Optical information recording medium

• US 4,900,648 A
• Filed: 02/26/1988
• Issued: 02/13/1990
• Est. Priority Date: 02/27/1987
• Status: Expired due to Term

• Current Assignee: Fujifilm Corporation (Fujifilm Holdings Corporation)
• Original Assignee: Fuji Photo Film Co Limited (Fujifilm Holdings Corporation)
• Inventors: Hioki, Takanori, Inagaki, Yoshio, Yabe, Masao
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): Buscher, Mark R.
• Application Number:
  US07/161,475
• Time in Patent Office: 718 Days
• Field of Search: 430/270, 430/495, 430/945, 430/75, 430/76, 430/77, 430/78, 346/135.1
• US Class Current: 430/270.19
• CPC Class Codes: C09B 23/02 the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
• CPC Class Codes: C09B 23/10 The polymethine chain containing an even number of >CH- groups styryl dyes C09B23/14, C09B23/14 takes precedence
• CPC Class Codes: Y10S 430/146 Laser beam

Abstract

The present invention relates to an optical information recording medium for carrying out recording, reproduction and erasing with laser beams which comprises a support having carried thereon at least one methine dye which consists of an azulene nucleus, at least one of 10 carbon atoms of which is replaced by chalcogen atom(s) and/or nitrogen atom(s), and further whose 7-membered ring part is substituted with a methine bond having at the terminal an auxochrome which forms a conjugated resonance chromophore together with a 10 π electron system of the nucleus.

Optical information recording media of the invention have adequate recording characteristics having high C/N, and have high stabilities against long-term preservation or against long-time reading.

Claims

1. An optical information recording medium for carrying out recording and reproduction with laser beams which comprises a support having carried thereon at least one methine dye which comprises an azulene nucleus, at least one of the two carbon atoms at the 1 and 3 positions of which is replaced by a chalcogen atom or a nitrogen atom, and further whose 7-membered ring part is substituted with a methine bond having at the terminal an auxochrome which forms a conjugated resonance chromophore together with a 10 π

electron system of the nucleus.

2. The optical information recording medium of claim 1, wherein when both carbon atoms at the 1- and 3-positions of the azulene nucleus are replaced by a chalcogen atom or a nitrogen atom, at least one of the replacing atoms is a nitrogen atom.

3. The optical information recording medium of claim 1, wherein the methine dye is represented by the following general formula (I):

##STR109## wherein E represents an auxochrome;

L represents a methine bond;

V₁, V₂, V₃, V₄ and V₅ independently represent hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, acyl groups, acyloxy groups, substituted or unsubstituted alkoxycarbonyl groups, substituted or unsubstituted carbamoyl groups, substituted or unsubstituted sulfamoyl groups, carboxyl groups, cyano groups, hydroxyl groups, amino groups, acylamino groups, substituted or unsubstituted alkoxy groups, alkylthio groups, alkylsulfonyl groups, sulfonic acid groups, or aryl groups, or alternatively two of V₁ to V₅ linking to adjacent carbon atoms may combine to form a condensed ring;

Y represents ##STR110## (wherein V has the same meaning as V₁, V₂, V₃, V₄ and V₅) or a nitrogen atom, Z represents ##STR111## (wherein V has the same meaning as V₁, V₂, V₃, V₄ and V₅), a chalcogen atom or a nitrogen atom, provided that Y and Z do not represent carbon atoms at the same time;

M represents a counter ion for charge balance, m is a number of 0 or more necessary for the balance of charge; and

bonding position of a methine bond L is representatively expressed as the 6-position in the formula (I), but may also be expressed as the 4-, 5-, 7- or 8-position.

4. The optical information recording medium of claim 3, wherein Z represents ##STR112## and R₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic ring group.

5. The optical information recording medium of claim 4, wherein R₁ is an unsubstituted alkyl group having 18 or less carbon atoms, or a sulfoalkyl group.

6. The optical information recording medium of claim 3, wherein the methine dye is represented by one of the following formula (II) to (IX):

##STR113## wherein V₁ to V₅, Y, Z, M and m have the same meanings as those in the general formula (I);

position of the methine bond may be any of the 4-, 5-, 6-, 7- and 8-positions, as is in the general formula (I);

Q₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing ring;

L₁, L₂, L₃, L₄ and L₅ each represent methine groups which may optionally be substituted;

R₂ represents a substituted or unsubstituted alkyl group;

l represents an integer of 0 to 3; and

n₁ represents 0 or 1;

##STR114## wherein V₁ to V₅, Y, Z, M and m have the same meanings as those in the general formula (I);

position of the methine bond may be any of the 4-, 5-, 6-, 7- and 8-positions, as is in the general formula (I);

Q₂ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing ring;

L₆, L₇, L₈, L₉ and L₁₀ have the same meanings with L₁, L₂, L₃, L₄ and L₅ ;

R₃ represents a substituted or unsubstituted alkyl group;

l₂ represents an integer of 0 to 3; and

n₂ represents 0 or 1;

##STR115## wherein V₁ to V₅, Y, Z, M and m have the same meanings as those in the general formula (I);

Y'"'"' and Z'"'"' have the same meanings with Y an Z, respectively;

position of the methine bond may be any of the 4-, 5-, 6-, 7- and 8-positions;

V₁ '"'"' to V₅ '"'"' have the same meanings with V₁ to V₅, respectively;

L₁₁, L₁₂ and L₁₃ have the same meanings with L₁, L₂, L₃, L₄ and L₅ ; and

l₃ represents an integer of 0 to 3;

##STR116## wherein V₁ to V₅, Y, Z, M and m have the same meanings as those in the general formula (I);

position of the methine bond may be any of the 4-, 5-, 6-, 7- and 8-positions, as is in the general formula (I);

D₁ and D₁ '"'"' each represent atomic groups necessary for forming an acidic nucleus, and may be non-cyclic or cyclic;

L₁₄, L₁₅, L₁₆ and L₁₇ have the same meanings with L₁, L₂, L₃, L₄ and L₅ ;

l₄ represents an integer of 0 to 3; and

n₃ represents 0 or 1;

##STR117## wherein V₁ to V₅, Y, Z, M and m have the same meanings as those in the general formula (I);

position of the methine bond may be any of the 4-, 5-, 6-, 7- and 8-positions, as is in the general formula (I);

R₄ and R₅ represent substituents known in general tertiary amines, and R₄ and R₅ may combine to form a ring;

L₁₈ and L₁₉ have the same meanings with L₁, L₂, L₃, L₄ and L₅ ; and

l represents an integer of 0 to 3;

##STR118## wherein E and E'"'"' each is E₁ or E₂, provided that at least one of E and E'"'"' is E₁ ;

V₁ to V₅, Y, Z, M and m have the same meanings as those in the general formula (I);

positions of the methine bond in E₁ may be any of the 4-, 5-, 6-, 7- and 8-positions, as is in the general formula (2);

W₁ represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring;

R₆ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a heterocyclic group;

Q₃ and R₇ have the same meanings with Q₁ and R₂ in the general formula (II), respectively;

L₂₀, L₂₁, L₂₂, L₂₃, L₂₄, L₂₅ and L₂₆ have the same meanings with L₁, L₂, L₁₃, L₁₄ and L₅ ;

l₆ and l₇ are integers of 0 to 3; and

n₄ is 0 or 1;

##STR119## wherein V₁ to V₅, Y, Z, M and m have the same meanings as those in the general formula (I);

position of the methine bond may be any of the 4-, 5-, 6-, 7- and 8-positions, as is in the general formula (I);

W₂ has the same meaning with W₁ ;

R₈ has the same meaning with R₆ ;

D₂ and D₂ '"'"' have the same meanings with D₁ and D₁ '"'"' in the general formula (V), respectively;

L₂₇, L₂₈, L₂₉, L₃₀, L₃₁ and L₃₂ have the same meanings with L₁, L₂, L₃, L₄ and L₅ ;

l₈ and l₉ are integers of 0 to 3; and

n₅ represents 0 or 1;

##STR120## ##STR121## wherein V₁ to V₅, Y, Z, M and m have the same meanings as those in the general formula (I);

position of the methine bond may be any of the 4-, 5-, 6- and 8-positions, as is in the general formula (I);

L₃₃ and L₃₄ have the same meanings with L₁, L₂, L₃, L₄ and L₅ ;

Ar represents an aromatic group; and

l₁₀ represents an integer of 0 to 3.

7. The optical information recording medium of claim 6, wherein V₁, V₂, V₃, V₄, V₅, V₁ '"'"', V₂ '"'"', V₃ '"'"', V₄ '"'"' and V₅ '"'"' independently represents hydrogen atoms, halogen atoms selected from the group consisting of chlorine atoms, fluorine atoms, and bromine atoms, unsubstituted alkyl groups having 10 or less carbon atoms, substituted alkyl groups having 18 or less carbon atoms, acyl groups having 10 or less carbon atoms, acyloxy groups having 10 or less carbon atoms, substituted or unsubstituted alkoxycarbonyl groups, substituted or unsubstituted carbamoyl groups, substituted or unsubstituted sulfamoyl groups, carboxyl groups, cyano groups, hydroxyl groups, amino groups, acylamino groups having 8 or less carbon atoms, substituted or unsubstituted alkoxy groups having 10 or less carbon atoms, alkylthio groups, alkylsufonyl groups, sulfonic acid groups or aryl groups.

8. The optical information recording medium of claim 6, wherein Q₁ or Q₂ comprises a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thiazoline nucleus, an oxazole nucleus, an oxazoline nucleus, a selenazole nucleus, a selenazoline nucleus, a tellurazole nucleus, a tellurazoline nucleus, a 3,3-dialkylindolenine nucleus, an imidazole nucleus, a pyridine nucleus, a quinoline nucleus, an imidazo(4,5-b)-quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus and a pyrimidine nucleus.

9. The optical information recording medium of claim 6, wherein R₂, R₃ and R₇ are selected from the group consisting of an unsubstituted alkyl group having 18 or less carbon atoms and a substituted alkyl group.

10. The optical information recording medium of claim 6, wherein D₁ and D₁ '"'"' or D₂ and D₂ '"'"' combine to form a nucleus comprising 1,3-dialkylbarbituric acid, 1,3-dialkyl-2-thiobarbituric acid or 3-alkylrhodanine.

11. The optical information recording medium of claim 6, wherein R₄ and R₅, which may be the same or different, comprise unsubstituted alkyl groups each having 18 or less carbon atoms, substituted alkyl groups, cyano groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, or R₄ and R₅ may combine together to form a heterocyclic ring with the proviso that the heterocyclic ring is not an aromatic heterocyclic ring.

12. The optical information recording medium of claim 1, which comprises a recording layer as the dye layer and a subbing layer provided on the support, a protective layer provided on the recording layer, and/or a reflecting layer provided on the support or on the recording layer.

13. The optical information recording medium of claim 1, wherein a single oxygen quencher is further carried thereon.

14. The optical information recording medium of claim 13, wherein the quencher is contained in the recording layer.

15. The optical information recording medium of claim 13, wherein the quencher is used in an amount of 0.05 to 12 moles per 1 mole of the methine dye(s).

16. The optical information recording medium of claim 1, wherein the film thickness of the recording layer is 0.01 to 2 μ

m.

17. The optical information recording medium of claim 1, wherein the chalcogen atom is selected from the group consisting of oxygen, sulfur, selenium and tellurium atoms.

18. The optical information recording medium of claim 1, further comprising a quencher represented by formulae (XXI) and (XXII):

##STR122## wherein (Cat₁) and (Cat₂) each represent a cation necessary for making each compound neutral, M₁ and M₂ each represent nickel, copper, cobalt, palladium or platinum, and n represents 1 or 2.

19. The optical information recording medium of claim 18, wherein the cations (Cat₁) and (Cat₂) are represented by formulae (XXIII-a), (XXIII-b), (XXIII-c), (XXIII-d) or (XXIII-e):

##STR123## wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² each represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and Z¹ and Z² each represent a nonmetal atomic group which forms a 5-membered or a 6-membered ring together with a nitrogen atom or a phosphorus atom in each formula.

20. The optical information recording medium of claim 18, wherein the quencher of formula (XXI) is selected from the group consisting of (XXI-1), (XXI-2), (XXI-3) and (XXI-4):

##STR124##