JP2982925B2 - Optical recording method and reproduction method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recording / reproducing information on / from an optical recording medium capable of performing recording with high sensitivity and excellent contrast.

[0002]

2. Description of the Related Art Conventionally, as a method of performing recording using light, for example, “Optical Engineering (Op Op.
physical Engineering), Vol. Fifteen
No. 2 March-April 1976, p.
p99-"Review and Analysis"
of Optical Recording Media
a), a type in which a recording layer of an optical recording medium is irradiated with a light beam, for example, a laser beam, to cause deformation or holes in the recording layer, a type in which a bubble is formed, and an optical type. Types and the like that change characteristics are known.

[0003] For example, as an optical recording medium of a type in which recording is performed by deforming a recording layer, low melting point metals such as Te, Bi, Sn, Sb, and In, cyanine-based, squarium-based, and the like are formed on a substrate. Dyes and pigments (organic dyes) such as phthalocyanine, tetradehydrocholine, polymethine, naphthoquinone, and benzenedithiol nickel complex;
And a composite thin film with these organic dyes.

An optical recording layer composed of these thin films is irradiated with a light beam, converted into thermal energy in accordance with the absorptance, and the recording layer is dissolved or sublimated by the heat mode to form recording pits.

In recent years, among the above-mentioned recording layer materials,
Organic dyes have attracted attention because they can provide inexpensive optical recording media. That is, a dye recording medium can be formed as a recording layer on a substrate by a solvent coating method, and is more excellent in mass productivity than a low melting point metal compound formed by a vacuum evaporation method.

In a recording pit portion of an optical recording medium using an organic dye for a recording layer, the reflectance decreases due to decolorization due to thermal decomposition of the organic dye, and the recording pit is reduced due to the effect of optical scattering due to deformation of the recording pit portion. Since the reflected light amount of the information reproducing laser beam in the section changes, the recorded information can be detected.

However, an organic dye generally used as a recording light source and having an absorption characteristic on a long wavelength side which is an oscillation wavelength of a semiconductor laser, has a wavelength of 830 nm for performing recording having a sufficient S / N ratio. The recording sensitivity is required to be 100 mJ / cm ² or more for the laser of the wavelength, and to record at high speed to increase the data transfer speed, a laser beam with a higher output is required, and the durability and compatibility of the hardware In consideration of this, it is necessary to increase the sensitivity of the recording medium.

An optical card having a card-like outer shape in an optical recording medium is an ISO (International).
Organization for Standard
The thickness of 0.74 to 0.76 mm is required from the standard of i. On the other hand, in order to reduce the influence of dust and scratches on the substrate surface of the optical recording medium, it is advantageous that the thickness of the substrate is as large as possible, usually 0.4 to 0.6 m.
A thickness of about m is suitable. The protective substrate is 0.15
A thickness of about 0.4 mm is required. Therefore, in order to obtain an optical card medium having the above thickness, an air gap structure in which a hollow portion having a thickness of about 0.5 to 1 mm is provided on a recording layer provided on a substrate, and a protective substrate is laminated thereon. It is difficult to do. Therefore, in a thin optical recording medium such as an optical card, it is necessary to have a close contact structure in which a protective layer is laminated on a recording layer via an adhesive layer.

However, when optical recording is performed on an optical recording medium having a close contact structure using a laser light source, heat generated by irradiation of laser light is applied to the close contact structure portion as compared with an optical recording medium having a hollow structure. Due to the structure that is rapidly diffused and adhered, the thermal deformation of the recording pit formed by the irradiation of the laser beam is suppressed, and the thermal decomposition of the dye recording medium and the like is also suppressed. As a result, the recording sensitivity of the optical recording medium having the contact structure is reduced to 1/3 to 1/5 as compared with the optical recording medium having the hollow structure.

In order to solve such a problem, the present applicant disclosed in Japanese Patent Application Laid-Open No. 62-239,637 a method in which a recording layer contains an organic dye and a free-radical-generating compound which generates radicals by heat. An optical recording medium with improved recording sensitivity, in which an organic dye reacts with a radical in an irradiated portion to form a decolorized portion and perform recording, is disclosed.

However, in this optical recording medium, it is considered that the reaction of the organic dye in the pit portion is not completely completed at the time of recording, and there is a problem that the recording contrast changes with time. There is a problem that a bleached area is also formed around the pit and the pit diameter is enlarged.

Also, Novotini and Alexandr (N
ovotny and Alexandru) "Journal of Applied Physics (Journal)
of Applied Physics) ", Vol. 5
0, No. 3, pp 1215- (March, 1979), a heat-resistant organic dye is laminated on a resin substrate, and the organic dye is diffused into the substrate by laser beam irradiation to change the spectral characteristics. A method for performing the recording is described. However, when the spectral characteristics change due to the diffusion of the organic dye into the optical recording medium substrate, a sufficient contrast ratio (for example, 0.1% in the case of an optical card).
4 or more) could not be recorded.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording method capable of performing recording showing an excellent S / N ratio on an optical recording medium having high recording sensitivity and excellent durability stability. It is in. Still another object of the present invention is to provide a reproducing method capable of reproducing with excellent contrast.

[0014]

That is, the present invention provides a substrate,
Contains an organic dye that exhibits an absorption maximum for light of the first wavelength
Recording layer, and a low molecular weight compound having a polar group and poly
Recording auxiliary layer including a marker and laminated on the substrate
Providing an optical recording medium comprising:
The recording medium is irradiated with a recording light beam, and the recording auxiliary layer and the recording
Including a state in which the organic dye and the organic dye are compatible with each other;
Form pits showing absorption maximum for light on the short wavelength side
Optical recording method of information characterized by having a process.
You.

In the optical recording method of the present invention, the optical recording
In the medium, the recording layer and the recording auxiliary layer are stacked with an isolation layer interposed therebetween.
A light beam for recording.
The recording layer destroys the recording layer and the organic dye in the recording layer.
Sufficient to interact with the auxiliary layer to form a compatible state
Those having strength are preferred.

Further , the present invention relates to a substrate and a light source having a first wavelength.
And a recording layer containing an organic dye exhibiting an absorption maximum, and
A low molecular compound having a polar group and a polymer, and
A recording auxiliary layer laminated on the substrate;
The first wave includes a state in which the auxiliary layer and the organic dye are compatible with each other.
A pit that shows an absorption maximum for light on the shorter wavelength side than longer
Therefore, the process of preparing an information record in which information is recorded
And irradiating the information record with reproduction light to the pit.
The change in the spectral characteristics from the surroundings in the
Reproducing the information.
It is a raw method.

In the reproducing method of the present invention, the information record
The recording layer is formed by stacking the recording layer and the recording auxiliary layer with an isolation layer interposed therebetween.
Having a layered structure, wherein the isolation layer is
The organic dye in the recording layer and the recording auxiliary layer
It is preferable to form a state in which it has been set. In addition, the reproduction light
Detects changes in the spectral characteristics of the pit from the surroundings.
The isolation in the non-pit areas sufficient to exit
Preferably, it has insufficient strength to break the layer.

Hereinafter, the present invention will be described in detail. The optical recording medium of the present invention is a type using a recording light beam having a predetermined wavelength and a reproduction light beam having the same wavelength as the predetermined wavelength or a reproduction light beam having a wavelength different from the predetermined wavelength, A substrate, and a multilayer film having a recording layer containing an organic dye and a recording auxiliary layer, wherein the recording auxiliary layer forms a compatible state with the organic dye by irradiation with the recording light beam. It causes an optically detectable change in the optical recording medium.

That is, the present invention does not record by reacting an organic dye in an irradiation portion of a recording light beam as in the above-mentioned conventional optical recording medium, but substantially destroys the structure of the organic dye. The interaction between the polar group contained in the recording auxiliary layer and the organic dye, more specifically, a compatible state in which the interaction between the polar group and the π electron in the organic dye occurs in the recording light irradiated part without performing Then, the recording is performed by shifting the absorption band of the organic dye to the longer wavelength side (deep color effect) or the shorter wavelength side (shallow color effect) and changing the spectral characteristics from those of the organic dye recording layer. According to the present invention, the compatibility state of the organic dye layer and the recording auxiliary layer is instantaneously formed by the irradiation of the recording light beam, and then rapidly cooled and fixed. An optical recording medium that can be stably retained over time and has excellent storage stability can be obtained.

Further, according to the present invention, the function of causing interaction with the organic dye is separated from the substrate, so that a material which brings about a compatible state which changes the spectral characteristics optimal for recording can be used. Is obtained.

Next, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing an optical recording medium of the present invention. FIG. 1A shows one embodiment of the optical recording medium of the present invention.
FIG. 1B is a schematic sectional view showing another embodiment.

The optical recording medium of the present invention shown in FIG.
A recording layer 3 and a recording auxiliary layer 5 containing a polymer containing a polar group are sequentially laminated on a substrate 2, and a protective substrate 7 is laminated via an adhesive layer 6.

Further, the optical recording medium of the present invention shown in FIG.
On top of this, there is provided a multilayer film 8 in which a recording layer 3 containing an organic dye, an isolation layer 4 and a recording auxiliary layer 5 containing a polymer containing a polar group are sequentially laminated on the recording layer 3, and further thereon. And a protective substrate 7 laminated with an adhesive layer 6 interposed therebetween.

The isolating layer 4 normally separates the recording layer 3 and the recording auxiliary layer 5 to prevent the interaction between the two layers, and the recording light beam 9 is applied to the optical recording medium. Irradiation is performed so as to be melted and destroyed by heat generated in the recording layer as shown in FIG. The recording auxiliary layer 5 comes into contact with the recording layer 3 as a result of the destruction of the isolation layer, and at least at the interface between the recording layer 3 and the recording auxiliary layer 5 by the irradiation of the recording light beam. The polar group acts on the organic dye to move the absorption band of the organic dye to form a compatible state that changes the spectral characteristics with respect to the light beam for reproduction, and the optically detectable change in the optical recording medium ( Pit 10).

In the method for recording information on an optical recording medium according to the present invention, the optical recording medium 1 is irradiated with a recording light beam 9 to at least record the recording layer 3 and a recording auxiliary layer containing a polymer containing a polar group. At the interface of No. 5, the polar group acts on the organic dye between the organic dye and the recording auxiliary layer to form a compatible state in which the spectral characteristics of the organic dye change with respect to the reproducing light beam. Recording. Alternatively, by irradiating the optical recording medium 1 with a recording light beam 9,
The separating layer 4 is destroyed, and a compatible state is formed between the recording layer and the recording auxiliary layer such that the polar group acts on the organic dye to change the spectral characteristics of the organic dye with respect to the reproducing light beam. Recording.

In the present invention, the compatible state means a mixed state in which an organic dye is diffused into a recording auxiliary layer, and / or a mixed state in which a polar group in the recording auxiliary layer is diffused in a recording layer. A state in which the organic dye is dissolved in the recording auxiliary layer and the polar group in the recording auxiliary layer acts on the organic dye to move the absorption band in the absorption spectrum of the organic dye.

In the present invention, the recording of information does not mainly consist of decolorization due to the reaction of the organic dye, but the above-mentioned organic dye in a compatible state and the polar group between the recording auxiliary layer and the π electron of the organic dye. The change in the spectral characteristics caused by the interaction is mainly used for recording, and since this compatibility state is excellent in thermal stability and also stabilized in energy,
A high-performance optical recording medium with good storage stability can be obtained.

In the present invention, the recording auxiliary layer may contain a polymer containing a polar group capable of shifting the absorption band of the absorption spectrum of the organic dye when formed in a state compatible with the organic dye. preferable. That is, the polymer containing the polar group is softened and melted by the irradiation of the recording light beam,
Form a compatible state with organic dye.

On the other hand, organic dyes generally have a conjugated double bond, and it is considered that light absorption and reflection occur due to the movement of π electrons in the molecule. In the compatible state in the present invention, the absorption band of the absorption spectrum of the organic dye has a shorter wavelength or a longer wavelength because the polar group inhibits or promotes the transfer of π electrons due to the approach of the organic dye and the polar group. It is thought to move to the side.

The polar group of the present invention includes, for example, a carboxyl group, which shifts the absorption band to the shorter wavelength side,
An amide group, an amine hydroxyl group and the like can be mentioned, and a group having a halogen and the like can be mentioned as one that moves the absorption band to a longer wavelength side.

In the present invention, the polymer containing a polar group refers to a polymer obtained by mixing the above compound having a polar group with a polymer or a polymer obtained by impregnating a polymer with the above compound having a polar group.

Specifically, maleic acid, phthalic acid, phthalic anhydride, maleic anhydride, terephthalic acid ester, fatty acid ester, propanol pentafluoride are used as polar compounds in nylon (polymer having an amide group) or polyester polymer. And 2 to 30% by weight, preferably 5 to 10% by weight,

As a polar compound in a polymer having a relatively large free volume (eg, cellulose derivative, aromatic amide, etc.), maleic acid, phthalic acid, maleic anhydride, terephthalic acid ester, phthalic anhydride, fatty acid ester, carboxylic acid An acid amide, propanol pentafluoride, etc. impregnated with 5 to 30 wt%, particularly 10 to 20 wt%, is used.

The polymer having a polar group can be produced by mixing a polymer pellet and a polar compound and then extruding the same, and the polymer can be produced by a solvent casting method. That is, formamide, water, magnesium perchlorate, potassium perchlorate, potassium chloride, and the like are added as a swelling agent in an organic solvent in an amount of 10 to 200% by weight, and the polymer is further dissolved. After the application, the solvent can be evaporated to form a porous film and immersed in the polar compound, or immersed in a solution in which the polar compound is dissolved in a poor solvent for the polymer.

In the present invention, when a cationic dye is used as the organic dye, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, terephthalic acid ester and fatty acid ester are mixed with nylon or polyester polymer. These are preferred because they can significantly shift the absorption band of the dye to the shorter wavelength side and have a stable compatibility state.

The organic dye used in the recording layer of the present invention includes, for example, anthraquinone derivatives (particularly those having an indathrene skeleton), dioxazine compounds and derivatives thereof, triphenodithiazine compounds, phenanthrene derivatives, polymethine compounds. , Cyanine compounds, merocyanine compounds, pyrylium compounds, xanthene compounds, triphenylmethane compounds, croconium dyes, azo dyes, crocones, azines, indigoids, polymethine dyes, azulene, squarium derivatives, sulfurization Dye and metal dithiolate complexes can be mentioned.

Among these organic dyes, cationic dyes typified by polymethine and cyanine are preferable in that they can stably maintain a mixed state with the recording auxiliary layer. It is particularly preferable because it can maintain excellent compatibility, can maintain the compatibility state extremely stably, and can record a good contrast because the spectral characteristics change more greatly.

The cationic dyes are listed below. A polymethine dye represented by the general formula (I).

[0039]

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In the formula, A, B, D and E represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, Or a group selected from an unsubstituted styryl group and a substituted or unsubstituted heterocyclic group. r ₁ ′ and r ₂ ′ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclic alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted Represents a group selected from aryl groups, k is 0 or 1, L is 0,
In 1 or 2, X ⁻ represents an anion.

A dye represented by the general formula (II):

[0042]

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In the formula, A, B, D, E and X ^- have the same meanings as described above, and r _{1 to} r ₅ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Show. Y represents a divalent organic residue having an atomic group necessary for completing a 5- or 6-membered ring. m and n are 0,
1 or 2.

A dye represented by formula (III):

[0045]

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Where A, B, D, E, r ₁ , r ₂ , r
_3, Y and X ^- is as defined above.

A dye represented by the general formula (IV).

[0048]

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Where A, B, D, E, r ₁ , r ₂ , r
₃ , r ₄ , m and n are as defined above, and Z ⁻ is

[0050]

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Is shown.

An azurenium-based dye represented by formula (V), (VI) or (VII).

[0053]

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[0054]

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[0055]

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In the formula, R _{1 to} R ₇ represent a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, an iodine atom) or a monovalent organic residue. The monovalent organic residue can be selected from a wide range.

R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R
_4, R ₄ and R _5, R ₅ and may form a condensed ring unsubstituted or substituted with at least one combination among the combinations of R ₆ and R ₆ and R _7. The condensed ring is a condensed ring of a 5-, 6-, or 7-membered ring; an aromatic ring (such as benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, or ethoxybenzene); Ring, benzofuran ring, pyrrole ring, thiophene ring, pyridine ring, quinoline ring, thiazole ring, etc.) and aliphatic ring (dimethylene, trimethylene, tetramethylene, etc.). And X ^- represents an anion as defined above.

F represents a divalent organic residue linked by a double bond. Specific examples of the present invention containing such F include those represented by the following general formulas (1) to (11). However, Q ⁺ in the formula represents the following azurenium salt nucleus, and F on the right side excluding Q ⁺ in the formula.

Azurenium salt nucleus (Q ⁺ )

[0060]

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General formula (1)

[0062]

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Formula (2)

[0064]

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Formula (3)

[0066]

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R ₁ ′ to R ₇ ′ have the same meaning as R _{1 to} R ₇ . Further, the azurenium salt nucleus represented by Q ⁺ and the azulene salt nucleus on the right side in the formula (3) may be symmetric or asymmetric.

General formula (4)

[0069]

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Formula (5)

[0071]

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General formula (6)

[0073]

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General formula (7)

[0075]

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In the formula, M represents a group of nonmetallic atoms necessary for completing the nitrogen-containing heterocyclic ring.

General formula (8)

[0078]

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In the formula, R ₁₀ represents a substituted or unsubstituted aryl group or a cationic group thereof. p represents an integer of 1 to 8. q is 1 or 2.

Formula (9)

[0081]

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In the formula, R ₁₁ represents a heterocyclic group or a cationic group thereof.

General formula (10)

[0084]

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In the formula, R ₁₂ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group.

General formula (11)

[0087]

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Formula (12)

[0089]

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Wherein Z ₂ represents an optionally substituted pyran, thiapiran, selenapyran, tellropyran, benzopyran, benzothiapiran, benzoselenapyran, benzotellopyran, naphthopyran, naphththiapyran or naphthoselenapyran, naphthotellopyran Atomic group. L represents a sulfur atom, an oxygen atom or a selenium atom, a tellurium atom. R ₁₃ and R ₁₄ are a hydrogen atom,
Represents an alkoxyl group, a substituted or unsubstituted aryl group, an alkenyl group, or a heterocyclic group.

Next, a preferred dye is represented by the general formula (VII)
The dyes represented by I), (IX), (X) and (XI) are shown.

Formula (VIII)

[0093]

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Formula (IX)

[0095]

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Formula (X)

[0097]

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Formula (XI)

[0099]

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The above general formulas (VIII), (IX),
In (X) and (XI), L ₁ and L ₂ represent a substituted nitrogen atom, sulfur atom, oxygen atom, selenium atom or tellurium atom, and Z ₁ represents an optionally substituted pyrylium, thiopyrylium, selenapyrium. Atomic group necessary for completing helium, telluropyrylium, benzopyrylium, benzothiopyrylium, benzoselenapyrylium, benzotelluropyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or naphthoterropyrylium, Z ₂ Is an optionally substituted pyran, thiopyran, selenapyran,
Telluropyran, benzopyran, benzothiopyran, benzoselenapyran, benzotelluropyran, naphthopyran,
The atom group required to complete naphthothiopyran, naphthoselenapyran or naphthotellopyran is shown below. s is an integer of 0 or 1. R ₁₅ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. r
₃ '~r _7' the above r ₁ ', r _2' is synonymous with.
K, n, M, r ₁ ′, r ₂ ′, r ₁ , Y, Z ⁻ and X ⁻ have the same meanings as described above.

The abbreviations in the above general formula will be described in more detail. A, B, D and E represent a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an is
o-propyl group, n-butyl group, sec-butyl group, i
a so-butyl group, a t-butyl group, an n-amyl group, a t-amyl group, an n-hexyl group, an n-octyl group, a t-octyl group, etc., and further another alkyl group such as a substituted alkyl group ( For example, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-sulfoethyl, 3-sulfoethyl Propyl group, 4-sulfobutyl group,
3-sulfatepropyl group, 4-sulfatebutyl group, N- (methylsulfonyl) -carbamylmethyl group,
3- (acetylsulfamyl) propyl group, 4- (acetylsulfamyl) butyl group, etc.), cyclic alkyl group (eg, cyclohexyl group), alkenyl group (vinyl, propenyl, butenyl, pentenyl) Hexenyl group, heptenyl group, octenyl group, dodecynyl group, prenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, etc.), substituted aralkyl group (eg, carboxy group) Benzyl, sulfobenzyl, hydroxybenzyl, etc.).

R ₁ ′, r ₂ ′, r ₃ ′, r ₄ ′, r
_{5 ', r 6', r} 7 ' is a hydrogen atom or an alkyl group (e.g., methyl group, ethyl group, n- propyl group, iso- propyl, n- butyl group, sec- butyl group, iso-
Butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group, etc.), and further another alkyl group, for example, a substituted alkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group , 4-sulfobutyl group, 3-
Sulfate propyl group, 4-sulfate butyl group,
N- (methylsulfonyl) -carbamylmethyl group, 3-
(Acetylsulfamyl) propyl group, 4- (acetylsulfamyl) butyl group, etc.), cyclic alkyl group (eg, cyclohexyl group), substituted or unsubstituted alkenyl group (vinyl group, propenyl group, butenyl group) Pentenyl group, hexenyl group, heptenyl group, octenyl group, dodecynyl group, prenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, etc.), substituted aralkyl group ( For example, a carboxybenzyl group, a sulfobenzyl group, a hydroxybenzyl group, etc.).

Further, R ₁ , R ₂ , R ₃ , R ₄ and R
₅ is a substituted or unsubstituted aryl group (for example, phenyl, naphthyl, tolyl, xylyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, dimethylaminophenyl, diethylaminophenyl, A dipropylaminophenyl group, a dibenzylaminophenyl group, a diphenylaminophenyl group, etc., a substituted or unsubstituted aryl group (phenyl group, α-naphthyl group, β-naphthyl group, tolyl group, xylyl group, ethylphenyl group, Methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibephenyl Shows Jill like aminophenyl group).

K and s are 0 or 1, and L, m and n are 0 and 1.
Or 2.

R ₁ , r ₂ , r ₃ , r ₄ , and r ₅ are a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (a methyl group, an ethyl group, an n-propyl group, an isopropyl group). Group, n-butyl group, t-butyl group, n
-Amyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, t-octyl group, etc., alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), substituted or unsubstituted aryl group (Phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, α
-Naphthyl group, β-naphthyl group, etc.).

Y is a divalent hydrocarbon group, for example,

[0107]

Embedded image —CH ₂ —CH ₂ —, — (CH ₂ ) ₃ —,

These 5- or 6-membered rings may be condensed with a benzene ring, a naphthalene ring or the like.

R _{1 to} R ₇ and R ₁ 'to R ₇ ' each represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom,
In addition to an iodine atom or the like, a substituted or unsubstituted alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-amyl group,
n-hexyl group, n-octyl group, 2-ethylhexyl group, t-octyl group, etc., substituted or unsubstituted alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), substituted or unsubstituted aryl Groups (phenyl, tolyl, xylyl, ethylphenyl,
Methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, diethylaminophenyl, α-naphthyl, β-naphthyl, dipropylaminophenyl, Benzylaminophenyl, diphenylaminophenyl group, etc., substituted or unsubstituted aralkyl group (benzyl group, 2-phenylethyl group, 2-phenyl-1-methylethyl group, bromobenzyl group, 2-bromophenylethyl group, methyl Benzyl group, methoxybenzyl group, nitrobenzyl group),
Acyl group (acetyl group, propionyl group, butyryl group,
Valeryl, benzoyl, trioil, naphthoyl, phthaloyl, furoyl, etc., substituted or unsubstituted amino (amino, dimethylamino, diethylamino, dipropylamino, acetylamino, benzoylamino, etc.) ), Substituted or unsubstituted styryl groups (such as styryl group, dimethylaminostyryl group, diethylaminostyryl group, dipropylaminostyryl group, methoxystyryl group, ethoxystyryl group, and methylstyryl group), nitro group, hydroxy group, carboxyl group,
A cyano group or a substituted or unsubstituted arylazo group (phenylazo group, α-naphthylazo group, β-naphthylazo group, dimethylaminophenylazo group, chlorophenylazo group, nitrophenylazo group, methoxyphenylazo group, tolylazo group, etc.); Unsubstituted heterocyclic groups (eg, pyridyl, quinolyl, lepidyl, methylpyridyl, furyl, thienyl, indolyl, pyrrole, carbazolyl, N-ethylcarbazolyl, etc.), 2,2 -Diphenylvinyl group, 2-phenyl-2-methylvinyl group, 2- (dimethylaminophenyl) -2-phenylvinyl group, 2- (diethylaminophenyl) -2-phenylvinyl group, 2- (dibenzylaminophenyl) -2-phenylvinyl group, 2,2-di (diethylaminophenyl ) Vinyl group, 2,2-di (methoxyphenyl) vinyl group, 2,2-di (ethoxyphenyl) vinyl group, 2- (dimethylaminophenyl) -2
-Methylvinyl group, 2- (diethylaminophenyl)-
2-ethylvinyl group).

R ₁ ′ to R ₇ ′ may form a condensed ring in the same manner as R _{1 to} R ₇ . R ₈ represents a hydrogen atom, a nitro group,
Represents a cyano group, an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group) or an aryl group (eg, phenyl group, tolyl group, xylyl group).

R ₉ represents an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), a substituted alkyl group (2
-Hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-chloropropyl group, 3-bromopropyl group, 3-carboxy Propyl group), cyclic alkyl group (cyclohexyl group,
Cyclopropyl group), allyl group, aralkyl group (benzyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, α-naphthylmethyl group, β
-Naphthylmethyl group), substituted aralkyl groups (methylbenzyl group, ethylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, chlorobenzyl group, bromobenzyl group, etc.), aryl group (phenyl group, tolyl group, xylyl group, α- A naphthyl group, β-naphthyl group) or a substituted aryl group (chlorophenyl group, dichlorophenyl group, trichlorophenyl group, ethylphenyl group, methoxyphenyl group, dimethoxyphenyl group, aminophenyl group, nitrophenyl group, hydroxyphenyl group, etc.) Express.

R ₁₀ is a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, α-naphthyl, β-naphthyl, anthralyl, pyrenyl, methoxyphenyl, dimethoxyphenyl, Trimethoxyphenyl group, ethoxyphenyl group, diethoxyphenyl group, chlorophenyl group, dichlorophenyl group,
Trichlorophenyl group, bromophenyl group, dibromophenyl group, tribromophenyl group, ethylphenyl group,
Diethylphenyl, nitrophenyl, aminophenyl, dimethylaminophenyl, diethylaminophenyl, dibenzylaminophenyl, dipropylaminophenyl, morpholinophenyl, piperidinylphenyl, piperazinophenyl, diphenyl Aminophenyl, acetylaminophenyl, benzoylaminophenyl, acetylphenyl, benzoylphenyl, cyanophenyl, etc.).

R ₁₁ represents a monovalent heterocyclic group derived from a heterocyclic ring such as furan, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine, phenoxazine and pyridine.

R ₁₂ is a hydrogen atom, an alkyl group (methyl group,
An ethyl group, a propyl group, a butyl group, etc. or a substituted or unsubstituted aryl group (phenyl group, tolyl group, xylyl group, biphenyl group, ethylphenyl group, chlorophenyl group, methoxyphenyl group, ethoxyphenyl group, nitrophenyl group, Aminophenyl, dimethylaminophenyl, diethylaminophenyl, acetylaminophenyl, α-naphthyl, β-naphthyl, anthralyl, pyrenyl, etc.).

R ₁₃ and R _{14 each} represent a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group);
Alkoxyl group (methoxy group, ethoxy group, propoxy group, ethoxyethyl group, methoxyethyl group, etc.), aryl group (phenyl group, tolyl group, xylyl group, chlorophenyl group, biphenyl group, methoxyphenyl group, etc.),
A substituted or unsubstituted styryl group (such as a styryl group, a p-methylstyryl group, an o-chlorostyryl group, and a p-methoxystyryl group), and a substituted or unsubstituted 4-phenyl-1,3-butadienyl group (4-phenyl1 , 3-butadienyl group, 4- (p-methylphenyl) -1,3-butadienyl group, etc.) or a substituted or unsubstituted heterocyclic group (quinolyl group, pyridyl group, carbazolyl group, furyl group, etc.).

M is pyridine, thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, imidazole, benzimidazole, naphthimidazole, 2-quinoline, 4-quinoline,
A group of atoms necessary to complete a nitrogen-containing heterocyclic ring such as quinoline, isoquinoline, or indole; a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (methyl group, ethyl group, propyl group, Butyl, etc.), aryl (phenyl, tolyl, xylyl, etc.) and aralkyl (benzyl, p-tolylmethyl, etc.).

X ^- is an anion which is a chloride ion, bromine ion, iodine ion, perchlorate ion, benzenesulfonate ion, P-toluenesulfonate ion, methyl sulfate ion, ethyl sulfate ion, propyl sulfate. Ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, oxalate Phosphate, succinate, malonate, oleate, stearate, citrate, monohydrogen diphosphate, dihydromonophosphate, pentachlorostannate Ion, chlorosulfonate ion, fluorosulfonate ion, trifluorometa Sulfonate ion, hexafluoroantimonate ion, molybdate ion,
Represents tungstate ion, titanate ion, zirconate ion and the like.

Specific examples of these organic dyes are shown in Table 1, but are not limited thereto. In addition, Z ^- is

[0119]

Embedded image

[0120] the time of the Za ^-, Z ^- is

[0121]

Embedded image

The time is expressed as Zb ⁻ .

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Table 6]

[0129]

[Table 7]

[0130]

[Table 8]

[0131]

[Table 9]

[0132]

[Table 10]

[0133]

[Table 11] In addition, together with these organic dyes, the spectral characteristics of the recording layer are changed from those of the recording layer consisting of the organic dye alone in order to improve the film formability and a stabilizer such as an infrared absorber for the purpose of improving light resistance. You may add the binder which does not make it do.

The thickness of the recording layer is set so that the recording layer has as high a reflectivity as possible with respect to the reproducing light beam, specifically 8% or more, so that the preformat formed on the substrate can be accurately reproduced. It is preferable that the film thickness has a reflectance of at least 10%, and it is particularly preferable that the film thickness has a maximum value of the reflectance.

Further, in the present invention, as the isolation layer 4,
The recording layer heats and causes melting, deformation or melting and deformation to connect the recording layer and the recording auxiliary layer, and when not recording, prevents interaction between the recording layer and the recording auxiliary layer, and further contacts the recording layer. Do not spread each other while
Alternatively, a material that hardly changes the spectral characteristics of the recording layer even when diffused is preferable.

As a material of such an isolation layer, for example, a polymer such as polyethylene, polypropylene, ethylene vinyl acetate, cellulose acetate, polycarbonate, and polystyrene, and an inorganic material such as SiO ₂ , SiO, CS ₂ , and Si ₃ N ₄ are used. be able to. The thickness of the isolation layer is usually 5 nm or more, because it is necessary that the hole is formed following melting or deformation or slight deformation of the recording layer due to heat generated in the recording layer during recording by laser light irradiation. 2
50 nm, especially 20 nm to 200 nm, preferably 30 nm
-100 nm is desirable.

By providing this isolating layer, the durability stability can be improved as compared with an optical recording medium in which the recording layer and the recording auxiliary layer are in direct contact. Further, by providing the recording layer with this isolating layer, the recording sensitivity can be substantially reduced as compared with the optical recording medium in which the recording layer and the recording auxiliary layer are in direct contact, and a high-intensity reproducing light beam is used. Even if the optical recording medium is not changed optically, a signal with high contrast can be reproduced.

When a polymer is used as the separating layer, a material that absorbs the recording light beam and generates heat, for example, an organic dye having an absorption maximum in the wavelength region of the recording light beam is contained in the polymer. To obtain a high-performance optical recording medium that can recover a certain degree of recording sensitivity lowered by the formation of an isolation layer, has good recording sensitivity, and can reproduce recorded information with a high contrast ratio. Can be. When the organic dye is dispersed in the separating layer, the content is preferably 1 to 5% by weight, particularly preferably 1 to 3% by weight, so that the spectral characteristics do not change due to diffusion due to contact with the recording auxiliary layer.

In the present invention, the substrate 2 is made of a glass plate, a transparent ceramic plate, PVC, polymethyl methacrylate,
A transparent plastic plate of polycarbonate, polysulfone, polyolefin resin, or the like can be used. In particular, polymethyl methacrylate which has no optical birefringence and is hard and hardly damaged is preferable. Preferably, the substrate is an optically transparent material. Further, tracking grooves, pre-pits and the like may be formed on the surface of these substrates.

Further, as the protective substrate 7, polymethyl methacrylate, polycarbonate, polysulfone, vinyl chloride, or the like can be used. Particularly, a thin protective substrate is highly resistant to bending and has good adhesion to printing ink and the like. It is preferable to use a low-cost and inexpensive polycarbonate.

Next, the optical recording medium of the present invention is prepared, for example, by coating the recording layer 3 containing an organic dye on the substrate 2 by a known coating method, for example, dip coating, spray coating, spinner coating, bar coating, blade coating. , A roll coat, a curtain coat or the like, or a vacuum film forming method such as vapor deposition or sputtering, to form a film having a predetermined thickness. Next, an isolating layer 4 is formed to a predetermined thickness by coating, vapor deposition, or laminating a film on the recording layer 3, and a recording auxiliary layer 5 is coated on the isolating layer 4 with the above-mentioned polymer or with the aforementioned polymer as a film. After laminating and forming
It can be manufactured by bonding the protective substrate 7 via the adhesive layer 6. When a film is used for the recording auxiliary layer 5,
The insulating layer 4 and the recording layer 3 are sequentially laminated on the film to form a multilayer film, and as shown in FIG. 1, the multilayer film is fixed on a substrate or a protective substrate using an adhesive layer 6. Can be manufactured.

The adhesive layer 6 is preferably of a type that cures and adheres at room temperature or a relatively low temperature, such as a silicon-based room-temperature curing adhesive, an epoxy-based room-temperature curing adhesive, or a hot-melt-based adhesive.

Next, a method for recording and reproducing information using the optical recording medium of the present invention will be described with reference to FIG. First, the information recording mode will be described. In FIG.
Reference numeral 1 denotes an optical recording medium according to the present invention, which is driven by a driving unit (not shown) of the recording / reproducing apparatus. The data sent from the host computer is converted from parallel data to serial data by a controller, an error correction code is added, and the like, and then the serial data is converted into a code signal by the modulation circuit 31. The optical head 30 is moved by a controller on a track for recording / reproducing on the optical recording medium 1 . The data converted to the code signal is sent to the laser diode 33 by the laser diode drive circuit 32, and a recording light beam whose intensity changes between a high level and a low level in accordance with the modulation of the data is emitted. .

After the recording light beam has passed through the polarizing beam splitter (PBS) 34, it is subjected to a 波長 wavelength plate (QWP) 3.
The light passes through 5 and is converted into circularly polarized light. The light is focused on a spot having a diameter of about 1 μm by the condenser lens 36 and is incident on the substrate 2 of the optical recording medium 1 to irradiate the recording layer 3. When the intensity of the recording light beam is at a high level, the heat generated in the recording layer of the optical recording medium destroys the isolation layer, so that the recording layer and the recording auxiliary layer are fixed in a compatible state, and are low. When at level, the isolation layer is not destroyed. As a result, the spectral characteristics of the recording layer change at the portion 10 'in the compatible state, information is recorded, and an information record is formed. At this time,
When an organic dye exhibiting an absorption maximum wavelength is contained in a region at or near the frequency of the recording light beam in the isolation layer, high recording sensitivity can be obtained. In the present invention, the recording auxiliary layer is preferably provided on the side opposite to the recording layer with respect to the incident direction of recording and / or reproduction light.

Next, a method for reproducing information recorded on the optical recording medium of the present invention will be described. That is, in the reproduction mode, the modulation and control systems 31, 32 of the laser diode 33 are controlled.
Is appropriately adjusted so that the intensity of the laser output does not fluctuate. Then, the output level from the laser diode is set to a value smaller than the level required to destroy the isolation layer of the information record. And the laser beam is PBS34, QWP3
5. The light is focused on the recording layer surface of the information record 1a via the substrate 2 via the condenser lens 36. Next, the light reflected by the recording layer surface passes through the QWP again, and the polarization plane
The light is reflected by the PBS 34 differently by 0 ° and enters the photodetector 37.

The intensity of light entering the photodetector 37 changes as the focused beam passes over the pit portion 10 of the recording layer having the pit 10. The output of the photodetector 37 is amplified by a preamplifier 38, and becomes a reproduction signal and signals for focus servo and tracking servo in a matrix circuit 38. Next, the reproduced signal output from the matrix circuit is converted into a digital signal by the comparator 39,
A clock signal is extracted by the L circuit, and the data synchronization detection system 40 performs synchronous demodulation of the reproduced signal using the clock signal. Then, the data is returned to the original data by the demodulation circuit 41 using an algorithm reverse to the modulation, and then sent to the optical disk controller and read by the host computer.

At this time, if the wavelength of the reproducing light beam is set at or near the reflection maximum wavelength of the non-recording portion of the recording layer, the contrast between the recording portion and the non-recording portion can be further improved.

The wavelengths of the recording light beam and the reproducing light beam may be changed, for example, the wavelength λ of the recording light beam.
_1, when the wavelength of the reproducing light beam and lambda _2, using an organic dye on the _second near the reflection maximum wavelength lambda as an organic dye used for the recording layer, an organic dye absorption maximum wavelength in the isolation layer is in the lambda ₁ near , The intensity of the reproducing light beam can be increased, so that the recording contrast is improved. At this time, the relationship between λ ₁ and λ ₂ is defined as λ ₂ ≦
If the lambda _1, it is possible to completely prevent the destruction of the isolation layer by the reproducing light preferred.

As described above, in the present description, since the recording auxiliary layer is laminated on the recording layer made of the organic dye via the isolation layer, the optical recording laser beam (for example, spot Diameter 3μm, laser power 3mW,
When the laser irradiation time is 10 to 50 μsec), a very small portion of the organic dye is thermally decomposed, and the generated heat melts the isolation layer formed between the recording layer made of the organic dye and the recording auxiliary layer. , A hole is formed. As a result, the molten dye molecules diffuse into the recording auxiliary layer and / or the recording auxiliary layer melts and diffuses into the dye layer, and the mixed state of the dye and the reactive recording layer is formed at the interface between the recording auxiliary layer and the dye layer. It is formed. As a result, the arrangement between the dye molecules changes due to the interaction between the polar groups (for example, amide group, ether group, and carbonyl group) in the recording auxiliary layer and the dye molecules. A change in reflectivity occurs and recording is performed.

According to the present invention, the recording is performed by utilizing the interaction between the organic dye and the recording auxiliary layer. Therefore, unlike the conventionally known formation of recording pits by thermal decomposition and thermal deformation of the dye, In a recording medium having a bonding structure, high-quality recording pits can be obtained even with a relatively low recording power.

Further, unlike the conventional recording method in which an organic dye is reacted with another substance to destroy the molecular structure of the organic dye and cause an optical change, the present invention does not change the molecular structure of the organic dye. Changes in spectral characteristics in the mixed state of the organic dye and the recording auxiliary layer are used for recording, and since this mixed state is thermally stable, an optical recording medium with excellent durability stability that does not change the recording contrast during storage. can get.

The optical recording medium of the present invention compensates for the small thermal deformation and the small decrease in the reflectance of pits formed by thermal decomposition in the optical recording medium having a close contact structure by the interaction of the organic dye-recording auxiliary layer. A large decrease in the reflectance of the dye occurs, and a sufficient recording contrast can be obtained.

That is, in the optical recording medium of the present invention, the reflectance change caused by the compatibility between the dye and the recording auxiliary layer is added to the reflectance change caused by the thermal deformation and thermal decomposition of the organic dye known in the art. Sufficient recording contrast can be obtained even with low recording energy.

Further, since the optical recording medium of the present invention has an isolation layer between the recording layer and the recording auxiliary layer, it prevents substances released from the recording auxiliary layer from coming into contact with the organic dye layer in a high temperature environment. Can improve the environmental resistance.

In the present invention, the recording sensitivity of the optical recording medium can be controlled by the sensitivity of the isolation layer to the recording light beam. A recording medium can be manufactured according to the purpose.

Furthermore, as shown in FIG. 5, a photo-curable resin layer 52 is formed on a
2 by a method of forming a track groove or the like (2P method)
Although the formed optical recording medium substrate is conventionally excellent in solvent resistance, it has a problem in that the deformation of the recording layer is strongly suppressed and the recording sensitivity is greatly reduced. A high-sensitivity optical recording medium can be obtained by using the optical recording medium substrate prepared in the above.

[0157]

The present invention will be described in more detail with reference to the following examples. Example 1 As a substrate, thickness 0.4 mm, size 85 mm × 54 mm
Thus, an optical card substrate of polymethyl methacrylate having a track groove with a width of 3 μm and a pitch of 12 μm on one side was prepared by casting. Next, a polymethine dye (organic dye No. 5) represented by the following structural formula was applied to the surface of the optical card substrate on which the track grooves were formed by a gravure coater to a thickness of 100.
0 ° to form a recording layer. The thickness is 8 wavelengths.
It shows the maximum reflectance for light of 30 nm (see FIG. 6). FIG. 7 is a graph showing the relationship between the reflectance and the wavelength of the thin film having a thickness of 1000 ° of the organic dye used in Example 1.

[0158]

Embedded image

Next, as a recording auxiliary layer, a film in which 10 wt% of phthalic anhydride was mixed with a 30 μm-thick polyester-based polymer (trade name: Chemit 248; manufactured by Toray Industries, Inc.) was laminated, and then a silicon-based adhesive (Shin-Etsu) was used. An optical card was obtained by laminating a 0.3 mm-thick polycarbonate protective substrate using silicone (TSE3033).

The optical card is inserted into an optical card recording / reproducing
Non-manufactured) and record it on the obtained optical recording medium.
User power 3mW, wavelength 830nm, pulse width 20μs
ec (laser beam irradiation time), semiconductor with spot diameter of 3 μm
Recording was performed by injecting a laser beam through the substrate.
Next, a wavelength of 830 nm and a reproducing laser power of 0.2 mW
When the recording section was reproduced with, the contrast ratio [(R₁−
R₂) / R₁] Was as good as 0.6. However, light car
Transport speed of 120 mm / sec for recording and 48 for reproduction
0 mm / sec. Also, R₁Is the output level of the non-recording part.
R₂ Is the output level of the recording unit. Also, the wavelength
Reflection of non-recording area for 830 nm light Is 16%, the record
Part reflectance Was 3%.

Next, the spectral transmittance of the recording layer of the non-recording portion of the optical card and the spectral transmittance of the laser beam irradiation portion (pit) were measured using an instantaneous multi-photometry system (trade name: MCPD model 1000; Otsuka Electronics Co., Ltd.). )). FIG. 4 shows the results. In FIG. 4, (a) the spectral transmittance of the recording layer of the non-recording portion, and (b) the spectral transmittance of the pit. Further, when the contrast was measured after leaving the optical card for 1000 hours under the condition of a temperature of 50 ° C. and an RH of 90%, the change of the contrast ratio was within 10% of the initial value.

Comparative Example 1 The organic dye used in Example 1 was applied on the optical card substrate used in Example 1 to a thickness of 1000 Å, and then 9 parts by weight of benzoyl peroxide as a compound generating radicals by light irradiation. It is dissolved and dispersed in a mixture of 1 part by weight of dichloroethane and 2 parts by weight of diacetone alcohol together with 1 part by weight of nitrocellulose, coated in the same manner with a gravure coater to form a benzoyl peroxide-containing layer having a dry film thickness of 750 °, and then carried out. An optical card was obtained by laminating a protective substrate in the same manner as in Example 1.
When recording and reproduction were performed on this optical card in the same manner as in Example 1, the reflectance of the pit portion was 8%, and the contrast ratio was 0.5. The spectral transmittance of the pit portion was measured in the same manner as in Example 1. The result is shown as (c) in FIG.

The above optical card was heated at a temperature of 50.degree.
When the durability of the optical card was examined under the condition of H90%,
At the endurance time of 1000 hours, the size of the recording pit was enlarged and the pit interval was changed from that at the time of recording, so that accurate information could not be reproduced.

4 (a) and 4 (b), it is observed that the waveform of the spectral transmittance (spectral absorption) of the organic dye recording layer shifts around the wavelength λ of the recording laser beam.
For light with a wavelength of 0 mm, the reflectivity drops from 16% to 3%. Further, since the phenomenon at the pit portion in Example 1 is different from the waveform of the spectral transmittance of the recording portion due to the decomposition of the organic dye shown in FIG. It is thought that a change different from that of the decomposition occurred.

Reference Example 1 No. 1 used in Example 1 was placed on a glass substrate. The organic dye No. 5 and the material of the recording auxiliary layer were dissolved and dispersed in dichlorobenzene at a ratio (weight ratio) of 1:20, and applied to a thickness of 1000 ° using a gravure coater to form a recording layer. Next, the spectral transmittance of this recording layer was measured. The measurement was performed through a glass substrate. The result is shown in FIG. 4 as (d).

Next, after extracting an organic dye from the recording layer with diacetone alcohol, a 100 μm thick
When the film was coated at 0 ° and its spectral absorption characteristics were measured, the maximum absorption wavelength coincided with the maximum absorption wavelength of the non-recording portion of the recording layer of Example 1, and its spectral absorption characteristics almost matched. From this, it can be seen that in the mixed state of the recording auxiliary layer and the organic dye, no reaction accompanied by the decomposition of the organic dye occurred.

Since the waveform of the spectral transmittance of Reference Example 1 shown in FIG. 4D substantially coincides with the waveform of the spectral transmittance of the pit portion of Example 1, the recording of the present invention was performed. It can be seen that this is not due to decomposition of the organic dye, but to a change in spectral characteristics due to diffusion of the organic dye and the recording auxiliary layer.

Example 2 A substrate having a thickness of 0.4 mm and a size of 85 mm × 54 mm was used.
Thus, an optical card substrate of polymethyl methacrylate having a track groove with a width of 3 μm and a pitch of 12 μm on one side was prepared by casting. Next, a polymethine dye (organic dye No. 5) represented by the following structural formula was applied to the surface of the optical card substrate on which the track grooves were formed by a gravure coater to a thickness of 100.
0 ° to form a recording layer.

[0169]

Embedded image

Next, on the above-mentioned recording layer, a deposited film of polyparaxylene having a thickness of 1000 ° was laminated as an insulating layer, and then a 30 μm-thick polyester polymer (trade name: Chemit 248; Toray Industries, Inc.) was formed as a recording auxiliary layer. )
Film) mixed with 10 wt% of phthalic anhydride, and then a silicone adhesive (Shin-Etsu Silicone, TS
Using E3033), a 0.3 mm thick polycarbonate protective substrate was laminated to obtain an optical card.

This optical card was mounted on an optical card recording / reproducing machine (manufactured by Canon Inc.), and the obtained optical recording medium was subjected to recording laser power of 3 mW, wavelength of 830 nm, and pulse width of 20 μs.
ec (laser beam irradiation time), recording was performed with a spot diameter of 3 μm, and reproduction was performed with a reproduction laser power of 0.2 mW.
The contrast ratio was as good as 0.6. However, the transport speed of the optical card is 100 mm / sec for recording and 40 mm for reproduction.
0 mm / sec.

The above optical card was heated at a temperature of 50.degree.
When the durability of the optical card was examined under the condition of H90%,
Even when the durability time was 1000 hours, the change in the contrast ratio was within 5% of the initial value.

Comparative Example 2 In the optical card of Example 1, except that the ethylene-vinyl acetate hot melt film (Hirodine 7580; manufactured by Hirodyne Co., Ltd.) was used as the adhesive layer except for the recording auxiliary layer. An optical card was produced in the same manner as described above. When recording and reproduction were performed using this optical card in the same manner as in Example 1, the contrast ratio was 0.3. Furthermore, the change rate of the contrast ratio after the durability test is a maximum of 20%.
Met.

Example 3 In the recording auxiliary layer of Example 2, the polyester polymer PH4 was used.
An optical recording medium having the same sensitivity as that of Example 1 could be obtained even when a film obtained by mixing maleic anhydride at 10 wt% with No. 13 (manufactured by Nippon Matai) was used.

Example 4 A phthalic anhydride was added to a polyamide-based polymer: diamide (manufactured by Daicel Chemical) for the recording auxiliary layer of the optical card of Example 2.
Even when recording was performed on an optical recording medium manufactured using a film in which wt% was mixed by the same method as in Example 2, a highly sensitive result with a recording contrast of 0.7 could be obtained.

Example 5 When a film obtained by adding 5 wt% of phthalic acid to an epoxy polymer PHE411 (manufactured by Nippon Matai) was used for the recording auxiliary layer of the optical card of Example 2 and recording was performed in the same manner as in Example 2, the recording contrast was increased. Of 0.5 was obtained.

Example 6 An optical recording medium equivalent to that of Example 2 was obtained even when the isolating layer of Example 2 was changed to a polystyrene film having a thickness of 500 °.

Example 7 In the optical card of Example 6, No. 1 was used as a recording layer for polystyrene as an isolation layer. 5 wt% of the organic dye was added, and 1 wt% was dissolved and dispersed in methyl ethyl ketone.
An optical card was produced in the same manner as in Example 6, except that the recording layer was spin-coated to a thickness of 500 °.

Under the recording / reproducing conditions of the second embodiment, the recording speed of this optical card was 120 mm / sec and the reproducing speed was 480.
A contrast ratio of 0.7 was obtained under the same conditions except for mm / sec. The change ratio of the contrast ratio after the durability was within 10%.

Example 8 As shown in FIG. 5, a substrate having a thickness of 0.4 mm and a size of 8 mm was used.
On a 5 mm × 54 mm polycarbonate resin substrate 51, an ultraviolet curable resin 52 having the following composition having a thickness of 40 mm
μm. Next, a groove width of 3 μm and a pitch of 12 μm
A stamper having a pattern corresponding to an optical card track groove having a groove depth of 3000 mm is adhered to the ultraviolet curable resin layer, and an ultraviolet ray (2 KW high-pressure mercury lamp, 300 m
W / cm ² ) to cure the ultraviolet curable resin, and then the stamper was peeled off to obtain the optical card substrate 2.

Composition of UV-curable resin Urethane acrylate 30 parts by weight Neopentyl glycol-modified trimethylolpropane diacrylate 67 parts by weight 1-hydroxycyclohexyl phenyl ketone 3 parts by weight

Next, a recording layer, an isolation layer, a recording auxiliary layer and a protective substrate were laminated on this optical card substrate in the same manner as in Example 2 to form an optical card. When recording and reproduction were performed on this optical card in the same manner as in Example 2, the contrast ratio showed a good value of 0.5.

Comparative Example 3 An optical card was prepared in Example 8 from which the isolation layer and the recording auxiliary layer had been removed, and recording and reproduction were performed in the same manner as in Example 8. The contrast ratio was 0.1. It did not become practical as an optical card.

Example 9 The absorption maximum wavelength of 86 was formed on the recording auxiliary layer used in Example 1.
0.05 wt% of an organic dye having the following formula at 0 nm:
A solution of 1 wt% of formamide, 1 wt% of cellulose acetate, and 97.8 wt% of acetone was applied to form a 1000Å thick isolating layer. Next, as recording layer No. 1 having a reflection maximum wavelength at 780 nm. A 3 wt% solution of 40 organic dyes in dichloroethane was applied on the substrate prepared in Example 8 to form a recording layer having a thickness of 600 °.

[0185]

Embedded image

Next, after the recording layer and the separating layer were overlapped so as to be in contact with each other, the protective substrate was attached to the recording auxiliary layer via a rubber-based hot melt adhesive (trade name: Meltron 3S42, manufactured by Diabond Industries, Ltd.). Were laminated to produce an optical card.

This optical card was mounted on an optical card recording / reproducing apparatus, and was conveyed at a transport speed of 120 mm / sec and a wavelength of 780 n.
m, laser power 3 mW, pulse width 20 μsec, spot diameter 3 μm, and then transport speed 48
0 mm / sec, wavelength 830 nm, laser power 0.
When reproduced at 3 mW, the contrast ratio was as good as 0.6, and almost no change in contrast after the durability test was observed.

Examples 10 to 13 In the optical card of Example 8, except that the materials shown in Table 1 were used as the organic dye layer, the separating layer and the recording auxiliary layer.
An optical card was produced in the same manner as described above. About this optical card
Recording and reproduction were performed under the same conditions as in Example 2 to measure the contrast ratio, and the change in contrast after the durability test was measured. Table 2 shows the above results.

Comparative Examples 4 to 7 In Examples 10 to 13, optical cards were prepared in which the recording auxiliary layer and the isolation layer were omitted, and optical cards were manufactured in the same manner as in Examples 10 to 13 above. The ratio and the change in contrast ratio after the durability test were measured. Table 3 also shows the results.

[0190]

[Table 12]

[0191]

[Table 13]

Example 14 A thickness of 1.2 mm, an outer diameter of 130 mm, and an inner diameter of 15 mm, one surface having a width of 0.6 μm, a pitch of 1.6 μm, and a depth of 11
A glass optical disk substrate having a spiral track groove of 00 ° was manufactured by a reactive ion etching method. The track No. is formed on the track groove forming surface of the optical disk substrate. 4 wt. Of dichloromethane of organic dye of 5
% Solution by a spin coater to form a recording layer having a thickness of 1000 °.

Next, an isolation layer of 100 ° was formed on the recording layer.
Is applied, and as a recording auxiliary layer, a 30 μm-thick film in which phthalic acid is mixed with 10% by weight of nylon is laminated, and a rubber hot-melt adhesive (trade name: Meltron 3S49; Diabond Kogyo Co., Ltd.) The protective substrate made of glass having a thickness of 1.2 mm and a diameter of 130 mm was adhered to the optical disk to manufacture an optical disk.

This optical disk was mounted on an optical disk evaluation device (trade name: OMS-1000; manufactured by Nakamichi Co., Ltd.), the wavelength was 830 nm, the beam diameter was 1.6 μm, and the power was 8.
Using a recording light beam of 0 mW, the optical disk was moved at a linear velocity of 7
The information was recorded at a recording pulse width of 0.2 μs while rotating at m / sec. Note that the recording light beam was incident so as to pass through the transparent substrate.

A reproducing light beam having a wavelength of 830 nm, a beam diameter of 1.6 μm, and a power of 0.5 mW was applied so as to pass through a transparent substrate to reproduce information, and the recording contrast was measured. Furthermore, this optical disk was heated at a temperature of 50 ° C.
The change in the reproduction signal (RF output) after leaving the apparatus to stand for 1000 hours under the condition of 90% RH was measured.

Comparative Example 8 An optical disk was prepared in Example 14 from which the isolation layer and the recording auxiliary layer were removed, recording and reproduction were performed under the same conditions as in Example 14, and the contrast was measured. did. Table 4 shows the above results.

[0197]

[Table 14]

[0198]

As described above , according to the present invention, a small thermal deformation and a small decrease in the reflectance of pits formed by thermal decomposition in an optical recording medium having an adhesive structure can be reduced by the organic dye-recording auxiliary layer. , The reflectance of a large dye is reduced, high-quality recording pits can be obtained even with a relatively low recording power, and a sufficient recording contrast can be obtained.

Further, in the present invention, the change in the spectral characteristics in the mixed state of the organic dye and the recording auxiliary layer is used for recording without changing the molecular structure of the organic dye, and this mixed state is thermally stable. It is possible to perform recording on an optical recording medium with excellent durability stability while the recording contrast does not change.
it can.

Further, according to the present invention, since the separation layer is provided between the recording layer and the recording auxiliary layer of the optical recording medium, the substance released from the recording auxiliary layer under high temperature environment can be an organic substance. Contact with the dye layer can be prevented, and environmental resistance is improved.

Further, according to the present invention, the above optical recording medium
It can be recorded indicating the excellent S / N ratio can be further performed better reproduction of contrast.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an optical recording medium of the present invention.

FIG. 2 is a schematic sectional view of a recording section of the optical recording medium of the present invention.

FIG. 3 is a schematic diagram of a recording / reproducing system for an optical recording medium according to the present invention.

FIG. 4 is a graph showing spectral transmittances of a non-recording portion of a recording layer, a recording portion of a conventional optical recording medium, and a recording portion according to the present invention.

FIG. 5 is a schematic sectional view showing another embodiment of the optical recording medium of the present invention.

FIG. 6 is a graph showing the film thickness dependence of the reflectance of the organic dye thin film used in Example 1 for light having a wavelength of 830 nm.

FIG. 7 is a graph showing the relationship between the reflectance and the wavelength of the thin film having a thickness of 1000 ° of the organic dye used in Example 1.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Optical recording medium 2 Substrate 3 Recording layer 4 Isolation layer 5 Recording auxiliary layer 6 Adhesive layer 7 Protective substrate 8 Multilayer film 9 Recording light beam 10 Pit 11 Hard coat layer 51 Flat substrate 52 Photocurable resin layer

Claims (11)

(57) [Claims] 1. A substrate having an absorption maximum for light of a first wavelength.
Having a recording layer containing an organic dye showing
Containing low molecular weight compound and polymer, and laminated on the substrate
An optical recording medium having a recording auxiliary layer
And irradiating the optical recording medium with a recording light beam.
This includes the state in which the recording auxiliary layer and the organic dye are compatible with each other.
Only the absorption maximum for light on the shorter wavelength side than the first wavelength.
Forming pits indicating
Optical recording method of information. 2. The optical recording medium according to claim 1 , wherein the recording layer and the recording auxiliary
Having a configuration in which layers are stacked with an isolation layer interposed therebetween
Wherein the recording light beam destroys the isolation layer and
The organic dye in the layer interacts with the recording auxiliary layer to form a compatible state.
Claims that have sufficient strength to form a state
2. The optical recording method according to 1. 3. The method according to claim 1, wherein the low molecular weight compound is maleic acid or maleic anhydride.
Inic acid, phthalic acid, phthalic anhydride, terephthalic acid ester
3. The method according to claim 1, which is an ester or a fatty acid ester.
Optical recording method. 4. A wherein the organic dye is a cationic dye
Item 4. The optical recording method according to any one of Items 1 to 3. 5. The optical recording method according to claim 4, wherein said cationic dye is a polymethine dye represented by the following general formula (I).
Law. Embedded image (Wherein A, B, D and E represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted R ₁ ′ and r ₂ ′ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclic alkyl group, a substituted styryl group and a substituted or unsubstituted heterocyclic group. Or a group selected from an unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl group, k is 0 or 1, L is 0, 1 or 2
And X ⁻ represents an anion. ) 6. The organic dye of the following general formula (II) or (II)
The optical recording method according to claim 1, which is represented by I) or (IV).
Law. Embedded image Embedded image Embedded image (Wherein, A, B, D, E and X ⁻ are as defined in claim 5, and r _{1 to} r ₅ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted .Y which an aryl group is a divalent organic residue having a group of atoms necessary to complete a 5- or 6-membered ring substituted or unsubstituted .Z ^- is embedded image Is shown. m and n are 0, 1 or 2. ) 7. The organic dye of the following general formula (V) or (V)
The optical recording according to claim 1, which is represented by I) or (VII).
How . Embedded image Embedded image Embedded image (Wherein, R _{1 to} R ₇ represent a hydrogen atom, a halogen atom or a monovalent organic residue, and R _{1 to} R ₇ may combine to form a substituted or unsubstituted fused ring. X ⁻ Represents an anion, and F represents a divalent organic residue.) 8. The organic dye according to the following general formula (VIII):
The optical recording method according to claim 1, which is represented by (IX), (X) or (XI). Embedded image Embedded image Embedded image Embedded image (Wherein L ₁ and L ₂ represent a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom, Z ₁ is a group of atoms necessary for forming an optionally substituted pyrylium-based skeleton, and Z ₂ is R ₁₅ represents an aryl group or a substituted or unsubstituted heterocyclic group, and ₁ M ₂ represents a nonmetallic atom required to complete a nitrogen-containing heterocyclic ring. _.r 1 '~r _7' is showing a group synonymous with _{r 1} 'according to claim ^{5, X -, Z -, Y} , of _{r 1} is claim 6, wherein each ^{X -, Z -, Y,} r Synonymous with ₁ , k and s are 0 or 1, L and n are 0, 1 or 2.) 9. The substrate has a maximum absorption for light of the first wavelength.
Having a recording layer containing an organic dye showing
Containing low molecular weight compound and polymer, and laminated on the substrate
Recording auxiliary layer, wherein the recording auxiliary layer and the organic
Including a state in which the dye is compatible with the dye, and having a shorter wavelength than the first wavelength.
Information is provided by a pit that shows the absorption maximum for long-side light.
Providing a recorded information record; and the information
The reproduction record is irradiated with the reproduction light to
To reproduce the information by detecting changes in
And a method for reproducing information. 10. The information record includes: the recording layer and the recording layer.
Having a structure in which the auxiliary layer and the isolation layer are stacked with the isolation layer interposed therebetween,
The isolation layer is destroyed at the pits, and
That the organic dye and the recording auxiliary layer are in a compatible state
The reproduction method according to claim 9 . 11. The method according to claim 1, wherein the reproduction light is a spectrum at the pit.
Is sufficient to detect changes in the characteristics of the
Insufficient strength to break the isolation layer in non-pit areas
10. The reproducing method according to claim 9, comprising: