JP2008188867A - Optical information recording medium, information recording method, metal complex compound and method of using the same - Google Patents

Abstract

【選択図】なしAn optical information recording medium excellent in recording characteristics and light resistance in information recording by irradiation with a short wavelength laser beam, and a novel compound suitable as a dye for a recording layer of the optical information recording medium.
An optical information recording medium having a recording layer on a substrate. The recording layer contains a metal complex compound represented by the following general formula (1). In the general formula (1), Q ¹ and Q ² each independently form a 5-membered monocyclic hetero ring excluding 1,3-thiazole, 1,3,4-thiadiazole and 1,3,4-triazole. Represents an atomic group, M represents a metal ion or a metal oxide ion, R represents a substituent, and n represents an integer in the range of 0-4. When n is an integer of 2 or more, a plurality of R may be the same as or different from each other.

[Selection figure] None

Description

  The present invention relates to an optical information recording medium capable of recording information by laser light irradiation and a method for recording information on the optical information recording medium by laser light irradiation. More specifically, the present invention relates to a heat mode type optical information recording medium suitable for information recording by irradiation with a short wavelength laser beam having a wavelength of 440 nm or less. Furthermore, the present invention relates to a metal complex compound suitable as a recording layer dye for an optical information recording medium and a method for using the same.

  Conventionally, a write-once CD (CD-R) and a write-once DVD (DVD-R) are known as optical information recording media capable of recording information only once with a laser beam. Information recording on a CD-R is performed by a near-infrared laser beam (usually a wavelength of about 780 nm), whereas information recording on a DVD-R is performed by a visible laser beam (about 630 to 680 nm). Is called. Since DVD-R uses laser light having a shorter wavelength than CD-R as recording laser light, DVD-R has the advantage that high-density recording is possible compared to CD-R. Therefore, in recent years, DVD-R has secured its position as a large-capacity recording medium to some extent.

  Recently, networks such as the Internet and high-definition TV are rapidly spreading. In addition, there is an increasing demand for a large-capacity recording medium for recording image information inexpensively and easily, with the upcoming broadcast of HDTV (High Definition Television). However, it cannot be said that the CD-R and DVD-R have a recording capacity that is large enough to meet future requirements. Therefore, in order to improve the recording density by using a laser beam having a shorter wavelength than that of the DVD-R, development of a large-capacity optical disc capable of recording with a short wavelength laser (for example, a wavelength of 440 nm or less) is in progress. As such an optical disk, for example, an optical recording disk called a Blu-ray system using a 405 nm blue laser has been proposed.

Patent Documents 1 and 2 propose an optical information recording medium for recording information by irradiating a short wavelength laser beam like the Blu-ray optical recording disk.
JP 2003-246141 A WO2005-068459

  In order to obtain good recording characteristics in optical information recording, it is preferable to use a dye having absorption near the wavelength of the recording laser light as the dye for the recording layer. As a result of the study by the present inventors, the dye used in the recording layer in the optical information recording media described in Patent Documents 1 and 2 has absorption in the short wavelength region, but cannot always obtain sufficient recording characteristics. It has been found. Further, as a result of the study by the present inventors, it has been found that since the above dye has insufficient light resistance, the recording layer containing this dye is inferior in light resistance storage stability.

  Accordingly, an object of the present invention is to provide an optical information recording medium excellent in recording characteristics and light resistance in information recording by irradiation with a short wavelength laser beam, and a novel compound suitable as a dye for a recording layer of the optical information recording medium. is there.

  As a result of intensive studies by the present inventors to achieve the above object, the reason why the recording characteristics of the optical information recording media described in Patent Documents 1 and 2 are low is that the thermal decomposability of the recording layer dye is low ( It was found that this was due to the high pyrolysis temperature. Therefore, the present inventors have further studied based on the above findings, and by using a predetermined metal complex compound having both excellent thermal decomposability and light resistance as a recording layer dye, recording by irradiation with short wavelength laser light is performed. The present invention has led to the completion of the present invention by finding an optical information recording medium exhibiting excellent recording characteristics and having excellent light resistance and a novel metal complex compound having both excellent light resistance and thermal decomposability. It was.

一般式（１）中、Q¹およびQ²は、各々独立に、1,3-チアゾール、1,3,4-チアジアゾールおよび1,3,4-トリアゾールを除く５員単環ヘテロ環を形成する原子群を表し、Mは金属イオンもしくは金属酸化物イオンまたはそれらの塩を表し、Rは置換基を表し、nは0〜4の範囲の整数を表す。nが2以上の整数であるとき、複数存在するRは互いに同じであっても異なっていてもよい。]
[２]一般式（１）で表される金属錯体化合物は、下記一般式（２）で表される金属錯体化合物である[１]に記載の光情報記録媒体。

[一般式（２）中、Q³およびQ⁴は、各々独立に、下記部分構造（A-1）または(A-2)で表される環を形成する原子群を表し、R、Mおよびnは、それぞれ一般式（１）における定義と同義である。]

[上記式中、＊は結合するN原子との結合位置を表し、R¹およびR²は、各々独立に、水素原子または置換基を表す。]
[３]前記Mは鉄イオンである[１]または[２]に記載の光情報記録媒体。
[４]前記基板上に、光反射層、前記記録層、バリア層、接着層または粘着層、およびカバー層をこの順に有する[１]〜[３]のいずれかに記載の光情報記録媒体。
[５]前記基板は、少なくとも一方の面にトラックピッチ５０〜５００ｎｍのプリグルーブを有し、前記記録層を、前記プリグルーブが形成された面上に有する[１]〜[４]のいずれかに記載の光情報記録媒体。
[６]前記記録層は、波長４４０ｎｍ以下のレーザー光により情報の記録が可能な層である[１]〜[５]のいずれかに記載の光情報記録媒体。
［７］基板上に記録層を有する光情報記録媒体に情報を記録する情報記録方法であって、
前記光情報記録媒体は、［１］〜［６］のいずれかに記載の光情報記録媒体であり、
前記情報を、前記光情報記録媒体に対してレーザー光を照射することにより、該記録層に記録する情報記録方法。
［８］前記レーザー光の波長は４４０ｎｍ以下である［７］に記載の情報記録方法。
[９]下記一般式（３）で表される金属錯体化合物。

[一般式（３）中、Q³およびQ⁴は、各々独立に、下記部分構造（A-1）で表される環を形成する原子群を表し、R、Mおよびnは、それぞれ一般式（１）における定義と同義である。]

[上記式中、＊は結合するN原子との結合位置を表し、R¹およびR²は、各々独立に、水素原子または置換基を表す。]
[１０][９]に記載の金属錯体化合物を、色素含有記録層を有する光情報記録媒体において、前記記録層用色素として使用する方法。 That is, the means for achieving the above object is as follows.
[1] An optical information recording medium having a recording layer on a substrate, wherein the recording layer contains a metal complex compound represented by the following general formula (1).

In the general formula (1), Q ¹ and Q ² each independently form a 5-membered monocyclic hetero ring excluding 1,3-thiazole, 1,3,4-thiadiazole and 1,3,4-triazole. Represents an atomic group, M represents a metal ion or metal oxide ion or a salt thereof, R represents a substituent, and n represents an integer in the range of 0-4. When n is an integer of 2 or more, a plurality of R may be the same as or different from each other. ]
[2] The optical information recording medium according to [1], wherein the metal complex compound represented by the general formula (1) is a metal complex compound represented by the following general formula (2).

[In General Formula (2), Q ³ and Q ⁴ each independently represent an atomic group forming a ring represented by the following partial structure (A-1) or (A-2), and R, M and n is synonymous with the definition in General formula (1), respectively. ]

[In the above formula, * represents the bonding position with the N atom to be bonded, and R ¹ and R ² each independently represents a hydrogen atom or a substituent. ]
[3] The optical information recording medium according to [1] or [2], wherein M is an iron ion.
[4] The optical information recording medium according to any one of [1] to [3], which includes a light reflecting layer, the recording layer, a barrier layer, an adhesive layer or an adhesive layer, and a cover layer in this order on the substrate.
[5] The substrate has a pregroove with a track pitch of 50 to 500 nm on at least one surface, and has the recording layer on the surface on which the pregroove is formed. An optical information recording medium described in 1.
[6] The optical information recording medium according to any one of [1] to [5], wherein the recording layer is a layer capable of recording information with a laser beam having a wavelength of 440 nm or less.
[7] An information recording method for recording information on an optical information recording medium having a recording layer on a substrate,
The optical information recording medium is the optical information recording medium according to any one of [1] to [6],
An information recording method for recording the information on the recording layer by irradiating the optical information recording medium with laser light.
[8] The information recording method according to [7], wherein the wavelength of the laser beam is 440 nm or less.
[9] A metal complex compound represented by the following general formula (3).

[In General Formula (3), Q ³ and Q ⁴ each independently represent an atomic group forming a ring represented by the following partial structure (A-1), and R, M and n are each a general formula It is synonymous with the definition in (1). ]

[In the above formula, * represents the bonding position with the N atom to be bonded, and R ¹ and R ² each independently represents a hydrogen atom or a substituent. ]
[10] A method of using the metal complex compound according to [9] as the recording layer dye in an optical information recording medium having a dye-containing recording layer.

According to the present invention, an optical information recording medium having excellent recording characteristics and high light resistance even after recording (particularly an optical information recording medium capable of recording information by irradiation with laser light of 440 nm or less) is provided. can do.
Furthermore, according to the present invention, a novel metal complex compound capable of providing an optical information recording medium having excellent recording characteristics and light resistance can be provided.

  Hereinafter, the present invention will be described in more detail.

  The present invention relates to an optical information recording medium having a recording layer on a substrate. The optical information recording medium of the present invention contains a metal complex compound represented by the following general formula (1) in the recording layer.

Below, general formula (1) is demonstrated.
In the general formula (1), Q ¹ and Q ² each independently form a 5-membered monocyclic hetero ring excluding 1,3-thiazole, 1,3,4-thiadiazole and 1,3,4-triazole. Represents an atomic group. The 5-membered monocyclic hetero ring excluding 1,3-thiazole, 1,3,4-thiadiazole and 1,3,4-triazole is not particularly limited, but the partial structures (A-1) to (A- And 5-membered monocyclic heterocycle represented by 4), pyrazole, imidazole and the like. The 5-membered monocyclic heterocycle formed by Q ^{1 and} the 5-membered monocyclic heterocycle formed by Q ² may be the same or different.

  The 5-membered monocyclic heterocycle is preferably a 5-membered monocyclic heterocycle represented by the partial structure (A-1) or (A-2), and is preferably a 5-membered monocyclic heterocycle represented by the partial structure (A-1). A ring heterocycle is more preferred.

  R represents a substituent. Although it does not specifically limit as a substituent, For example, halogen (for example, F, Cl, Br, I), an alkyl group (preferably C1-C30, more preferably C1-C20, especially preferably C1-C1). And examples thereof include a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, etc. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Pargyl group, 3-pentynyl group, etc.), aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl group, p -Methylphenyl group, naphthyl group, anthranyl group, pyridyl group, thiazole group, oxazole group, triazole group, etc.), alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, especially Preferably it is C1-C10, for example, a methoxy group, an ethoxy group, a benzyloxy group etc., an amino group (preferably C0-30, more preferably C0-20, especially preferably). The number of carbon atoms is 0 to 10, for example, methylamino group, ethylamino group, diethylamino group, diphenylamino group, methylphenyl An amino group, etc.), an acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as an acetyl group, a benzoyl group, a formyl group, A pivaloyl group, a trifluoromethylcarbonyl group, etc.), an alkylsulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonyl). Group, a trifluoromethanesulfonyl group, etc.), an arylsulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a phenylsulfonyl group) An alkoxycarbonyl group (preferably having a carbon number of 2 to 30, more preferably a carbon number). The number of carbon atoms is 2 to 20, particularly preferably 2 to 12, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group. ), An aminocarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as N, N-dimethylaminocarbonyl group, N, N-diethylcarbonyl group) Group), an aryloxycarbonyl group (preferably having a carbon number of 7 to 30, more preferably a carbon number of 7 to 20, particularly preferably a carbon number of 7 to 12, such as a phenyloxycarbonyl group). ), An alkoxysulfonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxysulfonyl group and an ethoxysulfonyl group). An aminosulfonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms); , For example, N, N-dimethylaminosulfonyl group, N, N sulfonyl group, etc.), non-aromatic heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, a piperidyl group, a morpholino group, and the like, a cyano group, and a silyl group (preferably having 3 to 40 carbon atoms). More preferably, it has 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group. These substituents may be further substituted.

  R is preferably halogen, alkyl group, aryl group, acyl group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group, alkylthio group, alkylsulfonyl group, arylsulfonyl group, aminosulfonyl group, amino group, and alkoxy group , An alkoxycarbonyl group, an aminocarbonyl group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, an aminosulfonyl group, and an amino group, and more preferably an alkoxy group, an alkylthio group, an alkylsulfonyl group, and an amino group. Of these, an alkylthio group and an alkylsulfonyl group are particularly preferable.

  n represents an integer in the range of 0 to 4, preferably an integer in the range of 0 to 3, more preferably an integer in the range of 0 to 2, and even more preferably 1 or 2. When n is an integer of 2 or more, a plurality of R may be the same as or different from each other. From the viewpoint of solubility, film stability (hardness of crystallization) and the like, n is particularly preferably 1.

  M represents a metal ion or a metal oxide ion. Examples of metal ions include Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Sr, Y, Zr, Nb, and Mo. , Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Ba, Pr, Eu, Yb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi And metal ions such as Th, and transition metal ions are preferred. The transition metal is an element having an incomplete d electron shell, and includes elements of Group IIIa to Group VIII and Group Ib of the periodic table. The transition metal ions are not particularly limited, but ions of Cr, Mn, Fe, Co, Ni, Cu, and Zn are preferable, ions of Fe, Co, Ni, Cu, and Mn are more preferable, Fe, Co, Ni, and Mu ions are more preferable, and Fe ions are particularly preferable.

As the metal ion, a divalent or trivalent metal ion is preferable, and a divalent metal ion is more preferable. Examples of the divalent or trivalent metal ions include Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Ni ²⁺ , Ni ³⁺ , Cu ²⁺ , Zn ²⁺ and Cr. ³⁺ , Ru ²⁺ , Rh ³⁺ , Pd ²⁺ , Ir ³⁺ , Pt ²⁺ , Re ^{+ and the} like, Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Ni ²⁺ , Ni ³⁺ , Cu ²⁺ , Zn ²⁺ are preferable, Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Co ³⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ are more preferable, and Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Ni ²⁺ , Ni ³⁺ , and Mn ²⁺ are more preferable. Fe ²⁺ and Fe ³⁺ are particularly preferable from the viewpoint of environmental hazards and effects on the human body. When the valence of the metal ion is 3+, the charge is not neutralized by the ligand, so a counter anion is present. The counter anion is not particularly limited.

  The metal complex compound represented by the general formula (1) is preferably a metal complex compound represented by the following general formula (2).

Below, general formula (2) is demonstrated.
In General Formula (2), Q ³ and Q ⁴ each independently represent an atomic group that forms a ring represented by the following partial structure (A-1) or (A-2).

In the above formula, * represents the bonding position with the N atom to which the ring is bonded. Q ³ and Q ⁴ heterocyclic 5-membered monocyclic ring form is preferably a 5-membered monocyclic hetero ring represented by the partial structure (A-1).

R ¹ and R ² each independently represents a hydrogen atom or a substituent. R ¹ is preferably a hydrogen atom, and R ² is preferably a substituent. Examples of the substituent include the substituents exemplified for R in the general formula (1).

R ² is preferably an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an alkylthio group or an amino group, more preferably an alkyl group, an alkoxycarbonyl group or an alkylthio group, and an alkyl group or an alkylthio group. More preferably, it is more preferably an alkyl group. Among the alkyl groups, a tertiary alkyl group is particularly preferable, and a tert-butyl group is most preferable.

  In general formula (2), R, M, and n have the same definitions as in general formula (1), and specific examples and preferred examples are also the same.

  In general formula (1) and general formula (2), the dotted line connecting M and N atoms represents a coordination bond, but the number of coordination bonds as a whole molecule is missing, resulting in a coordination bond. Even if the number is two or three, it is included in the compounds represented by the general formula (1) and the general formula (2).

  Specific examples of the metal complex compound represented by the general formula (1) and the general formula (2) are shown below. However, the present invention is not limited to the following specific examples.

  As a general synthesis method of the ligand of the metal complex compound represented by the general formula (1) and the metal complex compound represented by the general formula (2), J. Org. Chem., Vol. 42, No. 11, (1977) and the method described in WO2005-068459. However, it is not limited to these. As a method of obtaining a metal complex compound by reacting the obtained ligand with a metal compound, the metals described in JP-A-11-130970, JP-A-11-310728, and JP-A-2001-158862 are used. Examples include the same method as the synthesis method of the azo chelate dye. However, it is not limited to this, Other metal salt may be used and another reaction solvent may be used. Moreover, it can confirm that the target metal complex compound was synthesize | combined by well-known methods, such as NMR and mass spectrometry.

  Below, an example of the synthesis | combining method of the compound represented by General formula (2) is shown. However, the synthesis method of the metal complex compound represented by the general formula (2) is not limited to the method shown below.

The metal complex compound represented by the general formula (1) can exhibit excellent thermal decomposability, thereby providing an optical information recording medium having good recording characteristics. As an index of thermal decomposability, the thermal decomposition temperature can be used. The metal complex compound represented by the general formula (1) may have a thermal decomposition temperature of 200 to 400 ° C., for example. Furthermore, the metal complex compound represented by the general formula (2) can preferably have a thermal decomposition temperature of 230 to 370 ° C, more preferably 250 to 350 ° C. In addition, the thermal decomposition temperature in this invention shall say the value calculated | required by TG / DTA measurement. Specifically, for example, using an EXSTAR6000 manufactured by Seiko Instruments Inc., the temperature was raised at 10 ° C./min in the range of 30 ° C. to 550 ° C. under an N ₂ air flow (flow rate 200 ml / min), and the mass reduction rate was 10%. The thermal decomposition temperature can be obtained as the temperature at the time when the temperature reaches the value.

  The optical information recording medium of the present invention has a recording layer containing a metal complex compound represented by the general formula (1) on a substrate. The recording layer may contain one type of dye represented by the general formula (1), or may contain two or more types. The content of the metal complex compound represented by the general formula (1) in the recording layer is, for example, in the range of 1 to 100% by mass, preferably 70 to 100% by mass with respect to the total mass of the recording layer. It is a range, More preferably, it is the range of 80-100 mass%, Most preferably, it is the range of 90-100 mass%.

  The optical information recording medium of the present invention only needs to have at least one recording layer containing a metal complex compound represented by the general formula (1) on the substrate, and may have two or more recording layers. Alternatively, it is possible to have a recording layer other than the recording layer containing the metal complex compound represented by the general formula (1). In the recording layer containing the metal complex compound represented by the general formula (1), when another dye is used in combination as a recording dye, the ratio of the metal complex compound represented by the general formula (1) to the total dye component is: It is preferable that it is 70-100 mass%, and it is still more preferable that it is 80-100 mass%.

  In the present invention, when a dye other than the metal complex compound represented by the general formula (1) is used as the dye component, the dye preferably has an absorption in a short wavelength region of, for example, a wavelength of 440 nm or less. Examples of such dyes include, but are not limited to, azo dyes, azo metal complex dyes, phthalocyanine dyes, oxonol dyes, and cyanine dyes.

  In the optical information recording medium of the present invention, the recording layer containing the metal complex compound represented by the general formula (1) is a layer capable of recording information by laser light irradiation. Here, recording of information by laser light irradiation means that the portion of the recording layer irradiated with the laser light changes its optical characteristics. The change in the optical properties is caused by the portion of the recording layer irradiated with the laser light absorbing the light and locally raising the temperature, causing a physical or chemical change (for example, generation of pits). It is thought that. Reading (reproduction) of information recorded on the recording layer is not changed from a portion (recording portion) where the optical characteristics of the recording layer are changed by irradiating laser light having the same wavelength as that of the recording laser light, for example. This can be done by detecting a difference in optical characteristics such as reflectance from the portion (unrecorded portion). The metal complex compound represented by the general formula (1) has absorptivity with respect to a laser beam having a wavelength of 440 nm or less, for example. As described above, the optical information recording medium of the present invention having a recording layer containing a metal complex compound having an absorptivity in a short wavelength region can be recorded by a short wavelength laser such as a Blu-ray optical disk using a 405 nm blue laser. It is suitable as a large-capacity optical disk. The method for recording information on the optical information recording medium of the present invention will be described later.

  The optical information recording medium of the present invention has a recording layer containing at least a metal complex compound represented by the general formula (1) on a substrate. Further, in addition to the recording layer, a light reflecting layer, a protective layer, etc. Can also be included.

As the substrate used in the present invention, various materials used as substrate materials for conventional optical information recording media can be arbitrarily selected and used.
Specifically, glass; acrylic resin such as polycarbonate and polymethyl methacrylate; vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer; epoxy resin; amorphous polyolefin; polyester; metal such as aluminum; These may be used together if desired.
Among the materials, thermoplastic resins such as amorphous polyolefin and polycarbonate are preferable, and polycarbonate is particularly preferable from the viewpoints of moisture resistance, dimensional stability, and low price. When these resins are used, the substrate can be manufactured by injection molding.
The thickness of the substrate is generally in the range of 0.7 to 2 mm, preferably in the range of 0.9 to 1.6 mm, and more preferably 1.0 to 1.3 mm.
An undercoat layer can also be formed on the surface of the substrate on the side where the light reflecting layer, which will be described later, is provided for the purpose of improving flatness and adhesion.

  The surface on which the recording layer of the substrate is formed is usually provided with unevenness (pregroove) representing information such as tracking guide grooves or address signals. In order to achieve a higher recording density, the optical information recording medium of the present invention preferably uses a substrate on which a narrower track pitch is formed than CD-R and DVD-R. Details such as a preferable range of the track pitch will be described later.

  Preferred embodiments of the optical information recording medium of the present invention include the following embodiments (1) and (2).

Aspect (1): Optical information recording medium having a write-once recording layer containing a dye and a cover layer having a thickness of 0.01 to 0.5 mm in order from the substrate side on a substrate having a thickness of 0.7 to 2 mm Aspect (2): Optical information having a write-once recording layer containing a dye and a protective substrate having a thickness of 0.1 to 1.0 mm in order from the substrate side on a substrate having a thickness of 0.1 to 1.0 mm. recoding media

  In aspect (1), it is preferable that the track pitch of the pregroove formed on the substrate is 50 to 500 nm, the groove width is 25 to 250 nm, and the groove depth is 5 to 150 nm. In aspect (2), the substrate It is preferable that the track pitch of the pregroove formed is 200 to 600 nm, the groove width is 50 to 300 nm, the groove depth is 30 to 150 nm, and the wobble amplitude is 5 to 50 nm.

[Optical Information Recording Medium of Aspect (1)]
The optical information recording medium of aspect (1) is an aspect having at least a substrate, a write-once recording layer, and a cover layer. A specific example of the optical information recording medium of aspect (1) is shown in FIG. A first optical information recording medium 10A shown in FIG. 1 has a first light reflecting layer 18, a first write-once recording layer 14, a barrier layer 20, and a first adhesive layer or a first adhesive on a first substrate 12. It has the layer 22 and the cover layer 16 in this order.
Below, the material which comprises these is demonstrated one by one.

In the substrate of the substrate mode (1), pregrooves (guide grooves) having a shape in which the track pitch, groove width (half width), groove depth, and wobble amplitude are all within the following ranges are formed. . This pre-groove is provided to achieve a higher recording density than CD-R and DVD-R. For example, the optical information recording medium of the present invention is used as a medium corresponding to a blue-violet laser. It is suitable for use.

  The track pitch of the pregroove is in the range of 50 to 500 nm, and the upper limit is preferably 420 nm or less, more preferably 370 nm or less, and further preferably 330 nm or less. Further, the lower limit is preferably 100 nm or more, more preferably 200 nm or more, and further preferably 260 nm or more. If the track pitch is 50 nm or more, the pregroove can be formed accurately, and the occurrence of crosstalk can be avoided. If the track pitch is 500 nm or less, high-density recording can be performed.

  The groove width (half width) of the pregroove is in the range of 25 to 250 nm, and the upper limit is preferably 240 nm or less, more preferably 230 nm or less, and further preferably 220 nm or less. Further, the lower limit is preferably 50 nm or more, more preferably 80 nm or more, and further preferably 100 nm or more. If the groove width of the pregroove is 25 nm or more, the groove can be sufficiently transferred at the time of molding, and further, an increase in error rate at the time of recording can be suppressed. Furthermore, it is possible to avoid the occurrence of crosstalk due to the spread of pits formed during recording.

  The groove depth of the pregroove is in the range of 5 to 150 nm, and the upper limit is preferably 85 nm or less, more preferably 80 nm or less, and further preferably 75 nm or less. Further, the lower limit is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 28 nm or more. If the groove depth of the pregroove is 5 nm or more, a sufficient recording modulation degree can be obtained, and if it is 150 nm or less, a high reflectance can be obtained.

In addition, the groove inclination angle of the pregroove is preferably 80 ° or less, more preferably 75 ° or less, still more preferably 70 ° or less, and particularly preferably 65 ° or less. preferable. Further, the lower limit value is preferably 20 ° or more, more preferably 30 ° or more, and further preferably 40 ° or more.
If the groove inclination angle of the pregroove is 20 ° or more, a sufficient tracking error signal amplitude can be obtained, and if it is 80 ° or less, the moldability is good.

In the write-once recording layer of write-once recording layer mode (1), a dye is dissolved in a suitable solvent together with a binder or the like or without using a binder, and a coating solution is prepared. Or after apply | coating on the light reflection layer mentioned later and forming a coating film, it can form by drying. Here, the write-once recording layer may be a single layer or a multilayer. In the case of a multilayer structure, the step of applying the coating liquid is performed a plurality of times.
The concentration of the dye 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, most preferably. It is the range of 0.5-3 mass%.

Solvents used for preparing the coating solution include, for example, 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. Amides such as dimethylformamide; hydrocarbons such as methylcyclohexane; ethers such as tetrahydrofuran, ethyl ether and dioxane; alcohols such as ethanol, n-propanol, isopropanol and n-butanol diacetone alcohol; 2,2,3,3- Fluorinated solvents such as tetrafluoro-1-propanol; glycol agents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether And the like can be given; le compound.
Solvents can be used alone or in combination of two or more in consideration of the solubility of the dye used. In the coating solution, various additives such as a binder, an antioxidant, a UV absorber, a plasticizer, and a lubricant may be added according to the purpose.

Examples of the coating 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.
At the time of application, the temperature of the coating solution is preferably in the range of 23 to 50 ° C, more preferably in the range of 24 to 40 ° C, and particularly preferably in the range of 23 to 50 ° C.

The thickness of the write-once recording layer is preferably 300 nm or less, more preferably 250 nm or less, even more preferably 200 nm or less, and 180 nm or less on the land (the convex portion in the substrate). It is particularly preferred. The lower limit is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and particularly preferably 7 nm or more.
The thickness of the write-once recording layer is preferably 400 nm or less, more preferably 300 nm or less, and even more preferably 250 nm or less on the groove (the concave portion in the substrate). The lower limit is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 25 nm or more.
Further, the ratio of the thickness of the write-once recording layer on the land / the thickness of the write-once recording layer on the groove is preferably 0.1 or more, more preferably 0.13 or more, and More preferably, it is 15 or more, and it is especially preferable that it is 0.17 or more. The upper limit is preferably less than 1, more preferably 0.9 or less, still more preferably 0.85 or less, and particularly preferably 0.8 or less.

  The write-once recording layer can contain various anti-fading agents in order to further improve the light resistance of the write-once recording layer. As the anti-fading agent, a singlet oxygen quencher is generally used.

The cover layer of the cover layer mode (1) is usually bonded on the write-once recording layer described above or on the barrier layer as shown in FIG. 1 via an adhesive or an adhesive.
The cover layer is not particularly limited as long as it is a transparent film, but is not limited to acrylic resins such as polycarbonate and polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers; epoxy resins; amorphous polyolefins Polyester; cellulose triacetate or the like is preferably used, and among them, polycarbonate or cellulose triacetate is more preferably used.
Note that “transparent” means that the transmittance is 80% or more with respect to light used for recording and reproduction.

Further, the cover layer may contain various additives as long as the effects of the present invention are not hindered. For example, a UV absorber for cutting light having a wavelength of 400 nm or less and / or a dye for cutting light having a wavelength of 500 nm or more may be contained.
Further, as the surface physical properties of the cover layer, it is preferable that the surface roughness is 5 nm or less for both the two-dimensional roughness parameter and the three-dimensional roughness parameter.
Further, from the viewpoint of the concentration of light used for recording and reproduction, the birefringence of the cover layer is preferably 10 nm or less.

The thickness of the cover layer can be appropriately determined according to the wavelength and NA of the laser light irradiated for recording and reproduction, but is within the range of 0.01 to 0.5 mm in the present invention. It is preferable that the thickness is in the range of 0.05 to 0.12 mm.
The total thickness of the cover layer and the layer made of an adhesive or a pressure-sensitive adhesive is preferably 0.09 to 0.11 mm, and more preferably 0.095 to 0.105 mm.
The light incident surface of the cover layer may be provided with a protective layer (hard coat layer 44 in the embodiment shown in FIG. 1) for preventing the light incident surface from being damaged when the optical information recording medium is manufactured. Good.

In order to bond the cover layer and the write-once recording layer or barrier layer, an adhesive layer or an adhesive layer can be provided between the two layers.
As the adhesive used for the adhesive layer, it is preferable to use a UV curable resin, an EB curable resin, a thermosetting resin or the like, and it is particularly preferable to use a UV curable resin.
When a UV curable resin is used as an adhesive, the UV curable resin may be used as it is or dissolved in an appropriate solvent such as methyl ethyl ketone or ethyl acetate to prepare a coating solution, which may be supplied from the dispenser to the barrier layer surface. . Further, in order to prevent warpage of the produced optical information recording medium, it is preferable to use a UV curable resin having a low curing shrinkage rate as the UV curable resin constituting the adhesive layer. Examples of such UV curable resins include UV curable resins such as “SD-640” manufactured by Dainippon Ink & Chemicals, Inc.

The method for forming the adhesive layer is not particularly limited, but a predetermined amount of adhesive is applied on the surface (bonded surface) of the barrier layer or write-once recording layer, and a cover layer is placed thereon, followed by spin coating. It is preferable that the adhesive is cured after being spread uniformly between the bonded surface and the cover layer.
The thickness of the adhesive layer is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.5 to 50 μm, and still more preferably in the range of 10 to 30 μm.

  As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer, for example, an acrylic-based, rubber-based, or silicon-based pressure-sensitive adhesive can be used. From the viewpoint of transparency and durability, an acrylic pressure-sensitive adhesive is preferred. As an acrylic adhesive, 2-ethylhexyl acrylate, n-butyl acrylate and the like are the main components, and in order to improve cohesion, short-chain alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate, It is preferable to use a copolymer of acrylic acid, methacrylic acid, an acrylamide derivative, maleic acid, hydroxylethyl acrylate, glycidyl acrylate, or the like that can be a crosslinking point with a crosslinking agent. The glass transition temperature (Tg) and the crosslinking density can be changed by appropriately adjusting the mixing ratio of the main component, the short chain component and the component for adding a crosslinking point and the kind of the component.

The method of forming the adhesive layer is not particularly limited, but after applying a predetermined amount of the adhesive uniformly on the surface of the barrier layer or write-once recording layer (bonded surface), and placing the cover layer thereon, It may be cured, or beforehand, a predetermined amount of pressure-sensitive adhesive is uniformly applied to one side of the cover layer to form a pressure-sensitive adhesive coating film, and the coating film is bonded to the surface to be bonded. It may be cured.
Moreover, you may use the commercially available adhesive film in which the adhesion layer was previously provided for the cover layer.
The thickness of the adhesive layer is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.5 to 50 μm, and still more preferably in the range of 10 to 30 μm.
The cover layer may be formed by spin coating using a UV curable resin.

The optical information recording medium of the other layer mode (1) may have other arbitrary layers in addition to the essential layers as long as the effects of the present invention are not impaired. As other optional layers, for example, a label layer having a desired image formed on the back surface of the substrate (the non-formation surface side opposite to the side on which the write-once recording layer is formed) or the substrate and write-once type A light reflection layer (details will be described later) provided between the recording layer, a barrier layer (details will be described later) provided between the write-once recording layer and the cover layer, the light reflection layer and the write-once recording layer, And an interface layer provided between the two. Here, the label layer can be formed using an ultraviolet curable resin, a thermosetting resin, a heat drying resin, or the like.
The essential and optional layers described above may be a single layer or a multilayer structure.

  In the optical information recording medium of aspect (1), a light reflecting layer is formed between the substrate and the write-once recording layer in order to increase the reflectivity with respect to the laser beam and to provide the function of improving the recording / reproducing characteristics. It is preferable.

The light reflecting layer can be formed on the substrate by, for example, vacuum deposition, sputtering, or ion plating with a light reflecting material having a high reflectance with respect to laser light.
The thickness of the light reflecting layer is generally in the range of 10 to 300 nm, and preferably in the range of 50 to 200 nm.
The reflectance is preferably 70% or more.

  As a light reflective material having a high reflectance, 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, Sn, Bi, and the like, and metal and semi-metal or stainless steel. These light reflecting materials may be used alone, or may be used in combination of two or more kinds or as an alloy. Among these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable. Particularly preferred is Au, Ag, Al or an alloy thereof, and most preferred is Au, Ag or an alloy thereof.

Barrier layer (intermediate layer)
In the optical information recording medium of aspect (1), it is preferable to form a barrier layer between the write-once recording layer and the cover layer as shown in FIG.
The barrier layer can be provided for improving the storage stability of the write-once recording layer, improving the adhesion between the write-once recording layer and the cover layer, adjusting the reflectivity, adjusting the thermal conductivity, and the like.
The material used for the barrier layer is not particularly limited as long as it is a material that transmits light used for recording and reproduction and can express the above functions. For example, in general, It is a material with low gas and moisture permeability and is preferably a dielectric.
Specifically, a material made of nitride, oxide, carbide, sulfide, etc. such as Zn, Si, Ti, Te, Sn, Mo, Ge is preferable. MoO ₂ , GeO ₂ , TeO, SiO ₂ , TiO ₂ , ZuO, SnO ₂ , ZnO—Ga ₂ O ₃ , Nb ₂ O ₅ and Ta ₂ O ₅ are preferred, and SnO ₂ , ZnO—Ga ₂ O ₃ , SiO ₂ , Nb ₂ O ₅ and Ta ₂ O ₅ are more preferred.

The barrier layer can be formed by a vacuum film forming method such as vacuum deposition, DC sputtering, RF sputtering, or ion plating. Among these, it is more preferable to use sputtering.
The thickness of the barrier layer is preferably in the range of 1 to 200 nm, more preferably in the range of 2 to 100 nm, and still more preferably in the range of 3 to 50 nm.

[Optical Information Recording Medium of Aspect (2)]
The optical information recording medium of aspect (2) has at least a substrate, a write-once recording layer, and a protective substrate, and is preferably a bonded optical information recording medium. The typical layer structure is as follows.
(1) The first layer configuration is a configuration in which a write-once recording layer, a light reflection layer, and an adhesive layer are sequentially formed on a substrate, and a protective substrate is provided on the adhesive layer.
(2) The second layer configuration is a configuration in which a write-once recording layer, a light reflection layer, a protective layer, and an adhesive layer are sequentially formed on a substrate, and a protective substrate is provided on the adhesive layer.
(3) The third layer configuration is a configuration in which a write-once recording layer, a light reflection layer, a protective layer, an adhesive layer, and a protective layer are sequentially formed on a substrate, and a protective substrate is provided on the protective layer.
(4) In the fourth layer configuration, a write-once recording layer, a light reflecting layer, a protective layer, an adhesive layer, a protective layer, and a light reflecting layer are sequentially formed on a substrate, and a protective substrate is provided on the light reflecting layer. It is a configuration.
(5) The fifth layer configuration is a configuration in which a write-once recording layer, a light reflection layer, an adhesive layer, and a light reflection layer are sequentially formed on a substrate, and a protective substrate is provided on the light reflection layer.
Note that the layer configurations (1) to (5) above are merely examples, and the layer configuration is not limited to the order described above, but may be partially replaced or may be partially omitted. The write-once recording layer may also be formed on the protective substrate side. In this case, an optical information recording medium capable of recording and reproducing from both sides is obtained. Furthermore, each layer may be composed of one layer or a plurality of layers.

  Of the above, the optical information recording medium of aspect (2) will be described in detail below, taking as an example a configuration having a write-once recording layer, a light reflection layer, an adhesive layer, and a protective substrate in this order from the substrate side. . A specific example of the optical information recording medium having the above configuration is shown in FIG. A second optical information recording medium 10B shown in FIG. 2 includes a second write-once recording layer 26, a second light reflecting layer 30, a second adhesive layer 32, and a protective substrate 28 on a second substrate 24. Have in order.

The substrate in the substrate mode (2) is formed with a pregroove (guide groove) having a shape in which all of the track pitch, groove width (half width), groove depth, and wobble amplitude are in the following ranges. . This pre-groove is provided to achieve a higher recording density than CD-R and DVD-R. For example, the optical information recording medium of the present invention is used as a medium corresponding to a blue-violet laser. It is suitable for use.

  The track pitch of the pregroove is in the range of 200 to 600 nm, and the upper limit value is preferably 450 nm or less, and more preferably 430 nm or less. The lower limit is preferably 300 nm or more, more preferably 330 nm or more, and still more preferably 370 nm or more. If the track pitch is 200 nm or more, the pregroove can be formed accurately, and further, the occurrence of crosstalk can be avoided. If the track pitch is 600 nm or less, high-density recording can be performed.

  The groove width (half width) of the pregroove is in the range of 50 to 300 nm, and the upper limit is preferably 290 nm or less, more preferably 280 nm or less, and further preferably 250 nm or less. Further, the lower limit value is preferably 100 nm or more, more preferably 120 nm or more, and further preferably 140 nm or more. If the groove width of the pregroove is 50 nm or more, the groove can be sufficiently transferred at the time of molding, and further, an increase in error rate at the time of recording can be suppressed. It is possible to avoid the occurrence of crosstalk due to the spread of, and to obtain a sufficient degree of modulation.

  The groove depth of the pregroove is in the range of 30 to 150 nm, and the upper limit is preferably 140 nm or less, more preferably 130 nm or less, and further preferably 120 nm or less. The lower limit is preferably 40 nm or more, more preferably 50 nm or more, and further preferably 60 nm or more. If the groove depth of the pregroove is 30 nm or more, a sufficient recording modulation degree can be obtained, and if it is 150 nm or less, a high reflectance can be obtained.

  The thickness of the substrate is generally in the range of 0.1 to 1.0 mm, preferably in the range of 0.2 to 0.8 mm, and more preferably in the range of 0.3 to 0.7 mm.

An undercoat layer can be formed on the surface of the substrate on the side where a write-once recording layer, which will be described later, is provided for the purpose of improving flatness and adhesion.
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, chlorosulfone. Polymer materials such as chlorinated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate; silane coupling agents And the like.
The undercoat layer is formed by dissolving or dispersing the above materials in an appropriate solvent to prepare a coating solution, and then applying this coating solution to the substrate surface by a coating method such as spin coating, dip coating, or extrusion coating. can do.
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.

Details regarding the write-once recording layer in the write-once recording layer aspect (2) are the same as those of the write-once recording layer in aspect (1).

In the light reflection layer mode (2), a light reflection layer can be formed on the write-once recording layer in order to increase the reflectivity with respect to the laser light and to provide the function of improving the recording / reproducing characteristics. Details regarding the light reflecting layer of the aspect (2) are the same as those of the light reflecting layer of the aspect (1).

In the adhesive layer mode (2), an adhesive layer may be provided between the light reflecting layer and the protective substrate in order to improve the adhesion between the light reflecting layer and the protective substrate described later.
As a material constituting the adhesive layer, a photo-curing resin is preferable, and among them, a material having a small curing shrinkage rate is preferable in order to prevent warping of the disk. Examples of such a photocurable resin include UV curable resins (UV curable adhesives) such as “SD-640” and “SD-661” manufactured by Dainippon Ink.
Further, the thickness of the adhesive layer is preferably in the range of 1 to 1000 μm in order to give elasticity.

The protective substrate (dummy substrate) in the protective substrate mode (2) can be made of the same material and the same shape as the substrate described above. The thickness of the protective substrate is generally in the range of 0.1 to 1.0 mm, preferably in the range of 0.2 to 0.8 mm, and preferably in the range of 0.3 to 0.7 mm. More preferred.

Depending on the layer structure of the optical information recording medium of the protective layer mode (2), a protective layer may be provided for the purpose of physically and chemically protecting the light reflecting layer, the write-once recording layer, and the like.
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.
The protective layer can be formed, for example, by bonding a film obtained by plastic extrusion onto the light reflecting layer via an adhesive. Moreover, you may provide by methods, such as vacuum evaporation, sputtering, and application | coating.

Further, when a thermoplastic resin or a thermosetting resin is used as the protective layer, it is also formed by dissolving these in an appropriate solvent to prepare a coating solution, and then applying and drying the coating solution. be able to. When forming a protective layer using a UV curable resin, after preparing the coating solution by dissolving the UV curable resin as it is or in an appropriate solvent, the coating solution is applied and irradiated with UV light. It can also be formed by curing. 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 information recording medium of the other layer mode (2) may have other arbitrary layers in addition to the above layers as long as the effects of the present invention are not impaired. The details of the other optional layers are the same as those of the other layers in the aspect (1).

  Furthermore, the present invention relates to a method for recording information on an optical information recording medium having a recording layer on a substrate. In the information recording method of the present invention, information is recorded on the recording layer containing the metal complex compound represented by the general formula (1) by irradiating the optical information recording medium of the present invention with laser light.

Information is recorded on the optical information recording medium of the above-described preferred embodiment (1) or embodiment (2), for example, as follows.
First, while rotating the optical information recording medium at a constant linear velocity (for example, 0.5 to 10 m / sec) or a constant angular velocity, recording light such as semiconductor laser light is irradiated from the substrate side or the protective layer side. By this light irradiation, the optical characteristics of the laser light irradiated portion change and information is recorded. In the embodiment shown in FIG. 1, a recording laser beam 46 such as a semiconductor laser beam is irradiated from the cover layer 16 side through a first objective lens 42 (for example, a numerical aperture NA is 0.85). By the irradiation of the laser beam 46, the write-once recording layer 14 absorbs the laser beam 46 and the temperature rises locally, causing a physical or chemical change (for example, generation of pits) to change its optical characteristics. Thus, it is considered that information is recorded. Similarly, in the embodiment shown in FIG. 2, a recording laser beam 46 such as a semiconductor laser beam is irradiated from the second substrate 24 side through a second objective lens 48 having a numerical aperture NA of, for example, 0.65. By the irradiation of the laser beam 46, the second write-once recording layer 26 absorbs the laser beam 46 and the temperature rises locally, causing a physical or chemical change (for example, generation of pits) to change its optical characteristics. By changing, it is considered that information is recorded.

  In the present invention, it is preferable to record information by irradiating a laser beam having a wavelength of 440 nm or less. As the recording light, a semiconductor laser light having an oscillation wavelength in the range of 440 nm or less is preferably used. As a preferable light source, a blue-violet semiconductor laser light having an oscillation wavelength in the range of 390 to 415 nm, an infrared having a central oscillation wavelength of 850 nm is used. A blue-violet SHG laser beam having a central oscillation wavelength of 425 nm, which is a half wavelength of the semiconductor laser beam using an optical waveguide device, can be mentioned. In particular, it is preferable to use a blue-violet semiconductor laser beam having an oscillation wavelength in the range of 390 to 415 nm in terms of recording density. The information recorded as described above is reproduced by irradiating a semiconductor laser beam from the substrate side or the protective layer side while rotating the optical information recording medium at the same constant linear velocity as above and detecting the reflected light. Can be performed.

Recording of information on the recording layer in the present invention is preferably performed by forming voids (pits) in the portion of the recording layer irradiated with the laser beam. In the optical information recording medium of the aspect (1) described above, when information is recorded by forming a gap, an aspect having an adhesive layer between the barrier layer and the cover layer can perform good recording. When the pressure-sensitive adhesive layer is changed to an adhesive layer, the recording characteristics may be deteriorated. This is considered to be due to the following reasons.
Usually, the formation of voids by laser light irradiation is accompanied by deformation of the recording layer. Therefore, if the deformation of the recording layer is hindered, the voids are not formed satisfactorily, which is considered to cause a decrease in recording characteristics. In an optical information recording medium having a light reflecting layer, a recording layer, a barrier layer, an adhesive layer and a cover layer in this order on the substrate, the substrate and the light reflecting layer have higher rigidity than the adhesive layer and the barrier layer. Therefore, when a void is formed, the recording layer pushes up the barrier layer, causing a concave deformation in the adhesive layer. In this case, the formation of pits can be performed satisfactorily without preventing the formation of voids.
On the other hand, the adhesive layer is generally harder and less flexible than the adhesive layer. Therefore, in an optical information recording medium having a light reflecting layer, a recording layer, an adhesive layer, a barrier layer, and a cover layer in this order on the substrate, the recording layer cannot be deformed to the adhesive layer side, preventing the formation of voids. May be. Therefore, it is considered that it may be difficult to obtain good recording characteristics in an embodiment having an adhesive layer.
On the other hand, the recording layer containing the metal complex compound represented by the general formula (1) can satisfactorily form voids by laser light irradiation even in an optical information recording medium having a relatively rigid adhesive layer.

  Furthermore, this invention relates to the metal complex compound represented by following General formula (3).

In the general formula (3), Q ³ and Q ⁴ each independently represent an atomic group forming a ring represented by the following partial structure (A-1), and R, M, and n are each represented by the general formula ( It is synonymous with the definition in 1).

In the above formula, * represents the bonding position with the N atom to be bonded, and R ¹ and R ² each independently represent a hydrogen atom or a substituent.

The metal complex compound of the present invention has the above partial structure (A-1) as Q ³ and Q ⁴ in the metal complex compound represented by the general formula (2) described above. The metal complex compound of the present invention can be used in various applications such as pigments, photographic materials, UV absorbing materials, laser dyes, color filter dyes, and color conversion filters. Preferably, it is used as a recording layer dye in an optical information recording medium having a dye-containing recording layer. The details of the metal complex compound of the present invention and the method of using the same are as described above.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

Example 1: Synthesis of Exemplified Compound (M-1) (I) Synthesis of Ligand (1)

A 100 ml eggplant flask was charged with 1 g of compound (1), 1.41 g of compound (2), 58 mg of CaCl ₂ and 20 ml of 1-hexanol, and heated to reflux for 5 hours. The crystals that were returned to room temperature were filtered off, and the solvent of the filtrate was distilled off under reduced pressure. Purification was performed on a silica gel column using ethyl acetate / hexane = 1/4 (volume ratio) as an eluent, and dried to obtain 720 mg of ligand (1).

The compound was identified by 300 MHz ¹ H-NMR. The results are shown below. ¹ H-NMR (CDCl ₃ ) [ppm]; δ 8.40 (d, 1H), 8.30 (d, 1H), 6.13 (s, 1H), 6.07 (s, 1H), 4.63-4.53 (m, 1H), 2.16-2.00 (m, 1H), 1.77-1.62 (m, 1H), 1.40 (s, 18H), 1.33 (d, 3H), 1.06 (t, 3H)

(II) Synthesis of exemplary compound (M-1)

Next, 590 mg of ligand (1) and 10 ml of methanol were placed in a 50 ml eggplant flask, and 126 mg of FeCl ₂ .4H ₂ O was added with stirring, and the mixture was heated to reflux for 3 hours. Distilled water (50 ml) was added, the temperature was returned to room temperature, the precipitate was filtered, washed with distilled water and dried to obtain 410 mg (M-1). The compound was identified by MALDI-TOF-MS. The result was [M−H ⁺ ] = 1078.

Example 2: Synthesis of exemplary compound (M-2) 0.4 g of ligand (1) synthesized by the same method as in Example 1 and 10 ml of methanol were placed in a 50 ml eggplant flask and Ni (OAc) _{2 was} stirred. · 4H ₂ O 0.1 g was added and refluxed under heating for 3 hours. 50 ml of distilled water was added, the temperature was returned to room temperature, the precipitate was filtered, washed with distilled water and dried to obtain 300 mg (M-2). The compound was identified by MALDI-TOF-MS. The result was [M−H ⁺ ] = 1081.

Example 3 Synthesis of Exemplary Compound (M-5) Into a 50 ml eggplant flask, 0.4 g of the ligand (1) synthesized by the same method as in Example 1 and 10 ml of methanol were placed, and Co (OAc) _{2 was} stirred. · 4H ₂ O 0.1 g was added and refluxed under heating for 3 hours. 50 ml of distilled water was added, the temperature was returned to room temperature, the precipitate was filtered, washed with distilled water, and dried (M-5) to obtain 300 mg. The compound was identified by MALDI-TOF-MS. The result was [M−H ⁺ ] = 1081.

Example 4: Synthesis of Exemplified Compound (M-6) 0.4 g of ligand (1) synthesized by the same method as in Example 1 and 10 ml of methanol were placed in a 50 ml eggplant flask, and Mn (OAc) _{2 was} stirred. · 4H ₂ O 0.1 g was added and refluxed under heating for 3 hours. 50 ml of distilled water was added, the temperature was returned to room temperature, the precipitate was filtered, washed with distilled water and dried (M-6) to obtain 0.3 g. The identity of the compound was confirmed by MALDI-TOF-MS. The result was [M−H ⁺ ] = 1077.

Example 5: Synthesis of exemplary compound (M-9) (I) Synthesis of ligand (2)

A 100 ml eggplant flask was charged with 1 g of compound (3), 1.5 g of compound (2), 50 mg of CaCl ₂ and 20 ml of 1-hexanol, and heated to reflux for 5 hours. The crystals that were returned to room temperature were filtered off, and the solvent of the filtrate was distilled off under reduced pressure. Purification was performed on a silica gel column using ethyl acetate / hexane = 1/4 (volume ratio) as an eluent, and dried to obtain 0.6 g of ligand (2). The compound was identified by MALDI-TOF-MS. The result was [M−H ⁺ ] = 507.

(II) Synthesis of Exemplified Compound (M-9) 0.4 g of Ligand (2) and 10 ml of methanol were placed in a 50 ml eggplant flask, and 0.1 g of FeCl ₂ .4H ₂ O was added with stirring for 1 hour under reflux. I let you. Distilled water (50 ml) was added, the temperature was returned to room temperature, the precipitate was filtered, washed with distilled water and dried (M-9) to obtain 0.3 g. The compound was identified by MALDI-TOF-MS. The result was [M−H ⁺ ] = 1066.

Example 6: Production of optical information recording medium (production of substrate)
Thickness 1.1 mm, outer diameter 120 mm, inner diameter 15 mm, spiral pre-groove (track pitch: 320 nm, groove width: on-groove width 140 nm, groove depth: 45 nm, groove inclination angle: 65 °, wobble amplitude: 20 nm) An injection-molded substrate made of a polycarbonate resin was prepared. Mastering of the stamper used at the time of injection molding was performed using laser cutting (351 nm).

(Formation of light reflection layer)
An ANC light reflecting layer (Ag: 98.1 at%, Nd: 0.7 at%, as a vacuum film-forming layer having a film thickness of 100 nm was formed on the substrate by DC sputtering in an Ar atmosphere using Cube manufactured by Unaxis. Cu: 0.9 at%) was formed. The film thickness of the light reflecting layer was adjusted by the sputtering time.

(Formation of write-once recording layer)
2 g of the exemplified compound (M-1) synthesized in Example 1 was added and dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a dye-containing coating solution. And the prepared pigment | dye containing coating liquid was apply | coated on the conditions of 23 degreeC and 50% RH, changing the rotation speed to 300-4000 rpm with a spin coat method on the light reflection layer. Then, it was stored at 23 ° C. and 50% RH for 1 hour to form a write-once recording layer (thickness on the groove of 40 nm, thickness on the land of 15 nm).

  After the write-once recording layer was formed, annealing treatment was performed in a clean oven. The annealing treatment was performed by supporting the substrate on a vertical stack pole while leaving a gap with a spacer, and holding at 80 ° C. for 1 hour.

(Formation of barrier layer)
Thereafter, on the write-once recording layer, a Cubes made by Unaxis is used and made of ZnO—Ga ₂ O ₃ (ZnO: Ga ₂ O ₃ = 3: 7 (mass ratio)) by RF sputtering in an Ar atmosphere. A barrier layer having a thickness of 5 nm was formed.

(Covering the cover layer)
As the cover layer, a polycarbonate film (Teijin Pure Ace, thickness: 80 μm) having an inner diameter of 15 mm and an outer diameter of 120 mm and having an adhesive layer (glass transition temperature of −30 ° C.) on one side is used. The total thickness was set to 100 μm.
Then, the cover layer was placed on the barrier layer so that the barrier layer and the adhesive layer were in contact with each other, and then the cover layer was pressed and pressed with a pressing member. Through the above steps, an optical information recording medium having the layer structure shown in FIG. 1 was produced.

Comparative Examples 1 to 5: Production of optical information recording medium The same method as in Example 2 except that the comparative compound shown in Table 1 was used instead of the exemplified compound (M-1) as the dye used in the write-once recording layer. Optical information recording media of Comparative Examples 1 to 5 were produced.

<Evaluation of optical information recording media>
(1) C / N (carrier-to-noise ratio) evaluation The produced optical information recording medium was recorded using a recording / reproduction evaluation machine (manufactured by Pulstec: DDU1000) loaded with a 403 nm laser and NA 0.85 pickup. A signal (2T) of 0.16 μm was recorded at a linear velocity of 4.92 m / s, and the recorded pits were reproduced with a spectrum analyzer (FSP-3 type manufactured by Rohde & Schwartz). The 16 MHz output after recording was defined as Carrier output, the 16 MHz output before recording was defined as Noise output, and the output after recording−the output before recording was defined as the C / N value. Recording was done on the groove. The recording power was 7 mW and the reproducing power was 0.3 mW. The results are shown in Table 1.

(2) Light resistance evaluation The optical information recording medium after the evaluation in (1) above was subjected to xenon light using a light resistance tester (FAL-25AX-HCBECL type, using quartz + # 275 filter, manufactured by Suga Test Instruments Co., Ltd.). Were recorded for 55 hours, and the recorded pits were reproduced again with a spectrum analyzer (FSP-3, manufactured by Rohde & Schwartz). The 16 MHz output after recording was defined as Carrier output, the 16 MHz output before recording was defined as Noise output, and the output after recording−the output before recording was defined as the C / N value. The results are shown in Table 1.

<Light resistance evaluation of dye film>
The same pigment-containing coating solution as in Example 2 and Comparative Examples 1 to 5 was prepared, and the prepared pigment-containing coating solution was changed to a rotational speed of 500 to 1000 rpm by a spin coating method on a glass plate having a thickness of 1.1 mm. The coating was performed under the conditions of 23 ° C. and 50% RH. Then, after storing at 23 ° C. and 50% RH for 24 hours, a light resistance test was performed using a merry-go-round type light resistance tester (manufactured by Eagle Engineering Co., Ltd., cell test machine type III, with Schott WG320 filter). With respect to the dye film immediately before the light resistance test and the dye film after 48 hours of the light resistance test, the absorption spectrum of the dye film was measured using UV-1600PC (manufactured by SHIMADZU), and the change in absorbance at the maximum absorption wavelength was read.

<Measurement of thermal decomposition temperature>
TG / DTA measurement was performed on the exemplary compound (M-1) and the comparative compounds (A) to (E). Measurements were taken from Seiko Instruments Inc. Using EXSTAR6000 manufactured, the temperature was raised at 10 ° C./min in the range of 30 ° C. to 550 ° C. under N ₂ air flow (flow rate 200 ml / min). The temperature when the weight loss rate reached 10% was read, and the results are shown in Table 1.

＊＊＊Xe光照射４８時間後の色素残存率が９０％以上のときが◎、８０％以上９０％未満のときが○、７０％以上８０％未満のときが△、７０％未満のときは×。

*** When the dye residual ratio after 90 hours of Xe light irradiation is 90% or more, ◎, when 80% or more and less than 90%, ◯, when 70% or more and less than 80%, and when less than 70% X.

  As shown in Table 1, Exemplified Compound (M-1) had good solubility and was able to form a dye film satisfactorily. In addition, the dye film formed using the exemplary compound (M-1) had better light resistance than the dye films formed using the comparative compounds (A) to (E). Furthermore, the optical information recording medium of Example 2 had good recording characteristics (C / N) before and after irradiation with Xe light. The high recording characteristics of the optical information recording medium of Example 2 are considered to be due to the low thermal decomposition temperature (high thermal decomposition) of the exemplified compound (M-1) contained in the recording layer. Further, a high C / N ratio after Xe light irradiation indicates that the recording layer has high light resistance.

  Moreover, it replaces with exemplary compound (M-1), and the same evaluation is performed using exemplary compound (M-2), (M-4), (M-5), (M-9), and (M-22). As in the case of Exemplified Compound (M-1), good solubility and light resistance and good recording characteristics were obtained.

  According to the present invention, it is possible to provide an optical information recording medium having both excellent light resistance and recording characteristics. The optical information recording medium of the present invention is suitable as an information recording medium for recording / reproducing with a blue laser beam of 440 nm or less.

It is a schematic sectional drawing which shows an example of the optical information recording medium of this invention. It is a schematic sectional drawing which shows an example of the optical information recording medium of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10A ... 1st optical information recording medium 10B ... 2nd optical information recording medium 12 ... 1st board | substrate 14 ... 1st write-once recording layer 16 ... cover layer 18 ... 1st light reflection layer 20 ... Barrier layer 22 ... 1st adhesion layer 24 ... Second substrate 26 ... Second write-once recording layer 28 ... Protective substrate 30 ... Second light reflecting layer 32 ... Second adhesive layer 44 ... Hard coat layer

Claims (10)

An optical information recording medium having a recording layer on a substrate, wherein the recording layer contains a metal complex compound represented by the following general formula (1).

[In the general formula (1), Q ¹ and Q ² each independently form a 5-membered monocyclic hetero ring except 1,3-thiazole, 1,3,4-thiadiazole and 1,3,4-triazole. M represents a metal ion or a metal oxide ion, R represents a substituent, and n represents an integer in the range of 0-4. When n is an integer of 2 or more, a plurality of R may be the same as or different from each other. ] The optical information recording medium according to claim 1, wherein the metal complex compound represented by the general formula (1) is a metal complex compound represented by the following general formula (2).

[In General Formula (2), Q ³ and Q ⁴ each independently represent an atomic group forming a ring represented by the following partial structure (A-1) or (A-2), and R, M and n is synonymous with the definition in General formula (1), respectively. ]

[In the above formula, * represents the bonding position with the N atom to be bonded, and R ¹ and R ² each independently represents a hydrogen atom or a substituent. ] The optical information recording medium according to claim 1, wherein the M is an iron ion. The optical information recording medium according to any one of claims 1 to 3, further comprising a light reflecting layer, the recording layer, a barrier layer, an adhesive layer or an adhesive layer, and a cover layer in this order on the substrate. The said board | substrate has a pregroove with a track pitch of 50-500 nm on at least one surface, and has the said recording layer on the surface in which the said pregroove was formed. Optical information recording medium. The optical information recording medium according to claim 1, wherein the recording layer is a layer capable of recording information with a laser beam having a wavelength of 440 nm or less. An information recording method for recording information on an optical information recording medium having a recording layer on a substrate,
The optical information recording medium is the optical information recording medium according to any one of claims 1 to 6,
An information recording method for recording the information on the recording layer by irradiating the optical information recording medium with laser light. The information recording method according to claim 7, wherein a wavelength of the laser beam is 440 nm or less. A metal complex compound represented by the following general formula (3).

[In General Formula (3), Q ³ and Q ⁴ each independently represent an atomic group forming a ring represented by the following partial structure (A-1), and R, M and n are each a general formula It is synonymous with the definition in (1). ]

[In the above formula, * represents the bonding position with the N atom to be bonded, and R ¹ and R ² each independently represents a hydrogen atom or a substituent. ] A method of using the metal complex compound according to claim 9 as the recording layer dye in an optical information recording medium having a dye-containing recording layer.

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