautomers thereof.

[一般式（Ａ−１）〜（Ａ−１２）、（Ｂ−１）〜（Ｂ−１２）中、＊印は、上記酸性核がＭａ²⁴またはＭａ²⁶と連結する位置を表し、Ｒ^a1、Ｒ^a2、Ｒ^b1、Ｒ^b2、Ｒ^c1、Ｒ^c2、Ｒ^d1、Ｒ^d2、Ｒ^e1、Ｒ^e2、Ｒ^k、Ｒ^f1、Ｒ^g1、Ｒ^h1、Ｒ^j1、Ｒ^j2、Ｒ^k1、Ｒ^k2、Ｒ^k3、Ｒ^k4、Ｒ^m1、Ｒ^m2、Ｒ^m3、Ｒ^m4、Ｒⁿ¹およびＲⁿ²は、各々独立に、水素原子または置換基である。］

[In General Formulas (A-1) to (A-12) and (B-1) to (B-12), * represents a position where the acidic nucleus is linked to Ma ²⁴ or Ma ^26, and R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^k , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k1 , R ^{k2, R k3, R k4,} R m1, R m2, R m3, R m4, R n1 and R ⁿ² are each independently a hydrogen atom or a substituent. ]

Ma ²⁴ , Ma ²⁵ and Ma ²⁶ each independently represent a substituted or unsubstituted methine group. The details are as described for Ma ²¹ , Ma ²² and Ma ²³ in the general formula (I), and specific examples and preferred examples are also the same.

Ka ²² represents 2 or 3, and is preferably 2. In the dye represented by the general formula (II), a plurality of Ma ²⁵ and Ma ²⁶ may be the same or different.

Q ² represents a monovalent cation. The details are as described above for Q ¹ in the general formula (I), and specific examples and preferred examples are also the same.

  The dye represented by the general formula (II) is preferably a dye represented by the following general formulas (XIV) to (XVII).

In the general formulas (XIV), (XV), (XVI), (XVII), R ^{11 ′} , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} , R ^{15 ′} , R ^{16 ′} , R ^{17 ′} , R ^{18 ′} , R ^{21 ′} , R ^{22 ′} , R ^{23 ′} , R ^{24 ′} , R ^{25 ′} , R ^{26 ′} , R ^{27 ′} , R ^{28 ′} , R ^{31 ′} , R ^{32 ′} , R ^{33 ′} , R ^{34 ′} , R ^{41 ′} , R ^{42 ′} , R ^{43 ′} and R ^{44 ′} each independently represents a hydrogen atom or a substituent.
Details of R ^{11 ′ to} R ^{18 ′} in general formula (XIV) are as described above for R ^{11 to} R ¹⁸ in general formula (IV), and specific examples and preferred examples are also the same.
The details of R ^{21 ′ to} R ^{28 ′} in general formula (XV) are as described above for R ^{21 to} R ²⁸ in general formula (V), and specific examples and preferred examples are also the same.
The details of R ^{31 ′ to} R ^{34 ′} in general formula (XVI) are as described above for R ^{31 to} R ³⁴ in general formula (VI), and specific examples and preferred examples are also the same.
Details of R ^{41 ′ to} R ^{44 ′} in general formula (XVII) are as described above for R ^{41 to} R ⁴⁴ in general formula (VII), and specific examples and preferred examples are also the same.

Q ′ in the general formulas (XIV), (XV), (XVI), (XVII) represents a monovalent cation. The details are as described above for Q ¹ in the general formula (I), and specific examples and preferred examples are also the same.

Ka ²⁵ in the general formulas (XIV), (XV), (XVI), (XVII) represents 2 or 3, preferably 2.

  The dye represented by the general formula (II) is particularly preferably a dye represented by the following general formula (XVIII).

In the general formula (XVIII), R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ , R ¹⁵⁸ , R ¹⁵⁹ , and R ¹⁶⁰ each independently represent a hydrogen atom or a substituent. The substitution is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted acylamino group. Among them, R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ , R ¹⁵⁸ , R ¹⁵⁹ , R ¹⁶⁰ are all hydrogen atoms, and R ¹⁵¹ , R ¹⁵³ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁸ and R ¹⁶⁰ are preferably substituted with halogen atoms, and R ¹⁵² , R ¹⁵⁴ , R ¹⁵⁷ and R ¹⁵⁹ are preferably hydrogen atoms.
R ¹⁶¹ and R ¹⁶⁷ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, cyano group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkoxy group, substituted Alternatively, it represents an unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted acylamino group. Of these, a substituted or unsubstituted alkoxycarbonyl group is preferable, and an unsubstituted alkoxycarbonyl group is most preferable.

R ¹⁶² , R ¹⁶³ , R ¹⁶⁴ , R ¹⁶⁵ and R ¹⁶⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acylamino group, or substituted or unsubstituted An unsubstituted heterocyclic group is represented. R ¹⁶² , R ¹⁶³ , R ¹⁶⁵ and R ¹⁶⁶ are preferably all hydrogen atoms. R ¹⁶⁴ is preferably a hydrogen atom or a substituted or unsubstituted aryl group.

R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ , R ¹⁷⁵ , R ¹⁷⁶ , R ¹⁷⁷ , R ¹⁷⁸ , R ¹⁷⁹ , R ¹⁸⁰ , R ¹⁸¹ , R ¹⁸² , R ¹⁸³ , R ¹⁸⁴ , R ¹⁸⁵ , R ¹⁸⁶ , R ¹⁸⁷ And R ⁸⁸ each independently represents a hydrogen atom or a substituent. As the substituent, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a hydroxyl group, or a substituted or unsubstituted acylamino group is preferable. R ¹⁷¹ , R ¹⁷² , R ¹⁷⁵ , R ¹⁷⁶ , R ¹⁷⁷ and R ¹⁸⁰ are preferably all hydrogen atoms. R ¹⁷³ and R ¹⁷⁸ are each preferably a hydroxyl group. R ¹⁷⁴ and R ¹⁷⁹ are each preferably a phenyl group. R ¹⁸¹ , R ¹⁸² , R ¹⁸³ , R ¹⁸⁴ , R ¹⁸⁵ , R ¹⁸⁶ , R ¹⁸⁷ , and R ¹⁸⁸ are preferably all hydrogen atoms.

  Below, the specific example of the pigment | dye represented by general formula (II) is shown. However, the present invention is not limited to the following specific examples.

  Moreover, the following structure can also be mentioned as a specific example of the anion pigment | dye site | part in the pigment | dye represented by general formula (II). However, the present invention is not limited to the following specific examples.

  A general oxonol dye can be synthesized by a condensation reaction between a corresponding active methylene compound and a methine source (a compound used for introducing a methine group into a methine dye). Details of the method for synthesizing this type of compound are described in JP-B-39-22069, JP-A-43-3504, JP-A-52-38056, JP-A-54-38129, JP-A-55-10059, JP-A-58-35544. No. 49-99620, No. 52-92716, No. 59-16834, No. 63-316853, No. 64-40827, and British Patent No. 1133986, US Pat. Nos. 3,247,127, No. 4042397, Reference can be made to the specifications of U.S. Pat. Nos. 4,181,225, 5,213,956 and 5,260,179. Also described in JP-A-63-209995, JP-A-10-309871 and JP-A-2002-249674. A method for synthesizing a bis-type oxonol dye is disclosed in European Patent EP1424691A2.

Visible Information Recording Layer The optical recording medium of the present invention contains at least two dyes including the dye represented by the general formula (I) in the visible information recording layer. Each of the dyes absorbs the irradiated laser light and performs light-to-heat conversion, whereby the dye is decomposed by the generated heat, and the absorption of light in the visible light region can be reduced. Thereby, visible information such as an image can be formed on the visible information recording layer by causing a difference in color tone from the region colored by the undecomposed dye. By irradiating the visible information recording layer containing the two or more dyes with laser light, visible information with high contrast and excellent visibility and high light resistance can be formed.
The dyes represented by the general formulas (I) and (III) are yellow, magenta or cyan, and the dyes represented by the general formula (II) are magenta or cyan. The combination and mixing ratio of the dyes can be determined according to the desired color tone. A preferred combination for forming visible information having high contrast, excellent visibility, and excellent light resistance is a dye represented by the general formula (I) and / or a dye represented by the general formula (III). This is a combination of dyes represented by the general formula (II). When combining the dye represented by the general formula (I) and the dye represented by the general formula (II), Ka ²¹ in the general formula (I) represents an integer in the range of 0 to 2, and the general formula (II Ka ^{22 in (} ) preferably represents an integer in the range of 0 to 2 different from Ka ²¹ . As a more preferred combination, at least one dye selected from the group consisting of a dye represented by the general formula (III), a dye represented by the general formulas (IV) to (XII), and the general formula (II) The combination of the pigment | dye represented can be mentioned.

  The ratio of the dye represented by formula (I) in the dye in the visible information recording layer is preferably 10 to 100% by mass, more preferably 20 to 100% by mass. When the dye represented by the general formula (I) and the dye represented by the general formula (II) are used in combination, the mixing ratio is represented by the mass: the dye represented by the general formula (I): The pigment (II) to be used is preferably 10:90 to 90:10, more preferably 20:80 to 90:10. The mixing ratio of the dye represented by the general formula (III) is preferably 10 to 90% by weight, more preferably 20 to 90% by weight.

  The visible information recording layer preferably contains the dye as a main component. Here, “main component” means that the content of the dye with respect to the total solid content in the visible information recording layer is 50% by mass or more. The dye content in the visible information recording layer is preferably 80% by mass or more, more preferably 90 to 100% by mass. The visible information recording layer may contain a dye other than the dyes represented by the general formulas (I), (II), and (III), but the visible information has high contrast and excellent visibility and high light resistance. In order to form, it is preferable that the dye component contained in the visible information recording layer is composed of the dye.

  The visible information recording layer only needs to be able to record visible information such as characters, designs, and patterns in a visible manner. In order to form visible information with high contrast and excellent visibility, each of the dyes has a wavelength of 400 to 850 nm. It is preferable that it has a maximum absorption in the wavelength region of, and has an absorption of 0.5 or more (preferably 0.1 to 1.0) with respect to laser light in the wavelength region. When the dye contained in the visible information recording layer has the above absorption, visible information such as characters, images, and patterns having good visibility can be recorded by laser light irradiation.

  The visible information recording layer can be formed by applying a coating solution prepared by dissolving the dye in a solvent. As the solvent, various solvents that can be used for preparing the recording layer coating liquid described later can be used. Details of other additives, coating methods, and the like are as described later for the recording layer.

  The thickness of the visible information recording layer is preferably 0.01 to 200 μm, more preferably 0.05 to 100 μm, and further preferably 0.1 to 50 μm. The ratio of the thickness of the visible information recording layer to the recording layer (visible information recording layer thickness / recording layer thickness) is preferably 1/100 to 100/1, more preferably 1/10 to 10/1. More preferred.

  The visible information recorded in the visible information recording layer means visually recognizable information, and includes all visually recognizable information such as characters (columns), pictures, figures, and the like. In addition, as character information, usable person designation information, use period designation information, usable number designation information, rental information, resolution designation information, layer designation information, user designation information, copyright holder information, copyright number information, manufacturing Information, manufacturer date information, sales date information, dealer or seller information, use set number information, region designation information, language designation information, application designation information, product user information, use number information, and the like.

<Layer structure>
The optical recording medium of the present invention has, for example, a first substrate, a recording layer capable of recording and / or reproducing information by irradiating laser light, a reflective layer, a visible information recording layer, and a second substrate in this order. Can be. However, the optical recording medium of the present invention is not particularly limited as long as it has a visible information recording layer on a substrate and the visible information recording layer contains the dye, and the layer structure is not particularly limited. A layer structure can be taken. An example (schematic cross-sectional view) of the optical recording medium of the present invention is shown in FIG.

  The optical recording medium 10 shown in FIG. 1 includes a first substrate 16, a recording layer 18 formed on the first substrate 16, a first reflective layer 20 formed on the recording layer 18, and the first An adhesive layer 22 formed on the reflective layer 20, a second reflective layer 24 formed on the adhesive layer 22, the visible information recording layer 14 formed on the second reflective layer 24, and the visible layer. And a second substrate 26 formed on the information recording layer 14. The type of optical recording medium may be any of a read-only type, a write-once type, a rewritable type, etc., but a write-once type is preferred. In the case of the write-once type, the recording format is not particularly limited, such as a phase change type, a magneto-optical type, and a dye type, but is preferably a dye type.

Examples of the layer configuration of the optical recording medium of the present invention include the following configurations.
(1) The first layer configuration is such that, for example, as shown in FIG. 1, a recording layer 18, a first reflective layer 20, an adhesive layer 22, and a second reflective layer 24 are sequentially formed on a first substrate 16, The visible information recording layer 14 and the second substrate 26 are provided on the second reflective layer 24.
(2) Although the second layer configuration is not shown, the recording layer 18, the first reflective layer 20, and the adhesive layer 22 are sequentially formed on the first substrate 16, and the visible information recording layer 14 is formed on the adhesive layer 22. The second substrate 26 is provided.
(3) Although the third layer configuration is not shown, a recording layer 18, a first reflective layer 20, a protective layer, and an adhesive layer 22 are sequentially formed on the first substrate 16, and visible information is formed on the adhesive layer 22. The recording layer 14 and the second substrate 26 are provided.
(4) Although the fourth layer configuration is not shown, the recording layer 18, the first reflective layer 20, the first protective layer, the adhesive layer 22, and the second protective layer are sequentially formed on the first substrate 16, The visible information recording layer 14 and the second substrate 26 are provided on the second protective layer.
(5) In the fifth layer configuration, the recording layer 18, the first reflective layer 20, the first protective layer, the adhesive layer 22, the second protective layer, and the second reflective layer 24 are sequentially formed on the first substrate 16. The visible information recording layer 14 and the second substrate 26 are provided on the second reflective layer 24.
Note that the layer configurations of (1) to (5) above are merely examples, and these layer configurations are not limited to the order described above, and may be partially replaced. A part may be omitted. Furthermore, each layer may be composed of one layer or a plurality of layers.

When the optical recording medium of the present invention is a CD-R, a transparent film having a thickness of 1.2 ± 0.2 mm on which a pregroove 28 (see FIG. 1) having a track pitch of 1.4 to 1.8 μm is formed. The recording layer 18, the first reflective layer 20, the protective layer, the adhesive layer 22, the second reflective layer 24, the visible information recording layer 14 containing the dye, and the second substrate 26 are placed on the disc-shaped first substrate 16. It is preferable to have a configuration in order. Moreover, when applying to DVD-R, it is preferable that it is the following two aspects.
(1) A recording layer 18 and a light reflection layer are formed on a transparent disk-shaped first substrate 16 having a thickness of 0.6 ± 0.1 mm on which a pregroove 28 having a track pitch of 0.6 to 0.9 μm is formed. The two laminated bodies provided are joined so that the recording layer 18 is inside, and the thickness is 1.2 ± 0.2 mm. The visible information recording layer is formed on at least one of the first substrates 16. 14 is an optical information recording medium.
(2) The recording layer 18 and the light reflecting layer are formed on the transparent disk-shaped first substrate 16 having a thickness of 0.6 ± 0.1 mm on which the pregroove 28 having a track pitch of 0.6 to 0.9 μm is formed. The laminated body provided and a transparent disk-shaped protective substrate having the same shape as the disk-shaped first substrate 16 of the laminated body are joined so that the recording layer 18 is inside, and the thickness is 1.2 ± An optical information recording medium having a thickness of 0.2 mm and a visible information recording layer 14 provided on at least one of the substrates. Note that the DVD-R type optical information recording medium may have a configuration in which a protective layer is further provided on the light reflecting layer.

Hereinafter, each of the above layers and the substrate will be sequentially described.
<Recording layer>
The recording layer in the optical recording medium of the present invention is a layer capable of recording and / or reproducing information by irradiating a laser beam. The recording layer is a layer in which code information (coded information) such as digital information is recorded, and includes a write-once type (preferably a dye write-once type), a phase change type, a magneto-optical type, and the like. The pigment type is preferable.

  Specific examples of the dye contained in the dye-type recording layer include a cyanine dye, an oxonol dye, a metal complex dye, an azo dye, and a phthalocyanine dye. JP-A-4-74690, JP-A-8-127174, JP-A-11-53758, JP-A-11-334204, JP-A-11-334205, JP-A-11-334206, JP-A-11-334207, JP-A-2000- The dyes described in each publication such as 43423, 2000-108513 and 2000-158818 are preferably used.

  The recording layer is prepared by dissolving a recording substance such as a dye in a suitable solvent together with a binder and the like, and then coating the coating liquid on a substrate to form a coating film, followed by drying. Can be formed. The concentration of the recording substance in the coating solution is generally in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, and most preferably. Is in the range of 0.5-3 mass%.

  The recording layer can be formed by a method such as vapor deposition, sputtering, CVD, or solvent coating. Among these, it is preferable to use a solvent coating method. In this case, a coating solution is prepared by dissolving a quencher, a binder, and the like in a solvent in addition to the above-described pigment, and then coating the coating solution on the surface of the substrate to form a coating film, followed by drying. Thus, a recording layer can be formed.

Examples of the solvent of the coating solution include esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; dimethylformamide and the like Amides; Hydrocarbons such as methylcyclohexane; Ethers such as dibutyl ether, diethyl ether, tetrahydrofuran, and dioxane; Alcohols such as ethanol, n-propanol, isopropanol, n-butanol, and diacetone alcohol; 2,2,3,3- Fluorinated solvents such as tetrafluoropropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether And the like can be given.
The said solvent can be used individually or in combination of 2 or more type in consideration of the solubility of the pigment | dye to be used. Various additives such as antioxidants, UV absorbers, plasticizers, lubricants and the like may be further added to the coating solution depending on the purpose.

  When a binder is used, examples of the binder include natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin and rubber; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene and polyisobutylene; Vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride / polyvinyl acetate copolymer; acrylic resins such as polymethyl acrylate and polymethyl methacrylate; polyvinyl alcohol, chlorinated polyethylene, epoxy resin, bunalal resin, Examples include synthetic organic polymers such as rubber derivatives and initial condensates of thermosetting resins such as phenol / formaldehyde resins.

  When a binder is used in combination as a material for the recording layer, the amount of the binder used is generally in the range of 0.01 to 50 times the mass of the dye, preferably 0.1 to 5 times the amount. Is in range.

  Examples of the solvent application method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The recording layer 18 may be a single layer or a multilayer. The thickness of the recording layer 18 is generally in the range of 10 to 500 nm, preferably in the range of 15 to 300 nm, and more preferably in the range of 20 to 150 nm.

  The recording layer can contain various anti-fading agents in order to improve the light resistance of the recording layer. As the antifading agent, a singlet oxygen quencher is generally used. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used. The use amount of the antifading agent such as the singlet oxygen quencher is usually in the range of 0.1 to 50% by mass, preferably in the range of 0.5 to 45% by mass, more preferably, The range is 3 to 40% by mass, particularly preferably 5 to 25% by mass.

  Specific examples of the material constituting the phase change recording layer include Sb—Te alloy, Ge—Sb—Te alloy, Pd—Ge—Sb—Te alloy, Nb—Ge—Sb—Te alloy, Pd—Nb—. Ge—Sb—Te alloy, Pt—Ge—Sb—Te alloy, Co—Ge—Sb—Te alloy, In—Sb—Te alloy, Ag—In—Sb—Te alloy, Ag—V—In—Sb—Te An alloy, an Ag—Ge—In—Sb—Te alloy, and the like. The layer thickness of the phase change type recording layer 18 is preferably 10 to 50 nm, and more preferably 15 to 30 nm. The phase change type recording layer can be formed by a vapor phase thin film deposition method such as a sputtering method or a vacuum evaporation method.

<First substrate>
The first substrate 16 in the optical recording medium shown in FIG. 1 can be formed using a material arbitrarily selected from various materials used as a substrate of a conventional optical recording medium. Examples of the material of the first substrate 16 include acrylic resins such as glass, polycarbonate, and polymethyl methacrylate, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, amorphous polyolefins, and polyesters. These may be used together if desired. Note that these materials can be used as a film or as the rigid first substrate 16. Among the above materials, polycarbonate is preferable from the viewpoint of moisture resistance, dimensional stability, price, and the like.
The thickness of the first substrate 16 is preferably 0.1 to 1.2 mm, and more preferably 0.2 to 1.1 mm.

On the surface side (the surface side on which the pregroove 28 is formed) of the first substrate 16 on the side where the recording layer 18 is provided, for the purpose of improving the flatness, improving the adhesive force, and preventing the recording layer 18 from being altered, A coating layer may be provided.
Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chlorosulfonated. High molecular substances such as polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate; and silane coupling agents And the like. The undercoat layer is prepared by dissolving or dispersing the above substances in a suitable solvent to prepare a coating solution, and then applying this coating solution to the surface of the first substrate 16 by a coating method such as spin coating, dip coating, or extrusion coating. It can be formed by coating.
The thickness of the undercoat layer is generally in the range of 0.005 to 20 μm, and preferably in the range of 0.01 to 10 μm.

<First reflective layer>
As shown in FIG. 1, a first reflective layer 20 may be provided adjacent to the recording layer 18 for the purpose of improving reflectivity during information reproduction. The light reflective substance that is the material of the first reflective layer 20 is a substance that has a high reflectivity with respect to laser light. Examples thereof include Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Mention may be made of metals such as Sn, Bi and semi-metals or stainless steel. These substances may be used alone, in combination of two or more or as an alloy. The first reflective layer 20 can be formed on the first substrate 16 or the recording layer 18 by, for example, vapor-depositing, sputtering, or ion-plating the light reflective material. The layer thickness of the first reflective layer 20 is generally in the range of 10 to 300 nm, and preferably in the range of 50 to 200 nm.

<Adhesive layer>
As shown in FIG. 1, an adhesive layer 22 can be formed in order to improve the adhesion between the first reflective layer 20 and the second substrate 26.
The material constituting the adhesive layer 22 is preferably a photocurable resin, and in particular, a material having a small curing shrinkage rate is preferable in order to prevent the disk from warping. Examples of such a photocurable resin include UV curable resins (UV curable adhesive) such as “SD-640” and “SD-347” manufactured by Dainippon Ink and Chemicals, Inc. . The thickness of the adhesive layer 22 is preferably in the range of 1 to 1000 μm, more preferably in the range of 5 to 500 μm, and particularly in the range of 10 to 100 μm in order to provide elasticity. preferable.

<Second substrate>
As shown in FIG. 1, a second substrate 26 (protective substrate) can be provided for protecting the visible information recording layer 14. The second substrate 26 can be formed using the same material as the first substrate 16 described above.

<Protective layer>
A protective layer may be provided for the purpose of physically and chemically protecting the first reflective layer 20, the recording layer 18, and the like. It should be noted that a configuration similar to the case of manufacturing a DVD-R type optical recording medium, that is, a configuration in which two substrates (including the case where one is the second substrate 26) is bonded with the recording layer 18 inside is adopted. However, it is not always necessary to form a protective layer.
Examples of materials used for the protective layer include inorganic substances such as ZnS, ZnS—SiO ₂ , SiO, SiO ₂ , MgF ₂ , SnO ₂ , and Si ₃ N ₄ , thermoplastic resins, thermosetting resins, and UV curable materials. Organic substances such as resins can be mentioned.
When a thermoplastic resin or a thermosetting resin is used, it can be formed by dissolving these in a suitable solvent to prepare a coating solution, and then applying and drying the coating solution. . In the case of a UV curable resin, it can also be formed by preparing a coating solution as it is or by dissolving it in a suitable solvent, and then applying the coating solution and curing it by irradiation with UV light. In these coating liquids, various additives such as an antistatic agent, an antioxidant, and a UV absorber may be added according to the purpose. The thickness of the protective layer is generally in the range of 0.1 μm to 1 mm.
The optical recording medium of the present invention can also be applied as a so-called read-only optical information recording medium having a recording portion (pit) in which information reproducible by laser light is recorded.

[Visible information recording method]
The first visible information recording method of the present invention (hereinafter also referred to as “recording method I”) is a visible information recording method on the visible information recording layer of the optical recording medium of the present invention, wherein the visible information is Recording is performed using the same laser beam as that used for recording information on the recording layer.
The second visible information recording method of the present invention (hereinafter also referred to as “recording method II”) is a method of recording visible information on the visible information recording layer on a disc-shaped optical recording medium of the present invention, Visible information is recorded using laser light that oscillates in the radial direction of the optical recording medium and is irradiated a plurality of times on substantially the same locus. In Method II, it is preferable to record visible information using the same laser beam as that used for recording information on the recording layer, as in Method I.
Hereinafter, the recording methods I and II may be collectively referred to as the recording method of the present invention.

  According to the recording method I, visible information is recorded using the same laser beam (laser beam 12 in FIG. 1) as the laser beam (laser beam 12 in FIG. 1) used for recording information on the recording layer. Therefore, it is possible to share a laser light source in a single recording device, to minimize the hardware resources of the recording device, and for a general user to easily record an image using these devices. be able to. Furthermore, since the optical recording medium of the present invention contains the dye in the visible information recording layer, there is an advantage that an image having high contrast and excellent visibility can be formed. The recording of visible information such as an image on the visible information recording layer of the optical recording medium of the present invention is most preferably performed by the visible information recording method of the present invention, but is not limited thereto.

  In the recording method of the present invention, one optical disc drive (recording apparatus) having a recording function for both layers is used for recording visible information such as images on the visible information recording layer and recording optical information on the recording layer. Can be done. When one optical disk drive is used as described above, after recording on one of the visible information recording layer and the recording layer, the recording can be reversed and recording can be performed on the other layer. As an optical disc drive having a function of recording visible information on the visible information recording layer, for example, an optical disc drive described in JP 2003-203348 A, JP 2003-242750 A, or the like can be used. .

  Further, when recording visible information on the visible information recording layer, the recording device tracks the optical recording medium and the laser pickup by a tracking groove formed in the visible information recording layer, along the surface of the optical recording medium. It is possible to record a visible image by moving the laser beam relative to the relative movement and modulating the laser beam according to image data such as characters and pictures to be imaged and irradiating the laser beam toward the visible information recording layer. it can. Such a configuration is described in, for example, Japanese Patent Application Laid-Open No. 2002-203321.

In normal digital data recording, it is usual to irradiate a laser beam once with a substantially elliptical locus. In general, when forming pits in the dye recording layer, it is important to form pits with sufficient reflectivity and degree of modulation to be recognized by the drive. A dye that can obtain a sufficient reflectance and degree of modulation by one-time laser light irradiation is selected.
On the other hand, in recent years, a system described in JP-A-2002-203321 has been proposed as a new image forming method. In this system, visible information such as an image is recorded on a visible information recording layer containing a dye by irradiating a laser beam to a substantially same locus a plurality of times. In addition, since the position where pits are formed in the radial direction is specified in a normal optical disk, the laser beam cannot swing in the radial direction of the optical disk. Visible information is formed by oscillating in a radial direction and irradiating a substantially identical locus a plurality of times. The dyes used in the present invention are all suitable for the above-described system, and can form visible information with high contrast and clearness and excellent light resistance by the recording method described above.

Details of the image forming method will be described below with reference to FIGS.
FIG. 2 shows the locus of the laser light irradiated for image formation.
First, as shown in FIG. 2, the laser light source is positioned at a radial position where the first image forming portion is located on the inner circumference side of the optical disc, and then the circumferential position θ is detected and the radial position is indicated by image data. The laser power is switched to a predetermined high output (a value at which the visible light characteristic of the visible information recording layer changes, for example, a value of 1 mW or more) at each image forming position in the circumferential direction. As a result, the visible light characteristic of the visible information recording layer changes (discoloration or the like) at the portion irradiated with the high-power laser light, and image formation is performed.
Thereafter, when the optical disk rotates once and returns to the reference position in the circumferential direction, the laser light source is transferred to the outer circumference by a predetermined pitch Δr by a feed motor or the like, and each image formation in the circumferential direction instructed by the image data about the radial position is performed. The image is formed by switching the laser power to a predetermined high output at the position. Thereafter, this operation is repeated, and image formation is performed by sequentially moving in the outer circumferential direction at a predetermined pitch Δr every round. FIG. 2 shows the locus of laser light on the optical disk surface (surface on the visible information recording layer side, hereinafter also referred to as “label surface”) by this image forming operation. The laser power is switched to a high output at the portion drawn with a thick line, and image formation is performed. FIG. 3 is an enlarged view of the locus of the laser beam at the portion drawn by the bold line. As shown in FIG. 3, an image is formed by irradiating laser light multiple times in the radial direction of the optical disk and irradiating substantially the same locus. Here, the swinging width of the laser light and the number of times of irradiation with the laser light in substantially the same locus are set for each recording apparatus.

In the image forming method, a radial position where there is no image forming portion is not scanned, and the next image forming portion is moved to a certain radial position at a time to form an image. When the pitch Δr is large, even if the image should originally be formed in the radial direction, a gap occurs and an image is formed. If the pitch Δr is reduced, the gap can be made inconspicuous, but the number of rounds required to form an image on the entire label surface increases, and the image formation takes time. In the apparatus described in Japanese Patent Laid-Open No. 2002-203321, the tracking actuator is driven by a vibration signal (sine wave, triangular wave, etc.) generated from a vibration signal generation circuit during image formation, and the objective lens is vibrated in the disk radial direction. I am doing so. As a result, the laser beam vibrates in the disk radial direction, and an image can be formed without a gap (or with a small gap) even if the pitch Δr is relatively large. The frequency of the vibration signal can be set to about several kHz, for example. The pitch Δr can be set to about 50 to 100 μm, for example.
JP-A-2002-203321 can be referred to for details of the above image forming method.

  A recording apparatus for recording optical information (digital information) on a recording layer has at least a laser pickup that emits laser light and a rotating mechanism that rotates an optical recording medium, and rotates recording and reproduction on the recording layer. This can be performed by irradiating the recording layer of the optical recording medium in a state with laser light from a laser pickup. The configuration of such a recording apparatus itself is well known.

  Next, recording of information (digital information) on the recording layer will be described. When the recording layer is a dye type, first, laser light is irradiated from a laser pickup while rotating the above-mentioned optical recording medium that has not been recorded at a predetermined recording linear velocity. By this irradiation light, the dye in the recording layer absorbs the light and the temperature rises locally, and a desired void (pit) is generated and its optical characteristics are changed to record information.

The recording waveform of the laser beam may be a pulse train or one pulse when one pit is formed. The ratio to the actual recording length (pit length) is important.
The pulse width of the laser beam is preferably in the range of 20 to 95%, more preferably in the range of 30 to 90%, and still more preferably in the range of 35 to 85% with respect to the length to be actually recorded. Here, when the recording waveform is a pulse train, the sum is in the above range.

The power of the laser beam varies depending on the recording linear velocity, but when the recording linear velocity is 3.5 m / s, the range of 1 to 100 mW is preferable, the range of 3 to 50 mW is more preferable, and the range of 5 to 20 mW is further increased. preferable. When the recording linear velocity is doubled, the preferable range of the laser beam power is ^21/2 times, respectively. In order to increase the recording density, the NA of the objective lens used for the pickup is preferably 0.55 or more, and more preferably 0.60 or more. In the present invention, a semiconductor laser having an oscillation wavelength in the range of 350 to 850 nm can be used as the recording light.

  Next, a case where the recording layer is a phase change type will be described. In the case of the phase change type, it is composed of the above-described material, and the phase change between the crystalline phase and the amorphous phase can be repeated by laser light irradiation. At the time of information recording, a concentrated laser light pulse is irradiated for a short time to partially melt the phase change recording layer. The melted portion is rapidly cooled by thermal diffusion and solidified to form an amorphous recording mark. During erasing, the recording mark portion is irradiated with laser light, heated to a temperature below the melting point of the recording layer and above the crystallization temperature, and then cooled to crystallize the amorphous recording mark. Return to the unrecorded state.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the embodiments shown in the following examples.

(Disk 101)
A disk 101 is a DVD-R type optical recording medium having two layers bonded to each other and having the layer configuration shown in FIG. Hereinafter, a method for producing the disk 101 will be described.

A first substrate 16 having a thickness of 0.6 mm and a diameter of 120 mm having spiral grooves (depth: 130 nm, width: 300 nm, track pitch: 0.74 μm) is formed from polycarbonate resin by injection molding. did.
Thereafter, 1.5 g of each of the following two oxonol dyes is dissolved in 100 ml of 2,2,3,3-tetrafluoro-1-propanol to prepare a coating solution, and this coating solution is first coated by spin coating. The recording layer 18 having a layer thickness of 80 μm was formed by coating on the surface of the substrate 16 on which the pregroove 28 was formed.

  Next, silver is sputtered on the recording layer 18 to form a first reflective layer 20 having a thickness of 120 nm, and then an ultraviolet curable resin (SD318 (manufactured by Dainippon Ink and Chemicals)) is applied by a spin coating method. The first protective layer having a thickness of 10 μm was formed by irradiating with ultraviolet rays, and the first disk was manufactured by the above steps.

  Next, in order to form the visible information recording layer 14, 21.5 g of the dye D represented by the general formula (III) and 0.5 g of the following compound A are added to 100 ml of 2,2,3,3-tetrafluoro-1-propanol. A dissolved coating solution for a visible information recording layer was prepared. The visible information recording layer 14 having a thickness of 100 μm was formed on the second substrate 26 having a thickness of 0.6 mm and a diameter of 120 mm by spin coating with the visible information recording layer coating solution.

  Next, silver is sputtered on the visible information recording layer 14 to form a second reflective layer 24 having a film thickness of 70 nm, and then an ultraviolet curable resin (SD318 (manufactured by Dainippon Ink & Chemicals, Inc.) is applied by spin coating. After that, it was cured by irradiating with ultraviolet rays to form a second protective layer having a layer thickness of 10 μm.

  Next, the following steps were performed in order to bond the first disk and the second disk to complete a single disk. First, a slow-acting cationic polymerization adhesive (Sony Chemical Co., Ltd., SDK7000) was printed on the first protective layer of the first disk and the second protective layer of the second disk by screen printing. At this time, the mesh size of the screen printing plate was 300 mesh. Next, immediately after irradiating with ultraviolet rays using a metal halide lamp, the first disk and the second disk were bonded from the respective protective layer sides, pressed from both sides, and allowed to stand for 5 minutes, thereby producing the disk 101.

(Disk 102)
Except for using 0.5 g of the dye D1 represented by the general formula (I) and 1.0 g of the dye D2 represented by the general formula (III) as the visible information recording layer dye, the same method as that for the disc 101 was used. A disk 102 was produced.

(Disk 103)
Other than using 0.5 g of the dye D1 represented by the general formula (I), 0.4 g of the dye D3 represented by the general formula (III), and 1.1 g of the following compound B as the dye for the visible information recording layer Produced the disk 103 in the same manner as the disk 101.

(Disk 104)
As a dye for the visible information recording layer, 0.7 g of the dye D1 represented by the general formula (I), 0.9 g of the dye D2 represented by the general formula (III), and a dye represented by the general formula (II) A disc 104 was produced in the same manner as the disc 101 except that 0.4 g of D3 was used.

(Disk 105)
A disc 105 was produced in the same manner as the disc 101 except that 0.5 g of the following compound A and 1.5 g of the following compound B were used as the dye for the visible information recording layer.

Evaluation results (contrast evaluation)
The produced disc was recorded as follows.
An optical recording medium using a recording apparatus (laser is a semiconductor laser having a wavelength of 660 nm) having a laser pickup for emitting laser light and a rotating mechanism for rotating the optical recording medium described in JP-A-2002-203321 And the laser pickup are relatively moved along the surface of the optical recording medium, and the semiconductor laser light is modulated according to desired image data in synchronization with the relative movement, and the linear velocity is 3.5 m / s and the recording power is 8 mW. A visible image was recorded by irradiating the visible information recording layer 14 in a state of being focused on conditions. At this time, the laser beam swayed in the radial direction of the optical disk and irradiated on the substantially same locus a plurality of times to record the visible information. Further, electronic information can be recorded by rotating the optical recording medium with a rotating mechanism and irradiating the recording layer 18 with laser light from a laser pickup.
For each optical recording medium on which a visible image was recorded as described above, the absolute reflectances of the laser-irradiated portion and the laser-unirradiated portion of the visible information recording layer were measured, and Sv represented by the following formula was obtained. The contrast was evaluated according to the evaluation criteria.

＜評価基準＞
５（コントラスト優良） ： ０．２５以上
４（コントラスト良好） ： ０．２５未満〜０．２０以上
３（コントラスト実用十分）： ０．２０未満〜０．１５以上
２（コントラスト不十分） ： ０．１５未満〜０．１０以上
１（コントラスト不良） ： ０．１０未満

<Evaluation criteria>
5 (contrast excellent): 0.25 or more 4 (contrast good): less than 0.25 to 0.20 or more 3 (contrast practical enough): less than 0.20 to 0.15 or more 2 (contrast insufficient): 0. Less than 15 to 0.10 or more 1 (contrast defect): less than 0.10

(Light resistance evaluation)
The disk sample was irradiated with a Xe lamp (70,000 Lux) for 24 hours, and the reduction rate of dye absorption before and after Xe light irradiation was determined by measuring the reflection spectrum with an ultraviolet-visible spectrometer.

Evaluation results As shown in Table 2, laser light was applied to the disks 101 to 105 containing two or more dyes containing the dye represented by the general formula (I) and / or the general formula (III) in the visible information recording layer. By irradiation, visible information having high contrast and excellent visibility could be formed. Further, the disk 104 on which the visible information recording layer was formed using only the dyes represented by the general formulas (I), (II) and (III) showed excellent light resistance.

An example (schematic cross-sectional view) of the optical recording medium of the present invention is shown. The locus of the laser beam on the surface of the optical disc during image formation is shown. It is an enlarged view of the locus | trajectory of the laser beam in the part drawn with the thick line in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Optical recording medium 12 ... Laser beam 14 ... Visible information recording layer 16 ... 1st board | substrate 18 ... Recording layer 20 ... 1st reflection layer 22 ... Adhesion layer 24 ... 2nd reflection layer 26 ... 2nd board | substrate 28 ... Pregroove

Claims (16)

An optical recording medium having a visible information recording layer on a substrate,
The visible information recording layer contains at least two dyes, and at least one dye selected from the group consisting of dyes represented by the following general formula (I) and dyes represented by the general formula (III) An optical recording medium comprising:

[In the general formula (I), Za ²¹ and Za ²² each independently represent an atomic group forming an acidic nucleus, and Ma ²¹ , Ma ²² and Ma ²³ each independently represent a substituted or unsubstituted methine group. Ka ²¹ represents an integer in the range of 0 to 3, and Q ¹ represents a monovalent cation. However, when Ka ²¹ represents 2 or 3, the acidic nucleus formed by Za ²² is an acidic nucleus different from the tautomer of the acidic nucleus formed by Za ²¹ , and a plurality of Ma ²¹ and Ma ²² are Each of them may be the same or different, and when Ka ²¹ is 0 or 1, the acidic nucleus formed by Za ²² may be a tautomer of the acidic nucleus formed by Za ²¹ . It may be an acidic nucleus different from the body. ]

[In the general formula (III), Za ³¹ and Za ³² each independently represent an atomic group forming an acidic nucleus, and Ma ³¹ , Ma ³² and Ma ³³ each independently represent a substituted or unsubstituted methine group. L represents a divalent linking group that does not form a π-conjugated system with two bonds, Ka ³¹ represents an integer in the range of 0 to 3, and Q ³ represents a monovalent cation. Or 2Q ³ represents a divalent cation, and when Ka ³¹ is 2 or 3, a plurality of Ma ³¹ and Ma ³² may be the same or different from each other. ] In general formula (I), the acidic nucleus formed by Za ²¹ is an acidic nucleus represented by any one of the following general formulas (A-1) to (A-12), and the acidic nucleus formed by Za ²² is The optical recording medium according to claim 1, wherein the optical recording medium is an acidic nucleus represented by any one of the following general formulas (B-1) to (B-12).

[In General Formulas (A-1) to (A-12) and (B-1) to (B-12), * represents the position at which the acidic nucleus is linked to Ma ²¹ or Ma ^23, and R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^k , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k1 , R ^{k2, R k3, R k4,} R m1, R m2, R m3, R m4, R n1 and R ⁿ² are each independently a hydrogen atom or a substituent, an acidic nucleus and Za ²² which Za ²¹ is formed When the main skeletons of the acidic nuclei formed are the same, the plurality of acidic nuclei substituents may be the same or different. ] In general formula (III), the acidic nucleus formed by Za ³¹ is an acidic nucleus represented by any one of the following general formulas (A-1) to (A-12), and the acidic nucleus formed by Za ³² is The optical recording medium according to claim 1, wherein the optical recording medium is an acidic nucleus represented by any one of the following general formulas (B-1) to (B-12).

[In General Formulas (A-1) to (A-12) and (B-1) to (B-12), * represents a position where the acidic nucleus is linked to Ma ³¹ or Ma ^33, and R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^k , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k1 , R ^{k2, R k3, R k4,} R m1, R m2, R m3, R m4, R n1 and R ⁿ² are each independently a hydrogen atom or a substituent, an acidic nucleus and Za ³² which Za ³¹ is formed When the main skeletons of the acidic nuclei formed are the same, the plurality of acidic nuclei substituents may be the same or different. ] The dye represented by the general formula (I) is represented by the following general formula (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) or (XII). The optical recording medium according to claim 1, wherein the optical recording medium is a dye represented by formula (1).

[In formulas (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³¹ , R ³² , R ³³ , R ³⁴ , ^{R 41, R 42, R 43} , R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54, R 55, R 56, R 57 , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² and R ⁶³ each independently represents a hydrogen atom or a substituent, and Ma ²⁷ , Ma ²⁸ and Ma ²⁹ are each independently substituted or unsubstituted. Ka ²³ represents 0 or 1, Ka ²⁴ represents an integer in the range of 0 to 2, X ¹ represents an oxygen atom or CH ₂ , and Y ¹ represents an oxygen atom or a sulfur atom. Q is a monovalent cation Represent. ] The optical recording medium according to claim 1, wherein the visible information recording layer contains at least one dye represented by the following general formula (II).

[In the general formula (II), Za ²³ represents an atomic group forming an acidic nucleus, Za ^{23 ′} represents an atomic group forming an acidic nucleus that is a tautomer of the acidic nucleus formed by Za ²³ , and Ma ²⁴ , Ma ²⁵ and Ma ²⁶ each independently represent a substituted or unsubstituted methine group, Ka ²² represents 2 or 3, and a plurality of Ma ²⁵ and Ma ²⁶ may be the same or different. Often, Q ² represents a monovalent cation. ] The acidic nucleus Za ²³ in the general formula (II) to form the following general formula (A-1) ~ (A -12) The optical recording medium according to claim 5 is an acidic nucleus represented by one of .

[In General Formulas (A-1) to (A-12), * represents a position where the acidic nucleus is linked to Ma ^26, and R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ^c1 , R ^c2 , R ^d1 , R ^d2 , R ^e1 , R ^e2 , R ^f1 , R ^g1 , R ^h1 , R ^j1 , R ^j2 , R ^k1 , R ^k2 , R ^k3 , R ^k4 , R ^m1 , R ^m2 , R ^m3 , R ^m4 , ^Rn1 and ^Rn2 are each independently a hydrogen atom or a substituent. ] Ka ²¹ in the general formula (I) represents an integer in the range of 0 to 2,
The optical recording medium according to claim 5 or 6, wherein Ka ²² in the general formula (II) represents an integer in the range of 0 to 2 different from Ka ²¹ . The optical recording medium according to claim 5, wherein the dye represented by the general formula (II) is a dye represented by the following general formula (XVIII).

[In general formula (XVIII), R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ , R ¹⁵⁸ , R ¹⁵⁹ and R ¹⁶⁰ each independently represents a hydrogen atom or a substituent. R ¹⁶¹ and R ¹⁶⁷ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted alkoxy group Represents a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted acylamino group, and R ¹⁶² , R ¹⁶³ , R ¹⁶⁴ , R ¹⁶⁵ and R ¹⁶⁶ are each independently Hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted acylamino group, or substituted or unsubstituted hete It represents a cyclic ^{group, R 71, R 72, R} 73, R 74, R 75, R 76, R 77, R 78, R 79, R 80, R 81, R 82, R 83, R 84, R 85, R ⁸⁶ , R ⁸⁷ and R ⁸⁸ each independently represents a hydrogen atom or a substituent. ] The said visible information recording layer contains the pigment | dye represented by general formula (I) and / or general formula (III), and the pigment | dye represented by general formula (II). An optical recording medium according to 1. The optical recording medium according to any one of claims 1 to 9, wherein the visible information recording layer contains a dye represented by the general formula (I) and a dye represented by the general formula (III). The visible information recording layer is composed of a dye represented by general formula (III), at least one dye selected from the group consisting of dyes represented by general formulas (IV) to (XII), and general formula (II). The optical recording medium of any one of Claims 5-10 containing the pigment | dye represented. The optical recording medium according to claim 1, further comprising a recording layer capable of recording and / or reproducing information by irradiating a laser beam. The optical recording medium according to claim 12, comprising a first substrate, the recording layer, a reflective layer, the visible information recording layer, and a second substrate in this order. The optical recording medium according to claim 1, wherein the optical recording medium has a disk shape. A visible information recording method on the visible information recording layer of the optical recording medium according to any one of claims 12 to 14,
The visible information recording method, wherein the visible information is recorded using the same laser beam as that used for recording information on the recording layer. A visible information recording method on the visible information recording layer of the optical recording medium according to claim 14,
The visible information recording method, wherein the visible information is recorded by using laser light which is oscillated in a radial direction of the optical recording medium and irradiated a plurality of times on substantially the same locus.

Images