JP2001084594A - Optical recording medium and recording method thereon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a deviation problem of mark by recording the length of a data mark so that the difference between the time difference between an irradiation starting time and an irradiation ending time of a recording laser and the length of data mark is made shorter as the length of a data mark goes longer in the length range of the data mark to be recorded by the same recording pattern. SOLUTION: The jitter is rapidly deteriorated because that the pit deviation grows worse as the mark length goes longer in the case of an optical recording medium to use a derivative of porphyrin as the recording layer. The phenomenon to become physically shorter as the mark length goes longer, namely the diviation deterioration, can be prevented by controlling the time difference to satisfy the relational expression: (nT-Tint(nT))>=((nT+1)-Tint(nT+1))>=((nT +2)-Tint(nT+2)) in the length range of the data mark to be recorded by the same recording pattern when the recording laser irradiation starting time is defined as t top (nT), the recording laser irradiation ending time as t end (nT) and the difference between them as Tint (nT).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording medium,
The present invention relates to an optical recording medium recordable by laser light and a recording method thereof.

[0002]

2. Description of the Related Art As porphyrin derivatives, for example, phthalocyanine compounds have been put to practical use as recording materials for CD-Rs. This is because the phthalocyanine compound has characteristics such as abundant variation of substituents and extremely excellent light resistance. However, the porphyrin derivative is more likely to suppress the spread of the mark than, for example, an azo metal complex or a cyanine dye practically used in CD-R or DVD-R. For this reason, an optical recording medium made of a porphyrin derivative, for example, a DVD Specific
ations for Recordable Dis
k (DVD-R) Part 1 PHYSICAL
SPECIFICATIONS Version 1.
Bas as described in Jul. 1997
In the case of recording using ic Strategies (see FIG. 1), even when a good jitter value was obtained, there were cases where reproduction was impossible. JP-A-10-172181 describes that deterioration of mark deviation in a CD-R using a phthalocyanine compound can be improved by providing a thin film layer made of a metal or an alloy between a substrate and a recording layer.

However, this method may cause a decrease in productivity, for example, a process of providing a new thin film layer made of a metal or an alloy may be added, and a defect rate at the time of forming a recording layer may increase. This problem of poor reproduction occurred in the CD-R made of the porphyrin derivative, but in the DVD-R made of the porphyrin derivative, the poor reproduction occurred more remarkably. In addition, when a recording material having a small decomposition promoting effect is used instead of the porphyrin derivative, reproduction may not be possible even if a good jitter value is obtained. However, porphyrin derivatives have abundant variations including high light resistance and skeleton, substituents,
It has features such as being compatible with a wide wavelength range and having a high absorption coefficient, and is very useful for an optical recording medium.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention provides an optical information recording medium using a recording material having a small decomposition promoting effect as a recording layer, which has no mark de-biasing problem, Provide a recording method without a deviation problem. Similarly, in the present invention, in an optical information recording medium using a porphyrin derivative as a recording layer, an optical recording medium having no mark deviation problem and a recording method having no mark deviation problem are provided.

[0005]

Accordingly, the object of the present invention is to provide (1) a method of recording data with the same recording pattern in which the time difference between the recording laser irradiation start time and the recording laser irradiation completion time and the data mark length difference are different. An optical recording medium characterized in that the data recording length is shortened as the data mark length becomes longer within the mark length range. ", (2)" In an optical recording medium having a recording layer mainly composed of a porphyrin derivative, a recording laser The time difference between the irradiation start time and the recording laser irradiation completion time, and the difference between the data mark lengths are within the range of the data mark length to be recorded with the same recording pattern, and the recording is shortened as the data mark length increases. And (3) that the porphyrin derivative is a naphthalocyanine compound represented by the following formula (1). The optical recording medium according to claim (2) claim to.

[0006]

Embedded image (R _{1 to} R ₂₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group Represents a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or tetravalent metal atom optionally having oxygen or halogen, Or (OR ₂₅ ) p, (OSiR ₂₆ R ₂₇ R ₂₈ ) q,
(OPOR ₂₉ R ₃₀ ) r represents a metal atom which may have (OCOR ₃₁ ) s. R _{25 to} R ₃₁ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group,
p, q, r, and s represent an integer of 0 to 2. )), (4), wherein the porphyrin derivative is a phthalocyanine compound represented by the following formula (2):
The optical recording medium according to item 1.

[0007]

Embedded image (R _{1 to} R ₁₆ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group Represents a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or tetravalent metal atom optionally having oxygen or halogen, Or (OR ₁₇ ) p, (OSiR ₁₈ R ₁₉ R ₂₀ ) q,
(OPOR ₂₁ R ₂₂ ) r represents a metal atom which may have (OCOR ₂₃ ) s. R _{17 to} R ₂₃ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group,
p, q, r, and s represent an integer of 0 to 2. )), (5), wherein the porphyrin derivative is a porphyrazine compound represented by the following formula (3):
The optical recording medium according to item 1.

[0008]

Embedded image (R _{1 to} R ₈ are each independently a hydrogen atom, a halogen atom,
Nitro group, cyano group, hydroxyl group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted amino group, substituted or unsubstituted acyl group Represents M is two hydrogen atoms, or a divalent, trivalent or tetravalent metal atom which may have oxygen or halogen,
Or (OR ₉ ) p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OP
OR ₁₃ R ₁₄ ) represents a metal atom which may have r (OCOR ₁₅ ) s. R _{9 to} R ₁₅ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, p, q,
r and s represent an integer of 0 to 2. (6) The optical recording medium according to the above (2), wherein the porphyrin derivative is a porphyrin compound represented by the following formula (4).

[0009]

Embedded image (R _{1 to} R ₈ and X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. (7) The optical recording medium according to the item (2), wherein the porphyrin derivative is a porphycene compound represented by the following formulas (5) to (9).

[0010]

Embedded image

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image (R _{1 to} R ₈ and X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. ) "
(8) "The porphyrin derivative is represented by the following formula (10)-
The optical recording medium according to the above item (2), which is a corrole compound represented by (14).

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image (R _{1 to} R ₈ and X _{1 to} X ₃ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents three hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. ) ", (9)" The porphyrin derivative is
The optical recording medium according to the above (2), which is a monoazaporphyrin compound represented by the following formula:

[0020]

Embedded image (R _{1 to} R ₈ and X _{1 to} X ₃ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. (10) The optical recording medium according to the above (2), wherein the porphyrin derivative is a diazaporphyrin compound represented by the following formula (16).

[0021]

Embedded image (R _{1 to} R ₈ and X _{1 to} X ₂ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. ) "
Achieved by

The above-mentioned problem is also solved by the present invention in (11), wherein the difference between the time difference between the recording laser irradiation start time and the recording laser irradiation completion time and the data mark length is within the range of the data mark length recorded with the same recording pattern. Recording on an optical recording medium having a recording layer comprising a porphyrin derivative according to any one of the above items (1) to (10), wherein the recording is made shorter as the data mark length becomes longer. (12) "In a recording method using a recording strategy consisting of at least a first pulse portion and a last pulse portion, the first pulse irradiation time is increased as the data mark length becomes longer, and the recording is performed. A recording method for an optical recording medium having a recording layer comprising the porphyrin derivative according to any one of (1) to (10). "
(13) In the recording method using a recording strategy including at least a first pulse portion and a last pulse portion, the last pulse irradiation time is longer as the data mark length is longer, and the recording is performed. Through (1)
A recording method for an optical recording medium having a recording layer comprising the porphyrin derivative according to any one of the above items 0). Is achieved.

In the present invention, a recording material having a small decomposition promoting effect, or many porphyrin derivatives are used as DVD S
specifications for Recorda
ble Disk (DVD-R) Part 1 PH
YSICAL SPECIFICATIONS Ver
In the case where recording is performed using Basic Strategies as described in section 1.0 July 1997, even when a good jitter value is obtained, the cause of the reproduction failure is that the longer the mark, the longer the physical length of the recording mark. I found that it was getting shorter. Also, CD-Rs using a recording material having a small decomposition promoting effect or a porphyrin derivative as a recording layer have caused problems such as poor synchronization and deterioration of jitter. However, CD-Rs use EFM modulation as a modulation method. Since the longest mark is 11T, the DVD-R uses 8-16 modulation and the longest mark is 14T. Therefore, the deviation problem of this mark is caused by a recording material or a porphyrin derivative having a small decomposition promoting effect. It has been found that it becomes more prominent in the DVD-R used as the recording layer.

More specifically, this phenomenon is caused by DVD Speci.
fictions for Recordable
Disk (DVD-R) Part 1 PHYSIC
ALSPECIFICATIONS Version
1.0 as described in July 1997
It can be seen by measuring the difference between the space length and the mark length of the azo metal complex (FIG. 2) and the porphyrazine compound (FIG. 3) which is a porphyrin derivative when recording is performed at various recording powers using the asteric strategy. That is, in the case of the azo metal complex, the difference between the space length and the mark length hardly depends on the data mark length, whereas in the case of the porphyrazine compound, the difference between the space length and the mark length has a large data mark length dependency. .

According to FIG. 3, in an optical recording medium using a porphyrin derivative as a recording layer, the jitter value itself is largely governed by short marks, so even if a good value is obtained, it is used for the purpose of achieving frame synchronization. The 14T mark is determined to be significantly shorter, and the possibility of synchronization failure is high, and the pit deviation deteriorates as the mark length increases. It can be seen that is rapidly deteriorated. The phenomenon that this longer mark is physically shorter is that the time difference between the recording laser irradiation start time and the recording laser irradiation completion time, and the difference between the data mark lengths are within the range of the data mark length to be recorded with the same recording pattern. It has been found that the recording can be avoided by shortening the recording as the data mark length becomes longer, and a very excellent jitter value can be obtained. That is, when the recording pattern shown in FIG. 4 is used, the recording laser irradiation start time is set to t.
_top (nT), recording laser irradiation completion time to _end (nT)
Assuming that the time difference between them is T _int (nT), within the range of the mark length to be recorded with the same recording pattern,

[0026]

Expression (1) (nT−T _int (nT)) ≧ ((nT + 1) −T _int (nT + 1)) ≧ ((nT + 2) −T _int (nT + 2)) (I) Can be prevented (however, in the formula (I), not all inequality signs become =).

By the way, the same recording pattern in the present invention refers to the case where the structure and combination of laser irradiation pulses are the same, for example, a DVD Specialist.
ions for Recordable Disk
(DVD-R) Part 1 PHYSICAL SP
ECIFICATIONS Version 1.0J
As described in Uly 1997, a 3T mark is formed by a single pulse, and a 4T or more mark is recorded by a plurality of pulses. Therefore, a 4T mark or more is called the same recording pattern (3T is a 4T mark or more. It is not the same recording pattern). The data mark length nT is the length of data to be recorded (same as Twd (nT) in the figure). The recording laser irradiation start time is a time t _top at which laser light irradiation for forming a mark is started when a recording mark is formed from a simple rectangular wave as shown in FIG.
(NT), and when a recording mark is formed from a plurality of pulses as shown in FIG. 5, this is the time ts _top (nT) when laser irradiation of the first pulse is started. The recording laser irradiation completion time is defined as a time when a recording mark is formed from a simple rectangular wave as shown in FIG.
Time t when laser beam irradiation for forming a mark is completed
_In the case where a recording mark is formed from a plurality of pulses as shown in FIG. 5, this is the time te _end (nT) at which the laser irradiation of the last pulse is completed.

The modulation method applied to the DVD-R,
When the strategy is used, as shown in FIG. 5, the recording laser irradiation start time is ts _top (nT), the recording laser irradiation completion time is te _end (nT), and the time difference between the two is T _int (nT). ), The data mark length of 4T to 14T, which is within the range of the data mark length recorded in the same recording pattern,

[0029]

[Equation 2] (4T−T _int (4T)) ≧ (5T−T _int (5T)) ≧ (6T−T _int (6T)) ≧... ≧ (10T−T _int (10T)) ≧ (11T−) T _int (11T)) ≧ (14T−T _int (14T)) (II) can prevent the deterioration of the deviation (however, in equation (II), all inequality signs do not become “=”). ).

On the other hand, DVD Specificatio
ns for Recordable Disk (DV
DR) Part 1 PHYSICAL SPEC
IFICATIONS Version 1.0 Ju
Basic S as described in ly. 1997.
When using the strategy,

[0031]

[Equation 3] (4T−T _end (4T)) = (5T−T _end (5T)) = (6T−T _end (6T)) =... = (10T−T _end (10T)) = (11T−) _Tend (11T)) = (14T− _Tend (14T)) (III) Therefore, the longer the mark, the more the cooling effect by the multi-pulse is obtained, so that the mark is physically shorter.

In order to satisfy the relations of the above-described equations (I) and (II), as the data mark length becomes longer, t _top
The time of (nT) or ts _top (nT) may be advanced, or the time of t _end (nT) or te _end (nT) may be delayed, or a combination of both. However, as the data mark length nT becomes longer, t _top (n
If either T) or ts _top (nT) is advanced, or t _end (nT) or te _end (nT) is delayed, either the leading or trailing space depends on the mark length. In this case, t _top
It is necessary to limit the amount to advance the time of (nT) or ts _top (nT)) and to delay the time of t _end (nT) or te _end (nT) to some extent, and use them in combination.

When a setting is used in which all pulse irradiation times are based on the pulse irradiation end time, that is, the first pulse irradiation completion time te _top (nT) and the last pulse irradiation completion time te _end (nT) are fixed. When the first pulse irradiation time T _top and the last pulse irradiation time T _end are controlled by changing the first pulse irradiation start time ts _top (nT) and the last pulse irradiation start time ts _end (nT), the above-mentioned (II) is used. ) To make a relationship like the expression,

[0034]

[Formula 4] T _top (3T) ≦ T _top (4T) ≦ T _top (5T) ≦... ≦ T _top (10T) ≦ T _top (11T) ≦ T _top (14T) (IV) (However, in equation (IV), not all inequalities are equal to =). However, if T _top (nT) is set to be longer as the data mark length nT becomes longer, the difference in the preceding space may become larger depending on the mark length and jitter may be deteriorated. Therefore, the control amount of T _top (nT) is limited to some extent. There is a need to. In this case, the relation of the formula (IV) is set to an appropriate range, and the final pulse irradiation time T _end (xT) is set.

[0035]

[Equation 5] _Tend (3T) ≤ _Tend (4T) ≤ _Tend (5T) ≤ ... ≤ _Tend (10T) ≤ _Tend (11T) ≤ _Tend (14T) ... (V) This makes it possible to improve the deviation of the mark and to prevent the deterioration of the jitter due to the increase in the difference between the previous marks due to the recording mark length (however, in equation (V), all the inequality signs do not become =).

[0036]

[Equation 6] Or, conversely, in order to make the relationship as the above equation (2), T _end (3T) ≦ T _end (4T) ≦ T _end (5T) ≦ ... ≦ T _end (10T) ≦ T _end (11T) ≦ T _end (14T) (V) (however, not all inequalities become = in (V)). However, if you set longer as T _{end The} (nT) data mark length nT is increased, the rear space by mark length - since there is a case where the scan difference increases jitter deteriorates, the control amount of the T _{end The} (nT) Some restrictions are required. In this case, the relation of the equation (V) is set to an appropriate range, and the top pulse irradiation time T _top (xT) is set.

[0037]

[Equation 7] T _top (3T) ≦ T _top (4T) ≦ T _top (5T) ≦ ... ≦ T _top (10T) ≦ T _top (11T) ≦ T _top (14T)... (4) This makes it possible to improve the deviation of the mark and to prevent the deterioration of the jitter due to the increase of the post-mark difference due to the recording mark length (however, in equation (IV), all inequality signs do not become =). Of course,
The relationship of the formula (IV) or the relationship of the formula (V) may be used alone. In the above description, all pulse irradiation times are based on the pulse irradiation end time, that is, the first pulse irradiation completion time te _top (nT) and the last pulse irradiation completion time te
_end (nT) is fixed, and the first pulse irradiation time T _top and the last pulse irradiation time T _end are set to the first pulse irradiation start time ts
_The case where the control is performed by changing the _top (nT) and the final pulse irradiation start time ts _end (nT) has been described. However, this is merely an example, and the reference of the pulse irradiation position may be set anywhere.

The recording material having a small decomposition promoting effect according to the present invention means that the time difference between the recording laser irradiation start time and the recording laser irradiation completion time and the data mark length difference are within the range of the data mark length to be recorded with the same recording pattern. In the above, when recording is performed using a recording strategy having a constant value, a material that is recorded shorter as a long mark is a general term, and many porphyrin derivatives are included in a recording material having a small decomposition promoting effect.

R _{1 to} R ₂₄ and X _{1 to} X ₄ in the porphyrin derivative used in the present invention each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, It represents a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group.

Examples of the unsubstituted alkyl group and the alkyl group in the unsubstituted alkoxy group include a linear or branched alkyl group. As the substituted alkyl group and the substituted alkyl group in the substituted alkoxy group, Is a hydroxy-substituted alkyl group such as a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, and a 2-hydroxypropyl group; a carboxy group such as a carboxymethyl group, a 2-carboxyethyl group, and a 3-carboxypropyl group; Substituted alkyl group; cyano-substituted alkyl group such as 2-cyanoethyl group and cyanomethyl group; amino-substituted alkyl group such as 2-aminoethyl group; 2-chloroethyl group;
-Chloropropyl group, 2-chloropropyl group, 2,2,
Halogen-substituted alkyl groups such as 2-trifluoroethyl group; phenyl-substituted alkyl groups such as benzyl group, p-chlorobenzyl group and 2-phenylethyl group; 2-methoxyethyl group, 2-ethoxyethyl group, 2- ( n) propoxyethyl group, 2- (iso) propoxyethyl group,
2- (n) butoxyethyl group, 2- (iso) butoxyethyl group, 2- (2-ethylhexyloxy) ethyl group, 3-methoxypropyl group, 4-methoxybutyl group,
Alkoxy-substituted alkyl group such as 2-methoxypropyl group; 2- (2-methoxyethoxy) ethyl group, 2- (2
-Ethoxyethoxy) ethyl group, 2- (2- (n) propoxyethoxy) ethyl group, 2- (2- (iso) propoxyethoxy) ethyl group, 2- (2- (n) butoxyethoxy) ethyl group, 2 An alkoxyalkoxy-substituted alkyl group such as-(2- (iso) butoxyethoxy) ethyl group, 2- {2- (2-ethylhexyloxy) ethoxy} ethyl group; allyloxyethyl group, 2-phenoxyethyl group, 2-benzyl A substituted alkyl group such as an oxyethyl group; a 2-acetyloxyethyl group, a 2-propionyloxyethyl group, a 2- (n) butyryloxyethyl group,
Acyloxy-substituted alkyl groups such as 2- (iso) butyryloxyethyl group and 2-trifluoroacetyloxyethyl group; methoxycarbonylmethyl group, ethoxycarbonylmethyl group, (n) propoxycarbonylmethyl group,
(Iso) propoxycarbonylmethyl group, (n) butoxycarbonylmethyl group, (iso) butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, furfuryloxycarbonylmethyl group, tetrahydrofurfuryloxycarbonyl Methyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2- (n) propoxycarbonylethyl group, 2- (iso) propoxycarbonylethyl group, 2- (n) butoxycarbonylethyl group, 2- ( iso) a substituted or unsubstituted alkoxy group such as a butoxycarbonylethyl group, a 2- (2-ethylhexyloxycarbonyl) ethyl group, a 2-benzyloxycarbonylethyl group, or a 2-furfuryloxycarbonylethyl group; Bonyl-substituted alkyl group; 2-methoxycarbonyloxyethyl group, 2-ethoxycarbonyloxyethyl group, 2- (n) propoxycarbonyloxyethyl group, 2- (iso) propoxycarbonyloxyethyl group, 2- (n) butoxycarbonyl Substitution of an oxyethyl group, a 2- (iso) butoxycarbonyloxyethyl group, a 2- (2-ethylhexyloxycarbonyloxy) ethyl group, a 2-benzyloxycarbonyloxyethyl group, a 2-furfuryloxycarbonyloxyethyl group, or An unsubstituted alkoxycarbonyloxy-substituted alkyl group; and a heterocyclic-substituted alkyl group such as a furfuryl group and a tetrahydrofurfuryl group.

The cycloalkyl group includes a cyclopentyl group, a cyclohexyl group and the like.

The following are specific examples of the alkyl group in the alkyl group and the alkoxy group. Note that these alkyl groups may be substituted with a substituent such as a halogen atom. Methyl group, ethyl group, n
-Propyl, n-butyl, isobutyl, n-pentyl, neopentyl, isoamyl, 2-methylbutyl, n-hexyl, 2-methylpentyl, 3-
Methylpentyl group, 4-methylpentyl group, 2-ethylbutyl group, n-heptyl group, 2-methylhexyl group, 3
-Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, n-octyl group, 2-methylheptyl group, 3-
Primary alkyl groups such as methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 2-ethylhexyl group, 3-ethylhexyl group, n-nonyl group, n-decyl group and n-dodecyl group; isopropyl group, sec -Butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1,
2-dimethylpropyl group, 1-methylheptyl group, 1-
Ethylbutyl group, 1,3-dimethylbutyl group, 1,2-
Dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1-methylhexyl group, 1-ethylheptyl group, 1
-Propylbutyl group, 1-isopropyl-2-methylpropyl group, 1-ethyl-2-methylbutyl group, 1-propyl-2-methylpropyl group, 1-methylheptyl group,
1-ethylhexyl group, 1-propylpentyl group, 1-
Isopropylpentyl group, 1-isopropyl-2-methylbutyl group, 1-isopropyl-3-methylbutyl group,
Secondary alkyl groups such as 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3-methylbutyl group; tert-butyl group, tert
Tertiary alkyl groups such as -hexyl group, tert-amyl group and tert-octyl group; cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4
And cycloalkyl groups such as -tert-butylcyclohexyl group, 4- (2-ethylhexyl) cyclohexyl group, bornyl group, isobornyl group and adamantane group.

Examples of the aryl group include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, tert-butylphenyl, di (tert-butyl) phenyl, butylphenyl, and methoxyphenyl. And a dimethoxyphenyl group, a trimethoxyphenyl group, a butoxyphenyl group, and the like. These aryl groups may be substituted with a substituent such as halogen.

In the formulas (1) to (16), M is two hydrogen atoms (wherein chemical formulas (10) to (14) are three hydrogen atoms) or divalent or trivalent which may have oxygen or halogen. Value, or 4
Valent metal atom, or (OR _a ) p, (OSiR _b R
_c R _d ) q, (OPOR _e R _f ) r, and a metal atom which may have (OCOR _g ) s. R _{a to} R _{g each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 2. Specifically, M includes Ib group, IIa group, IIb group, IIIa group, IVa group, I
Group Vb, Vb, VIb, VIIb, and VIII metals, oxides of these metals, halides of these metals, hydroxides of these metals, and the like. Some have. The above metals include C
u, Zn, Mg, Al, Ge, Ti, Sn, Pb, C
r, Mo, Mn, Fe, Co, Ni, In, Pt, Pd
And oxides such as TiO and VO, and halides such as AlCl, GeCl _{2 ,} SiCl ₂ , and the like.
There are FeCl, SnCl ₂ , InCl and the like, and hydroxides are Al (OH), Si (OH) ₂ , Ge (OH) ₂ , Sn (O
H) ₂ etc. Further, when the metal has a substituent,
Examples of the metal include Al, Ti, Si, Ge, and Sn, and examples of the substituent include an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, and a triaryloxy group. Examples include a siloxyl group, a trityloxyl group, and an acyloxyl group.

[0045]

EXAMPLES First, it was confirmed that the longer the recording mark of the porphyrin derivative, the longer the mark. Thickness 0.6mm, track pitch 0.74 (μ
m) on a polycarbonate substrate (for 4.7 GB), a porphyrazine compound of the following formula (17) and the following formula (1)
The azo metal complex of 8) was formed into a film by spin coating, and a gold reflective layer and a protective layer made of an ultraviolet-curable resin were further provided thereon by sputtering to prepare an optical recording medium. The recording / reproducing device is DDU-1000 manufactured by Pulstec Industrial.
(Wavelength: 635 (nm), NA: 0.60). For recording, a strategy as shown in FIG.
Only a 14T mark was recorded at a recording power of 11.0 (mw) with a multipulse length of 00 (T) and a multipulse length of 0.60 (T).

[0046]

Embedded image

[0047]

Embedded image

This result shows that, as shown in FIG. 6, the porphyrazine compound, which is clearly a porphyrin derivative,
The length of the recorded mark is shorter than that of the azo metal complex, and the position of the slice level is not at the level determined to be shorter than the long mark due to asymmetry deviation, etc., but the mark is recorded physically shorter. It is clear that.

Next, on a polycarbonate substrate having a thickness of 0.6 mm and a track pitch of 0.74 (μm) (4.7 G
B), a porphyrazine compound represented by the following formula (19) or the following formula (20) is formed into a film by spin coating, and a gold reflective layer and a protective layer made of an ultraviolet curable resin are further provided thereon by sputtering, and optical recording is performed. Created media. The recording / reproducing apparatus is a DDU1000 (wavelength 63
5 (nm), NA 0.60), and the jitter was measured using a time interval analyzer TA320 manufactured by Yokogawa Electric Corporation.

[0050]

Embedded image

[0051]

Embedded image

The DVD Spec of the compound of the formula (19)
ifations for Recordable
Disk (DVD-R) Part 1 PHYSI
CAL SPECIFICATIONS Version
n 1.0 July 1997
The optimum condition in c Strategies is that when the recording power is 11.0 (mw), 1.04-1.00-0.5
4, a DVD of the compound of formula (20)
Specifications for Recor
double Disk (DVD-R) Part 1
PHYSICAL SPECIFICATIONS V
optimal 1.0 in Basic Strategy described in version 1.0 July 1997 is as follows:
When the recording power is 11.5 (mw), 1.01-1.0
0-0.56 (see Table 2).

[0053]

[Table 1]

[0054]

[Table 2] Jitter under this optimum recording condition (Data to Cloth)
ck Jitter) is a compound of formula (19).
9%, and the compound of the formula (20) was 10.6%. In addition, detailed playback conditions are DVD Specific.
ations for Recordable Dis
k (DVD-R) Part 1 PHYSICAL
SPECIFICATIONS Version 1.
0 The specified value described in July 1997 was used.
As a result of measuring the deviation of the mark under the optimum recording conditions, the compound of the formula (19) obtained the result as shown in FIG. 7, and the compound of the formula (20) obtained the result as shown in FIG. . Both the compounds of the formulas (19) and (20) are DVD
Specifications for Recor
double Disk (DVD-R) Part 1P
HYSICAL SPECIFICATIONS Ve
Rsion 1.0 July B described in July 1997
Although very good jitter values can be obtained with the asic strategy, it has been confirmed that long marks such as 11T and 14T are shorter than the theoretical value (the deviation from the theoretical value increases as the mark length increases). .

Next, the effect of the recording strategy provided by the present invention was confirmed. The strategy as shown in Table 3 was used for the compound of formula (19), and the strategy as shown in Table 4 was used for the compound of formula (20).

[0056]

[Table 3]

[0057]

[Table 4] T _top in Tables 1-4 is the irradiation time of the top pulse, T _mp
Is the irradiation time of the multi-pulse, and T _end is the irradiation time of the last pulse. In Tables 1 to 4, the data mark lengths nT (= T _wd ) and T _int (Ts _top and Te _end ) defined in the present invention, together with T _top , T _mp and T _end in FIG.
(Time difference). Using the strategies shown in Tables 2 and 4, the deviation of the mark was measured. Note that the recording power of Expression (19) is 11.0 (mw)
And the recording power of the compound of the formula (20) is 11.5
(Mw).

The results are as shown in FIG. 8 for the compound of the formula (19) and FIG. 10 for the compound of the formula (20). By using the strategy of the present invention, the DVD Sp
educations for Recordab
le Disk (DVD-R) Part 1 PHYS
ICAL SPECIFICATIONS Versi
on 1.0 July 1997
The deviation of the mark became very small as compared with the recording in the ic strategy. As described above, the data mark length nT (= T _wd ) and T _int specified in the present invention.
It became clear that the deviation of the mark can be improved by shortening the difference between (Ts _top and Te _end ) as the data mark length increases. Further, using the strategies shown in Tables 2 and 4, the jitter when the recording power was changed was measured.

FIG. 11 shows the result of equation (19), and FIG. 12 shows the result of equation (20). The abscissas in FIGS. 11 and 12 represent the recording power normalized by the optimum recording power (the optimum recording power of the compound of the formula (19) is 11.0).
(Mw), and the optimum recording power of the compound of the formula (20) is 11.5 (mw)). As a result, the minimum jitter of the compound of the formula (19) is 10.2%, and the minimum jitter of the compound of the formula (20) is 9.8%, and the data mark length nT (= T _wd ) and T _int (Ts _top
It has been found that the jitter as well as the deviation of the mark can be improved by shortening the difference between the data mark length and the time difference of Te _end as the data mark length increases. In this example, the effectiveness of the strategy of the present invention in a porphyrazine compound was shown. Since the basic skeleton structure is the same and the decomposition behavior in thermogravimetric analysis is similar, a similar effect can be obtained by the strategy of the present invention.

[0060]

As apparent from the detailed and specific explanations above, an optical recording medium using a recording material having a small decomposition promoting effect of the present invention as a recording layer, or an optical recording medium using a porphyrin derivative as a recording layer. According to the medium, there is no mark deviation problem, an optical recording medium excellent in jitter can be provided, and a recording method for an optical recording medium using a recording material having a small decomposition promoting effect of the present invention as a recording layer, or a porphyrin derivative. By using the recording method for the optical recording medium used as the recording layer, it is possible to provide an optical recording medium having no mark deviation problem and excellent jitter, and the present invention has a very rich variation of the basic skeleton and the substituent. A porphyrin derivative that can widely correspond to a red region to a blue region as a recording / reproducing wavelength is widely used as an optical recording medium. It is intended to achieve the excellent effect that it is possible to apply.

[Brief description of the drawings]

FIG. 1 shows one Basic Stra in the prior art.
It is a figure showing a tee.

FIG. 2 is a diagram showing a 1-azo metal complex in the prior art.

FIG. 3 is a diagram showing a porphyrazine compound which is a 1-porphyrin derivative in the prior art.

FIG. 4 is a diagram showing one recording pattern used in the present invention.

FIG. 5 is a diagram showing a strategy in the related art.

FIG. 6 is a view showing one recording mark of a porphyrin derivative in the present invention.

FIG. 7 is a diagram showing a result of measurement of a mark deviation using a strategy according to the present invention.

FIG. 8 is another diagram showing the result of measuring the deviation of a mark using the strategy in the present invention.

FIG. 9 is yet another diagram showing the result of measuring the deviation of a mark using the strategy in the present invention.

FIG. 10 is still another view showing the result of mark deviation measurement using the strategy in the present invention.

FIG. 11 is a diagram showing a result of measuring jitter when recording power is changed using a strategy according to the present invention.

FIG. 12 is another diagram showing the result of measuring the jitter when the recording power is changed using the strategy in the present invention.

Claims (13)

[Claims] 1. A time difference between a recording laser irradiation start time and a recording laser irradiation completion time and a data mark length difference are shortened as the data mark length becomes longer within a range of the data mark length to be recorded by the same recording pattern. An optical recording medium characterized by having been recorded by recording. 2. In an optical recording medium having a recording layer mainly composed of a porphyrin derivative, a time difference between a recording laser irradiation start time and a recording laser irradiation completion time and a data mark length difference are the data mark lengths to be recorded in the same recording pattern. An optical recording medium characterized in that the recording is shortened as the data mark length increases within the range of (1). 3. The optical recording medium according to claim 2, wherein the porphyrin derivative is a naphthalocyanine compound represented by the following formula (1). Embedded image (R _{1 to} R ₂₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group Represents a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or tetravalent metal atom optionally having oxygen or halogen, Or (OR ₂₅ ) p, (OSiR ₂₆ R ₂₇ R ₂₈ ) q,
(OPOR ₂₉ R ₃₀ ) r represents a metal atom which may have (OCOR ₃₁ ) s. R _{25 to} R ₃₁ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group,
p, q, r, and s represent an integer of 0 to 2. ) 4. The optical recording medium according to claim 2, wherein the porphyrin derivative is a phthalocyanine compound represented by the following formula (2). Embedded image (R _{1 to} R ₁₆ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group Represents a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or tetravalent metal atom optionally having oxygen or halogen, Or (OR ₁₇ ) p, (OSiR ₁₈ R ₁₉ R ₂₀ ) q,
(OPOR ₂₁ R ₂₂ ) r represents a metal atom which may have (OCOR ₂₃ ) s. R _{17 to} R ₂₃ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group,
p, q, r, and s represent an integer of 0 to 2. ) 5. The optical recording medium according to claim 2, wherein the porphyrin derivative is a porphyrazine compound represented by the following formula (3). Embedded image (R _{1 to} R ₈ are each independently a hydrogen atom, a halogen atom,
Nitro group, cyano group, hydroxyl group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted amino group, substituted or unsubstituted acyl group Represents M is two hydrogen atoms, or a divalent, trivalent or tetravalent metal atom which may have oxygen or halogen,
Or (OR ₉ ) p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OP
OR ₁₃ R ₁₄ ) represents a metal atom which may have r (OCOR ₁₅ ) s. R _{9 to} R ₁₅ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, p, q,
r and s represent an integer of 0 to 2. ) 6. The optical recording medium according to claim 2, wherein the porphyrin derivative is a porphyrin compound represented by the following formula (4). Embedded image (R _{1 to} R ₈ and X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. 7. The optical recording medium according to claim 2, wherein the porphyrin derivative is a porphycene compound represented by the following formulas (5) to (9). Embedded image Embedded image Embedded image Embedded image Embedded image (R _{1 to} R ₈ and X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. 8. The porphyrin derivative represented by the following formula (1)
The optical recording medium according to claim 2, wherein the optical recording medium is a corrole compound represented by any one of (0) to (14). Embedded image Embedded image Embedded image Embedded image Embedded image (R _{1 to} R ₈ and X _{1 to} X ₃ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents three hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. ) 9. The porphyrin derivative according to the following formula (1)
The optical recording medium according to claim 2, wherein the optical recording medium is a monoazaporphyrin compound represented by (5). Embedded image (R _{1 to} R ₈ and X _{1 to} X ₃ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R _{15 each} independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s each represent an integer of 0 to 2. ) 10. The optical recording medium according to claim 2, wherein the porphyrin derivative is a diazaporphyrin compound represented by the following formula (16). Embedded image (R _{1 to} R ₈ and X _{1 to} X ₂ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or M represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group, M represents two hydrogen atoms, or a divalent, trivalent, or oxygen- or halogen-containing group; Tetravalent metal atom, or (OR ₉ ) p, (OSiR ₁₀ R
₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R ₁₅ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 2. ) 11. The time difference between the recording laser irradiation start time and the recording laser irradiation completion time and the difference between the data mark lengths are shortened as the data mark length increases within the range of the data mark length to be recorded with the same recording pattern. A recording method for an optical recording medium having a recording layer comprising a porphyrin derivative according to any one of claims 1 to 10, wherein the recording is performed by recording. 12. A recording method using a recording strategy comprising at least a first pulse portion and a last pulse portion,
11. The recording method for an optical recording medium having a recording layer comprising a porphyrin derivative according to any one of claims 1 to 10, wherein recording is performed by increasing the irradiation time of the first pulse as the data mark length increases. 13. A recording method using a recording strategy comprising at least a first pulse portion and a last pulse portion,
11. The recording method for an optical recording medium having a recording layer comprising a porphyrin derivative according to any one of claims 1 to 10, wherein recording is performed with the last pulse irradiation time lengthened as the data mark length increases.