JPS59171690A - Optical recording medium - Google Patents

Abstract

PURPOSE:An optical recording medium of the heat mode or the like enhanced in S/N ratio, preservability and heat resistance and reduced in deterioration on erasing, wherein a recording layer comprising a petroleum resin and a dye is provided on a base. CONSTITUTION:The recording layer comprising a petroleum resin (a 5C base resin, a 9C base resin, a 5-9C copolymer base resin or a cyclopentadiene base resin preferably having a number average molecular weight of 500-3,000, a softening point of 40-200 deg.C and a bromine value of not larger than 200) and a dye (preferably, a carbocyanine dye) and optionally comprising a quencher (preferably, a transient metal chelated compound) is provided on the base to obtain the objective optical recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to an optical recording medium, particularly a heat mode optical recording medium.

Optical technology Optical recording media have the characteristic that the recording medium does not deteriorate due to wear and tear because there is no contact between the medium and the reading or reading head.For this reason, research and development of various optical recording media are being carried out. .

Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing using a filling chamber.

This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium to form a pit. Some devices perform writing by forming small holes, record information using the pits, and read out information by detecting the pits with readout light.

As an example of such pit-forming media,
There is known a method in which a recording layer made of a thermal 5f plastic resin and a light-absorbing dye is coated on a substrate, and the recording layer is melted to form pits.

It has been confirmed that such a medium can be erased by refilling the once formed pits and flattening the surface of the recording layer using heat or light, and then writing and reading can be performed again.

However, when forming a recording layer using a dye and a normal thermo-++7 plastic resin, such as polystyrene,
In particular, it is insufficient in terms of compatibility.

Therefore, when the medium is stored for a long time, the aging sensitivity, read S/N ratio, etc. deteriorate.

Also, the read S/N ratio is low.

Furthermore, since heat resistance is low, sensitivity and S/N ratio deteriorate even with heat.

In addition, repeated erasing causes significant erasure deterioration in which sensitivity and S/N ratio decrease.

Then, by repeatedly irradiating the readout light, the S/N
There is also a disadvantage that the Jf ratio deteriorates significantly, and the sensitivity and S/N ratio deteriorate when exposed to light.

■■ Purpose of the Invention The present invention has been made in view of the above-mentioned circumstances, and its second purpose is to provide an optical recording medium that thermally irritates a recording layer consisting of a plastic resin and a carbocyanine dye. The objective is to improve the read S/N ratio, improve storage stability, improve heat resistance, and reduce erase deterioration.

The second invention has achieved these objects and further aims to reduce playback deterioration and improve the light resistance of the beak.

Such objects are achieved by the invention described below.

That is, the first invention is an optical recording medium characterized in that a recording layer 41 containing a petroleum resin and a dye is formed on a substrate.

A second invention is an optical recording medium characterized in that it has a recording layer on a substrate that includes a petroleum resin, a dye, and a quencher.

m Specific configuration of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

A dye is contained in the recording layer of the optical recording medium of the present invention.

There are no particular restrictions on the dyes to be used, including carbocyanine, phthalocyanine, naphculocyanine, anthraquinone, choline or chorol, azo, triphenylmethane, pyrylium or thiapyrylium salts,
It may be either azomethine type, styryl type, etc.

However, if the dye is a carbocyanine dye, the effects of the present invention will be even greater.

Among the carbocyanine dyes, those represented by the following formula (1) are preferred.

In the formula (I) Φ-L-heavy (X-) (formula CI), ψ and Φ are an indole ring to which an aromatic ring, such as a '-nzene ring, a naphthalene ring, a phenanthrene ring, etc., may be fused; Includes thiazole ring, oxazole ring, selenazole ring, imidazole ring, pyridine ring, etc.

These Φ and ψ may be the same or different, but
They are usually the same, and various substituents may be bonded to these rings.

Note that Φ indicates that the nitrogen atom in the ring has ten charges, and ψ indicates that the nitrogen atom in the ring is neutral.

As these Φ and flat skeletal rings, the following formula [Φ]
It is preferable that it is represented by ~[Φdouble].

In addition, in the following, the structure is shown in the form of Φ.

1 [ΦII) R2(
R4) q 1 [Φ■] (R4) q 1 [Φ■] ■ 1 1 R1 1 [Φtwin] R1' A1 In these various rings, nitrogen atoms in the ring (in the imitasol ring, two nitrogen atomsノ+'lR+ that binds to atom)
(R+, R+') is a substituted or unsubstituted alkyl group (or aryl group).

bonded to the nitrogen atom in such a ring), (R1, R1
There is no particular restriction on the number of carbon WX atoms in '.

In addition, this), (if it further has a substituent, the substituent is sulfonic acid),! , an alkylcarbonyloxy group, an alkylamide group, an alkylsulfonamide group, an alkoxyoxy group, an alkylanino group, an alkylcarbamoyl group, an alkylsulfamoyl group, an alkylcarbonyl group, a halogen atom, etc.

Note that when m described below is O, J(R) bonded to the nitrogen atom in Φ is a substituted alkyl or aryl group and has a charge at -.1'.

For example, if the rings of Φ and ψ are fused or non-fused,
- If it is a ring (formula (Φwork) ~ [ΦIV)'),
At the 3rd position there are two substituents R2.

Preferably, R3 is bonded. In this case, it is preferable that the two substituents R2 and R3 which are bonded to the 3rd position are an alkyl group or an aryl group. Among these, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred.

On the other hand, at a predetermined position in the ring represented by Φ and weight,
Furthermore, another substituent R4 may be bonded. Such substituents include various substituents such as alkylno, (, aryl group, heterocyclic residue, halogen atom, alkoxy group, alkylthio group, alkyloxycarbonyl group, alkylcarbonyloxy group, carboxylic acid group, etc.). and the number of these substituents (p, q.

r, s, t) are usually 0 or about 1 to 4. Note that when p, q, r, S, and t are 2 or more, the plurality of R4s may be different from each other.

Among these, those having a fused or non-fused indole ring of the formulas [Φ■] to [Φ■] are preferred. This is because these materials have excellent coating properties and stability, exhibit extremely high reflectance, and have an extremely high readout C/N ratio.

On the other hand, L represents a linking group that forms a mono-, di-, tri- or tetracarbocyanine dye, and in particular, a linking group of the formula (L
Any one of I) to [L■] is preferable.

Formula (LI) CH= CH-C)l= C)l-C= CH-CH=
CH-C)1 formula (LII) C:)l=cH-CH
=(, -CH=CH-CH formula (Lm) formula (LrV) CH3(JJ3 ■ formula (LVII[) CH-C=CH-CH where, Y
represents a hydrogen atom or a monovalent group. In this case, 1
Examples of the valent group include lower alkyl groups such as methylpenta, lower alkoxy groups such as methoxy group, dimethylamine group, diphenylamino, JJ (, methylphenylamino2 group, morpholino group, imidaturidine group, ethoxycarbonylpiperazine group, etc.). Preferable examples include a di-substituted amine group, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as a methylthio group, a cyano group, a nitro group, and a halogen atom such as Br and CI.

In addition, among these formulas (LI) to [L■], tricarbocyanine linking groups, special formulas CLII) and (L[) are preferred.

Further, X- is an anion, and preferable examples thereof include I-, Br CI 04-, and B F4-.

etc. can be bowed.

Note that m is 0 or 1, but when m is 0, R1 of Φ usually has one charge and becomes an inner salt.

Next, specific examples of the light-absorbing dye of the present invention will be given, but the present invention is not limited to these.

Pigment amount Φ, ψ R,, RI
R2, R3D1 [ΦI'l CH3CH
3D2 (ΦI) CH3CH3D3
(ΦI:] C2H5CH3D5
(ΦII) CH3CH3010 (C2Hb
)3 D8 (4)III″l C2H5CH3
D 9 C0III) (CH2)30C
OCH3CH3010(Om) CH3CH3
0l l (OIII) CH3CH3
R4L Y
X-, (LII) HI-CLTI)
HC104-(Lm)-N
<C6 old 010'-(LIl)
I]--[:LII) HClO
4-, CLII) H-\□-/-(LIT) HBF4(LIII
) N< :6 is Cl 04-
(L II) ) (Cl 04-
(LII)' HID12 [
ΦI''” 17”35 CH301
0 [Φ■] C4H9CH3 010 [ΦI) CHOCOCHs C
H316 D15 [ΦI) C7H, CH20HCH301
0 [ΦII) C8H17CH3D18 f:(
1) m) //
CH3D18 [Φm] CHCoo(, R5C
H314 D20 [Φm] C3H1, CH3010 D22 [Φ■] C3H1□ C
H3010 [ΦI) CHCOOCH3CH37
34 --(LIT) H,1-(Ll
l) HC104-(Lll)
HI(Lll'l
HClO4-(Lll)
H-(LII) HBF4-
- (LII) H, Cl
O4-(LII) HI-(LI
I) H, ID24 [ΦI)
CHOCOCH3CH3-816 D25 [ΦI) C8H,7C2H4i -D26
[ΦI] C7H, 5C2H5-D27 [ΦID
CHCOOCH3CH3-1? 34 D28 [ΦIl] CHCH0COCHCH
3-81823 D28 [ΦI■] C17H35CH3-D 30
(ΦIT) CHCOOCH3C2H5-
14 D31 [Φm″l C7) (,4C,H20HC
H3-DBP [Φm] CHCH0COC2H
5CH3-7142 D33 ((I)m) CHC00C,,I5
CH3-734 D34 [Φ■] C17H35CH3-D35 [
Φn[c7H,5C2H5=(Lll)
H■(L II)
HI(Lll) HC104
(Lll) HCl04(LI
I) HC104(L II
) HI(L, l11)
-N<Ro:H:1(LIV)
H1 (L II ) HI
D36 [Φ■] C7H15CH3D37 [ΦI
T) C7) I5 CH3D
38 [Φrv) c,. I35,
CH3D39 [ΦIV] CHCH
OCOCH3CH37342 D40 (ΦV'l C,, H5D41 [Φ
■] CH3 D42 [Φ■] C2H3 D43 [Φ■] C2H3 D44 [Φ■] C2H3 D45 [Φ■] C2H3 D46 [Φ■] C2H3 D47 [ΦVI ) C2H5 -(L II
) HI-(LII)
) (CIO.

-(LII) HC104-(L II
) HI4-CH3(Lll)
HI4-CH3(, LII)
HI-(LIT) HCl045-C
1(Lm) N(C8)15)2 Cl04
5-OCH3(LII) HI(5-(L17)-□
I-(L II) HID48 [Φ
VI:] C2H3D49 [Φ■] C2
H3 D50 [ΦVT] C2H3 D51 [ΦVj) C21-15D52 [Φ
■] C2H3 D53 [Φ■) (CH2) 30 COC1(
3~-D54 [ΦVl) C1-12CH20
HD55 [Φ■] C2H3 D5B, CΦIX) C21 (5D57 [
ΦIX) C, H5 D58 [Φ■] C2H3 D58 [ΦX) C, H5 -(L I ) HCIO4(LI
T) CH3I-(LV) H1-(LV) HI-[L■]
■-(Lm) N (Cs Hh
)2 C1045-CI (Lll
) HCIO.

-(Lll:] HCI 04--
(LII) HI-CL
III) OCH3I-(Ill
) HID80 (Φn) C
H2CH20HD61 (OXII) C2H
3DC2 [Φ■:] (CH2) 30. COCH
3-D63 [Φ bar] CH□ 5 D64 [φ store] CH2CH2CH2503H-D
65 [φ store:] C2H3 D66 [φ store) C2H3 DB7 (φ φ] C2H3 D68 [φ ■] C3H17 D69 [φ ■] CL8H37 D70 [φVL) C8H, □ D71
T) C3H1゜-(LII) H
Cl0n--CLll) )l
I---(Lll) HI---1 (Lm) N(C6H5)2
ClO4---(LIII)N(C8
H5)2 I-(LII) H
ClO4--(Lll) HClO2-4
-CH3(LII) HI--(LII)
MCl04--
- (LTI) HClO4-
5-C1(LII) HCI04-5-C
1(Lll) )72[Φ■] Cl8H3□ 5-OCH3(Lll) )73 [:OVI) 0s HI3 (
6-OCH3〕74〔ΦVI) C3H175-O
CH3CLIV))? 5 (OVI) C8H1
75-C1-I:Lm)]76[Φ■]Cl8H3□
5-CI-CI,III)--(L II
)]77[Φ■] C8H17 - [L +1) ]78[Φ■) C3H17 D78[ΦV'l) Cl8H3゜ 5-C
I-[:LII:]D80[ΦVT]C,
8H375-Cl -(Lll)-(LV) D81 [Φ”) C8H17 -(L Vl] DBP [ΦVT) C8H,□-(L■] D83 [Φ■] C3H17 HI HI □ I-N (
C8H5)2 Cl04-N (C6
F(h)2 CXO<HI HCIo, + 1(I HI □ ■□
(Lm] D84 [Φ■) C8H17 □ -~ [LIl] D85 [Φ■] Cl8H3□ --- (L If ) D86 [Φ■) C13H27 (L 11 ) ] 87 Φ■] C13H27 (L III)] 88 [ΦVll) C8H,.

CLm) 〕88〔Φ■) C3H1□ [: L II ) 〕90〔Φ■〕 Cl8H3□ (L II ) 〕91〔Φ■〕 C3H1□ (LIII) 〕92〔Φ■) Cl8H3□ CL II)] 83 [Φ”) C8H17 - (LI+] ] 94 [Φ cut] C8H17 -CL [[)] 95 [Φ cut] C3H1□ N (C6Hb) 2 C1,04HC1○
4 HCl0i 1-T ■QCH3工H■ N(C6H5)2 C104HC104 H■ Da e [o i ) c I 3 H2
7~D87 [φ■] c8H17- Da8 [ΦW) C, 8H3゜-D98 [ΦXI
V) C8H,7-Dloo (ΦXv)
c a H] 7 -DIOI CΦv
) c8H17- D+02 CΦ■) C8H,7-D103
[ΦXll1)c8H17- 5-C1(LII) H1-(LIII)
N (Cs R5) 2 C104-
(Lm) N (C6Hb)2 1-
(LH) HC104-[LI engineering]
Hclo6 (LII:] HClO4 -(Lll) HClO4 -(Lll) HClO4 Such carbocyanine dyes can be prepared according to the method described in Dai Organic Chemistry (Breakfast Shoten) Nitrogen-Containing Heterocyclic Compounds I 4" page 32, etc. Can be easily synthesized.

That is, first, the corresponding Φ'-CH3 (Φ' is 1) IJ
represents a ring corresponding to the notation Φ. ) to the excess R,I (R
t is an alkyl group or an aryl group), R1 is introduced into the nitrogen atom in Φ' to obtain Φ-CH5I-. Next, this may be subjected to dehydration condensation using an unsaturated dialdehyde and an alkali catalyst.

On the other hand, the thermoplastic resin contained in the recording layer is petroleum resin.

Petroleum resin is a polymer obtained by processing fractions whose main components are low-value-added by-products produced in the petroleum refining and petrochemical industries.

Various petroleum resins have a J7J capacity, but their number average molecular weight is 500 to 3000, especially 6
It is preferable that it is 00-2500.

At this time, compatibility with the dye is improved, heat resistance is improved, and deterioration due to erasure and the like is reduced.

In addition, the softening point of petroleum resin according to JIS K 2531 tube method is 40 to 200' C1, especially 50 to 180
Preferably it is ℃.

At this time, the erasing performance, especially the erasing performance during full-surface thermal erasing, is improved.

Further, the bromine number of the petroleum resin according to ASTM D 1159 is preferably 200 or less, particularly 180 or less. In this case, the bromine number may be 0 due to hydrogenation or the like.

This improves thermal and chemical stability and weather resistance.

Although there are no particular restrictions on the composition of such petroleum resins, the following are particularly preferred.

1) C5 system 2) C9 system 3) C3-C9 copolymer system 4) Dicyclopentadiene system 5) Any of -1-1) to 4), other fractions and various vinyl monomers, Copolymers with various diene monomers, etc. 6) Modified products of the above 1) to 5), such as hydrogenated products.

Modified products by reaction with unsaturated carboxylic acids and acid anhydrides such as acrylic acid, methacrylic acid, maleic acid, tetrahydrophthalic acid, fumaric acid, citraconic acid, itaconic acid, maleic anhydride, and tetrahydrophthalic anhydride.

Ester modified product by reaction with alcohol.

Modified product with unsaturated polyhydric alcohol.

Modified product with phenolic resin.

Other products modified with various amines, isocyanates, halides, etc.

Such a dye and the above-mentioned petroleum resin are usually provided in a heavy chain ratio of 1:0.05 to 100.

Preferably, such a recording layer further contains a quencher.

As a result, regeneration deterioration is slightly reduced and light resistance is improved.

Various quenchers can be used, but especially when the dye is excited and singlet oxygen is generated, -
It is preferable that the quencher is a singlet oxygen quencher that undergoes electron transfer or energy transfer from heavyt oxygen to become excited, returns to the ground state by itself, and converts -singlet oxygen to a triplet state.

Various singlet oxygen quenchers can be used, but transition metal chelate compounds are particularly preferred because they reduce regeneration deterioration and have good compatibility with dyes. . In this case, the central metal is preferably Ni, Co, Cu, Mn, etc., and the following compounds are particularly preferred.

■) Artylacetonate chelate QINi (I
I) Acetylacetonate Q2 Cu(II) Acetylacetonate Q3 Mn(III) Acetylacetonate Q4CO(H) Acetylacetonate 2) Bisdithio-α-diketone system where R(IL R(4) is substituted or It represents an unsubstituted alkyl group or an aryl group, and M represents a divalent transition metal atom.

In this case, M has a single charge and may form a salt with a quaternary ammonium ion or the like.

Q5Ni(II) dithiobenzyl Q6Ni(II) dithiobiacetyl 7 9 N” ( c 4os ) 4 3) Bisphenyldithiol system (5) (8) Here, R and R are an alkyl group such as a methyl group, Alternatively, it represents a halogen atom such as C1, and M represents a divalent transition metal atom such as Ni.

Furthermore, a and b are each O or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with an anion, and further, other ligands may be bonded above and below M.

As such, the following are commercially available.

QIOPA-fool (product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002 (same 1-) Q12
PA-1003 (same) Q13 PA-1
005 (same - h) Q14 FA-1006 (same 1
-)Q15 Co-bis(Hensea-1,2-dithiol)tetrabutyl ammonium salt Q16 Co-bis(0-xy1/7-4.5-dithiol)tetra(shi-butyl)ammonium salt Q17 Ni-bis( Benzene-1,2-dithiol)tetrabutyl ammonium salt Q18 Ni-bis(0-xy1y7-4,5-dithiol)tetrabutyl ammonium salt! Crystal Q19Ni-bis(5-chlorobenzene-1,2-dithiol)tetrabutylammonium salt Q2ONi-bis(3,4,5,6-titramethylbenzene-1,2dithiol)te(-butylammonium salt Q21 Ni
-bis(3,4,,5,6-titrachloropensen-1
．． 2-dithiol) TeI-raftyl ammonium 1!14) Dithiocarbamine-1-system (7), (8) Here, R and R represent an alkyl group. Further, M represents a divalent transition metal element r-.

Q22Ni-bis(dibutyl dithiocarbamic acid) [
Antigen MBC (manufactured by Sumitomo Kagakuin Co., Ltd.) 5) Hisphecol thiol Q23 Ni-his(octylphenyl) sulfide 6) Thiocatechol chelate-1 system Here, M represents a divalent agricultural metal atom . Also, M
has a charge of -・' and may form a salt with an anion, and the benzene ring may be

Q24 Ni-bis(thiocatechol)tetrabutyl ammonium salt 7) Salicylaldehyde oxime system (9) Here, R and R (10) represent alkylno, (, and M represents a divalent transition metal atom.

Q25 Ni (II) 0- (N-isopropylformimidoyl)phenol Q26 Ni (II) O-(N-dodecylformimidoyl)phenol Q27 Co (II) O-(N-F decylpol 1,
imidoyl)phenol Q28 Cu ('TI)O-(N-dodecylformimidoyl)phenol Q29 N1(II)2.2'-(ethylenebis(nitrilomethylidine))]-diphenol Q30 Co(II)2.2 ′-(ethylene his(
di[・lylomethylidine)] -diphenol Q31 Ni (II) 2.2' -(
1,8-Naphthylenebis(dil-lilomethylisin)]-diphenol Q32 Ni(II)-(N-phenylformimidoyl)phenol Q33 Co(II)-(N-fecholform Q3
4 Cu (IT) -(N-phe-ruho)ly muimidoyl)phenol Q35 N1(II) salicylaltehy1miphenylhydrazino Q36 N1(II) salicylaldehyde oxime 8) Thiobisfer-tokyle-1・system R(11 )R(
12) (11) Here, 2M is the same as above, and R and R(1'2) represent an alkyl group. Further, M has one charge and may form a salt with an anion.

Q37 Ni (II) n-butylamino [2゜2
'-Thiobis(4-tert-octyl)-2-elt) ((1:yasorb-UV-1084 (American Schiffus Mid Co., Ltd.) )Q
38 Co(II) n-butylamino: 2゜2'-
Thiobis(4-tert-octyl)-ferulate] Q39 Ni (II) -2,2' Thiobis(4
-tert-octyl)-nert9) Phosphite butychelate system (13) Here, M is the same as above, and R (14) and R represent a substituent such as an alkyl group or a hydroxyl group.

40 In addition to this, other quenchers include the following.

10) Benzony 1/type Q51 Existing chemical substance 3-3040 [:Chikubin-
120 (manufactured by Chihegaiki Co., Ltd.)] 11) Hindered Amine Q52 Existing Chemical Substance 5-3732 (5ANOL S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)) Such an encher is synthesized according to a known method.

The quencher is generally contained in an amount of about 0.05 to 12 moles, particularly about 0.1 to 1.2 moles, per mole of the dye.

In order to form such a recording layer, it is generally sufficient to apply the coating according to a conventional method, and the thickness thereof is generally set to be 0.03 to 100 m.

The thickness of the recording layer is usually about 0.03 to 10 gm.

In addition, such a recording layer may contain other polymers or oligomers, various plasticizers, surfactants, .:i? Antistatic agents, lubricants, flame retardants, stabilizers, dispersants, crosslinking agents, etc. may be contained.

To form such a recording layer, it may be applied onto the substrate using a predetermined solvent and dried.

Examples of solvents used for coating include ketone systems such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester systems such as butyl acetate, ethyl acetate, carpitol acetate-1, and butyl carpitol acetate-1, methyl cellosolve, and ethyl acetate. Ether systems such as Selonlube, aromatic systems such as toluene and xylene, halogenated alkyl systems such as dichloroethane, alcohol systems, etc. may be used.

When forming such a recording layer, there is no particular restriction on the material of the body, and it may be made of any of various resins, glass, ceramics, metals, etc.

In addition, the shape varies depending on the purpose of use, such as tape, disk,
It may be a drum, a belt, etc.

Note that the base body usually has a groove for tracking.
Further, if necessary, it may have a base layer such as a reflective layer, a heat storage layer, a light absorption layer, etc.

In addition, the substrate material is epoxy resin with high heat resistance,
A groove-free substrate without grooves, such as polycarbonate resin, polysulfone resin, polyethersulfone, methylpentene polymer, etc., can be suitably used.

These substrates can also be coated with a primer to improve solvent resistance, wettability, surface tension, thermal conductivity, and the like.

As the primer, for example, titanium-based, silane-based, or aluminum-based coupling agents, various photosensitive resins, etc. can be used.

In addition, on the recording layer, if necessary, a reflective layer that functions as a back surface when using a transparent substrate, various layer protective layers, etc.
It is also possible to provide a half-mirror layer.

The medium of the present invention may have the above recording layer 41 on one side L of such a base, or may have a recording layer on the inner surface thereof.

In addition, two substrates with recording layers coated on one side of the substrate are used, and the recording layers are placed facing each other with a predetermined gap between them, and the substrate is sealed to prevent dust and scratches. You can also choose not to have one.

(2) Specific Effects of the Invention The medium of the present invention is irradiated with recording light in pulses while running or rotating. At this time, the heat generated by the dye in the recording layer melts the thermoplastic resin and the dye, forming pits.

The focus formed in this manner is also read out by detecting reflected or transmitted light of the readout light, particularly repulsed light, while the medium is running or rotating.

In this case, recording and reading may be performed from the base side or from the recording layer side.

Then, the pits formed in the - and B recording layers can be erased with light or heat to perform rewriting.

Note that a semiconductor laser, a He-Ne laser, an Ar laser, a He-Cd laser π; can be used as the recording or reading light.

■Specific Effects of the Invention According to the present invention, the compatibility between the dye and the ico oil resin is high, so even if the medium is stored for a long time, the reading sensitivity and S
/N ratio deterioration is extremely small.

Furthermore, the read S/N ratio is extremely high.

Furthermore, it has extremely high heat resistance, and the deterioration of sensitivity and S/N due to storage at high temperatures is extremely small.

In addition, erasure degradation is extremely low.

Such an effect is not achieved when other thermoplastic resins or other dyes are used.

In addition, according to the second invention, regeneration deterioration is significantly reduced,
Extremely high light resistance.

The present inventors conducted various experiments to confirm the effects of the present invention.

An example is shown below.

Example Petroleum resins shown in Table 1 below were used.

These petroleum resins and the dye No. D2. Dlo, D.
70 was dissolved in dichloroethane at a weight ratio of resin/dye = 8/2, and this was coated on an epoxy resin substrate of 15 cm diameter to a thickness of 0.1 lm to form a recording layer.

Separately, for comparison, a medium was prepared in the same manner except that the carbocyanine dye was replaced with the dye exemplified as Quencher-Qll.

Further, a medium was produced in the same manner except that the petroleum resin was replaced with polystyrene (PS) having a number average molecular weight of 1000.

While rotating each of these media at 60 Orpm, the semiconductor laser was focused on Igmφ with a condensing power of 10 mW).
, 300 n5ec width pulses were irradiated at a predetermined frequency to write through the substrate.

Next, the above-mentioned laser was focused on Igmφ (condenser power: 1 mW), readout was performed from the back side of the substrate, and the C/N ratio of the reflected light of the readout light was measured.

Each medium was then incubated at 60°C and 70% relative humidity.
After storage for 0.01 days, the C/N ratio was measured, and the deterioration (dB) of the C/N ratio was calculated.

In addition, after erasing by heating on a hot plate °C for 60 seconds, 1B was written and read again, and the C/N ratio of the read after erasing a total of 3 times was Ml! Degradation of C/N ratio (dB)
was calculated.

These results are shown in Table 2.

From the results shown in Table 2, the effects of the present invention are clear.

Example Quencher Q14 was added to the recording layer of medium No. 1 in Experimental Example 1, and the weight ratio of resin/dye/quencher was 8.
The power was measured at a ratio of 2:1 (between media, 11).

Medium No. 1 and No. 11 were irradiated with a readout laser beam for 5 minutes, and the S/N ratio of 1 was set to 111.
When added, the results shown in Table 3 below were obtained.

Table 3 1 50 42 11 50 50 From the results shown in Table 3, the effect of the second invention is clear.

Note that the heat resistance and erase deterioration of media 11 are between media 1b,
It was equivalent to 1.

Applicant TK Co., Ltd. Agent Patent Attorney Yo Ishii =-+Itoune City,
, rE'7! :; (, spontaneous)
6.

June 2, 1983 Director General of the 5th Office of the Japanese Patent Office Kazuo Wakasugi Kei 1, Indication of the case Patent Application No. 45640 of 1988 ■) r Optical recording medium P (3. Relationship with the amended person case Patent application human pillar place
Nihonbashi-chome 13-1, Chuo-ku, Tokyo Name
(306) Representative of TDC Co., Ltd.
Kan Otoshi 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
Goyabe Building 1st floor Telephone: 988-1680"; Zu: ]) Taichi;-← ]-Detail 1 of the contents of the amendment, (:'s γ3, Detailed explanation of the invention" column below) Correct as described below.

On page 31, line 1q, FNi, Co, Cu.

+j, 1JNi, Co, Cu, Mn.

1. Correct as Ptj.

[) Acetylacetonate chelate QINi (II
) Acetylacetonate Q2 Cu (II) Acetylacetonate Q3 Mn (m) Acetylacetonate Q4 CO (TI) Acetylacetonate 2) Hisdithio-α-diketone system where R (ILR (4) is substituted or unsubstituted represents an alkyl group or an aryl group, M is Ni, Co,
Represents a transition metal atom such as Cu, Pd, or Pt.

In this case, M has a single charge and may form a salt with a cation such as a quaternary ammonium ion.

Q5Ni(II) dithiobenzyl Q6Ni(II) dithiobiacetyl 7 N''(04H9)4 3) Hisphenyldithiol system (5) ''(8) Here, R and R are an alkyl group such as methyl, or 0 Represents a halogen atom etc. such as a sentence,
M is Ni, Co.

Represents a transition metal atom such as Cu, Pd, or Pt. Furthermore, a and b are each O or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with a cation, and further, another ligand may be bonded under F of M.

Examples of this include the following:

QIO PA-fool (Product name: Manufactured by Mitsui Toatsu Fine Co., Ltd.)
Toluene dithiol) tetra(butyl)ammonium] Q12 PA-1003 (same j2) Q1
3 PA-1005C Same as above Ni-His(dichlorobenzene)tetra(t-butyl)ammonium] Q14 PA-1006(Same as above Ni-bis(trichlorobenzenedithiol) Tetra(E-butyl)ammonium) Q15 Co-Bis(benzene -1,2-dithiol)tetrabutylammonium Q16 Co-bis(0-xylene-4,5-dithiol)tetra(t-butyl)ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18Ni-bis (o-xyL/:/-4.5-dithiol)tetraptylammonium 1, Q19Ni-his(5-chlorohensen-1,2-dithiol)teI-butylammonilla 1, Q2ONi-his(3,4, (S ) Here, R and R represent an alkyl group. Moreover, M is Ni, Co, or Cu.

Represents a transition metal atom such as Pd, P, etc.

Q22Ni-bis(digtyl dithiocarbamic acid) [
Antigen NEC (manufactured by Sumitomo Chemical Co., Ltd.) 5) Bisphenylthiol-based Q23Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate-based where M is Ni, Co, Cu, Pd.

Represents a transition metal atom such as pt. Further, M has a single charge and may form a salt with a cation, and the benzene ring may have a substituent.

Q24 Ni-bis(thiocatechol)tetrabutylammonium salt 7) Salicylaldehyde oxime system (9) (10) Here, R and R represent an alkyl group, and M is Ni, Co, Cu.

Represents a transition metal atom such as Pj or PL.

Q25 Ni(II)O(N-isopropylformimidoyl)phenol Q26 Ni(H)o-(N-dodecy)Lrformimidoyl)phenol Q27 Co(II)o-(N-dodecylformimidoyl)phenol Q28 Cu(II)o -(N-dodecylformimidoyl)phenol Q29 N1(II)2.2'-(trilomethylidine on ethylenebis)]-diphenol Q30 Co(II)2,2'-(xchiL/ 7
Bis(21-IJ lomethylidine)) -diphenol Q31 Ni(II)2.2'-(1,8-
Naphthylenebis trilomethylidine)]-diphenol Q32 Ni (II)-(N-phenylporumimidoyl)phenol Q33 Co (II) (N7 x
Nyl*)Iy Muimidoyl) Phenol Q34 Cu (TI) -(N-7z-Im-Lupol A imidoyl) Phenol Q35 N1(II) Salicylaldehyde Phenylhydrason Q36 N1(II) Salicylaldehyde oxime 8) Thio 1 spher- Tochelate type R(11)R
(12) Here, M is the same as above, and R (11), (12) and R represent an alkyl group. Further, M has a single charge and may form a salt with a cation.

Q37 Ni (II) n-butylamino [2゜2
'-Thiobis(4-tert-octyl)-felt] (Cyasorb-UV-1084 (American Cyanamid Co., Ltd.)) Q3
8 Co(II) n-butylamino [2゜2-thiohis(4-tert-octyl)-fer-1.] Q39 Ni(II) -2,2'-thiobis(
4-te, rt-octyl)-ferulate 9) Phosphonous chelate-resistant system where M is the same as above, R(13) and R(
+4) represents a substituent such as an alkyl group or a hydroxyl group.

40 In addition to this, other quenchers include the following.

10) Henshade Q41 Existing chemical substance: 3-3040 (Tinuvin-120 (manufactured by Ciba Geigy)) II) Hindered amine Q42 Existing chemical substance 5-3732 (5ANOLL)
S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)]j

Claims (1)

[Claims] 1. An optical recording medium characterized by having a recording layer containing a petroleum resin and a dye on a substrate. 2. The optical recording medium according to claim 1, wherein the petroleum resin has a number average molecular weight of 500 to 3,000. 3. The optical recording medium according to claim 1 or 2, wherein the petroleum resin has a softening point of 40 to 200°C according to JIS K 2531. 4- The optical recording medium according to any one of claims 1 to 3, wherein the petroleum resin has an odor value of 200 or less according to ASTM D 1159. 5. Claims 1 to 4, wherein the petroleum resin is a C5 type, C9 type, C5-c, q copolymer type, or dicyclopentadiene type, or a copolymer or modified product thereof. The optical recording medium according to any one of the above. 6. The optical recording medium according to any one of claims 1 to 5, wherein the dye is a carbocyanine dye. 7. An optical recording body characterized by having a recording layer containing a petroleum resin, a dye, and a quencher as a base.
. 8. The optical recording medium according to claim 7, wherein the petroleum resin has a number average molecular weight of 500 to 3,000. 9. The optical recording medium according to claim 7, Da 1 or 8, wherein the petroleum resin has a softening point of 40 to 200°C according to JIS K 2531. 10. The optical recording medium according to any one of claims 7 to 9, wherein the petroleum resin has a bromine number of 200 or less according to ASTM D 1159. 11. Petroleum resins are C5 series, C9 series, and C5-c9 1
Polymer or dicyclopentadiene, or a copolymer or modified product of these! l\, I'+ The optical recording medium according to any one of claims 7 to 10. 12. 4 yen allowance J1 where the dye is carbocyanine dye
- The optical recording medium according to any one of the desired ranges 7 to 11. 13. The optical recording medium according to claims 7 to 12, wherein the quencher is a transition metal chelate compound.