JPS6189891A - optical information recording medium - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to an optical information recording medium containing a specific polymeric substance in its recording layer. More specifically, the present invention relates to an optical information recording medium with improved storage stability and photostability.

[Prior art]

2. Description of the Related Art Conventionally, an information recording and reproducing apparatus is known that records and reproduces information by irradiating a laser beam onto a disk-shaped information recording medium that rotates six times. As a recording layer of an information recording medium used in this type of information recording device, a recording layer using a low melting point metal or a low melting point metal and a dielectric material has been proposed.

However, these have poor storage stability and low resolution.

It has drawbacks such as low recording density and high cost.

Furthermore, it has recently been proposed to use an organic dye thin film whose physical properties can be changed by relatively long wavelength light in the recording layer.

Although this organic dye thin film eliminates the above-mentioned drawbacks, organic dyes that generally have absorption characteristics on the long wavelength side have problems such as low stability against heat and light.

〔the purpose〕

The present invention has been made in view of the above problems, and its purpose is to improve storage stability and light stability (reducing reproduction deterioration) in recording media using organic dyes.

〔composition〕

As a result of conducting various studies to achieve the above object, the inventor of the present invention found that by incorporating a polymer substance having a repeating unit of the following formula into the recording layer, the reproduction deterioration of the organic dye was reduced and the light resistance was significantly improved. They discovered what they could do and completed the present invention.

That is, the present invention provides an optical information recording medium in which a recording layer is provided directly or via an undercoat layer on a substrate, and a protective layer is further provided thereon as required, in which an organic dye and a formula ( In the formula, 1M represents Ni, Pd or pt, X and Y represent 0 or S, and φ represents an atomic group necessary to form a conjugated system. An object of the present invention is to provide an optical information recording medium characterized by the following.

Representative examples of polymeric substances having repeating units of the above formula in the present invention include, but are not limited to, the following.

t The recording layer in the present invention is capable of causing some optical change by irradiation with a laser beam and recording information based on the change, and the recording layer contains an organic dye and the above-mentioned polymeric substance. is necessary. Further, in forming the recording layer, two or more organic dyes and polymer substances can be used in combination.

Additionally, metals and metal compounds such as In.

Sn, To, Bi, AI, Se, TeO2,
It may be mixed and dispersed or laminated with SnO, As, Cd, etc. Furthermore, the polymeric substance of the present invention is a polymeric material such as an ionomer resin, a polyamide resin, or a vinyl resin.

It may be used by mixing and dispersing it in various materials such as natural polymers, silicones, liquid rubbers, silane coupling agents, etc., or it may be used as a stabilizer 1 dispersant, flame retardant, lubricant, antistatic agent, etc. for the purpose of improving properties. It can also be used together with agents, surfactants, plasticizers, etc.

Typical examples of organic dyes to be contained in the recording layer in the present invention are listed below as I-2, but the invention is not limited thereto.

(2) Dicroconium dye However, X represents a chromophore, a cape represents a cation, and Yo represents an anion; however, when an anion is contained in the chromophore, Ye is not present.

■, azulene dye, R1, R2, R5, R4 and R5 are hydrogen atoms,
Indicates an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group.

m, Tri-7-D/Dithiazine Compound However, R1 and R2 may be the same or different, and each is a hydrogen atom, a hydrogen atom, an alkyl group, a phenyl group, and an alkyl group.

Flukoxy, carboxyl, carboxylic acid base.

It may be substituted with one or more of halogen, hydroxyl group, sulfonic acid group and sulfonic acid group.

■Phthalocyanine compounds However, MFi hydrogen, vanadium oxide, copper, beryllium, magnesium, calcium, zinc.

Cadmium, barium, aluminum, tin, lead.

Examples include vanadium, chromium, manganese, iron, cobalt, nickel, tin halide, and aluminum halide, with hydrogen, lead, nickel, cobalt, copper, vanadium oxide, aluminum chloride, and tin chloride being particularly preferred. . X is hydrogen, chlorine, bromine,
represents a halogen such as iodine and fluorine, and n is 1 to 1
It is an integer of 6.

■, Tetradehydrocholine compound CH5CHs, where R is alkyl, carbalkoxy e.g. COO
Represents C2H5, etc., R4 represents hydrogen, alkyl, etc., M is H, N1(If), Co(II), C
o(In), etc., and X represents Br, ClO
4 etc.

(2) Dioxazine compounds and their derivatives a) Aromatic amines and fluocinyl. Chloranil.

Condensation ring-closing reaction product A with bromanyl and iodoanil: residues of unsubstituted or substituted aromatic amines
Ct, -Br, -1 b) X: -F, -CL, -8r, -X R2 -H, -No2, -NH2, -0CR
,,-QC2H,.

-F, -CL, -Br, -I, aromatic group m, n: 1-4 (1), anthraquinone derivative It can be represented by the following structural formulas III) and (It, l).

Structural formula CI) However, XI, X2. XR and X4 are each hydrogen.

represents an alkyl group, a hydroxyl group, a nitro group, an amino group, a cyano group, and a norogen; YH represents hydrogen and a sulfonate group; Ar1 is hydrogen, a phenyl group,
It represents a naphthyl group and their sulfonated products and salts, and the phenyl group is an alkyl group, an alkoxy group, or an amino group.

Ar2 may be substituted with an alkylcarbonyl group, a methylthio group, a 710ge/and a phenylcarbonyl group, and Ar2 is hydrogen, a phenyl group.

and their sulfonates and salts.

The phenyl group may be substituted with an alkyl group, an alkoxy group, an amino group, an alkylcarbonyl group, a phenylcarbonyl group, or a halogen.

Structural formula (II) However, x, , X2, XS and x4 have the same meanings as above, and Xs represents hydrogen and -NH-Ar1.

2 represents hydrogen, -NH-Ar1 and -8-Ar1, and Ar1 has the same meaning as above.

In particular, compounds with an indanthrene skeleton like Structural Formula [II] have a maximum absorption wavelength around 800 nm, so
It is ideal as a material for semiconductor lasers.

Examples of anthraquinone derivatives represented by the above structural formulas CI) and (II) are shown below.

1-amino-4-(4-sulfonic acid phenylamino)
-6,7-sinitroanthraquinone sodium salt, 1-
Sodium anilino-2-sulfonate-4-(4-methylphenylamino)anthraquinone, 8.17-bis-(4-methoxyphenylamino)-indanthrene,
1,4-bis(sodium 3-sulfonate-4-methoxyphenylamino) -6,7-diciatua/traquinone, 1,4-his(sodium 3-sulfonate/4-chlorophenylamino) -5,8-' ) 7 mouths [anthraquinone, sodium 1-(2-methylphenylamino)-2-sulfonate-4-(4-aminophenylamino)
-6,7-sinitroa〉traquinone, 1,4-bis(3
-Sodium sulfonate-4-anilino-1-anthraquinolyl amino)
, sodium sulfonate-phenylamino)-1-anthraquinolyl amino)benzene, and the like.

■, xanthine compound R,: -OH, -0, -N(R)2 (R=01~C
to alkyl group) R2: =N0(R)2.X-(X-
= acid 7ion, R = c1-c1゜alkyl group) R5: H, C1-C2, alkyl, SO3Na,
S○3H.

802N(R)2 (R==C, ~C'jo alkyl group), C0OH.

COONa, CoOx ■ Triphenylmethane compound R1: H, -N(R)2 (R= C1-C1o alkyl group), c, <2° alkyl, -0H R2: H, -N(R)2(R =C, ~C1o alkyl group), C, -C2゜alkyl, -OH R3: H, C1~C2, alkyl, haloken, 5O
5H.

-NCR)2 (R=Ct~C''+o alkyl group)xe
: acid anion X, pyrylium compound e e in the formula.

Xl and X2: represent a sulfur atom, an oxygen atom or a selenium atom.

Pyrylium, thiopyrylium, which may be substituted with Zl: W
Selenapyryllium, Benzopyrylium, Benzothiopyrillium, Benzoselenapyrylium, Su7topyrylium,
Indicates a hydrocarbon group consisting of the necessary atomic groups to complete naphthothiopyrylium or nandoselenapyrylium.

Z2: optionally substituted pyran, thiopyran/, selenapyran, ninzopyran, benzothiopyran, benzoselenapyran, naphtopyran/.

Indicates a hydrocarbon group consisting of the atoms necessary to complete naphthothiopyran or naphthoselenapyran.

R1, R2, R, and R4: hydrogen atom, substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group.

R5, R, and R7: hydrogen atom, halogen atom, #-substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted aralkyl group.

m and t: 1 or 2.

n: Indicates 0, 1 or 2.

°C, cyanine dye or (in the formula, R1 and R2 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or an alkenyl group; z5 represents an atomic group necessary to complete a substituted or unsubstituted 5-membered ring or 6-membered ring.

Further, the 5-membered ring or 6-membered ring may be fused with an aromatic ring, R5 represents a hydrogen atom or a halogen atom,
R4 and R5 represent a hydrogen atom, )/rogen atom, hydroxy group, carboxyl group, alkyl group, substituted or unsubstituted aryl group or acyloxy group, Xe represents an acid anion, and m and n are 0 or 1
).

(2) represents merocyanide/dye, and the benzene ring and the 7-tyl ring in the above formula may be substituted.

2H5 2).

Xll1. ) Liphenylamine dye NL (R1)
n-xe (R2)a-n (wherein, X represents an acid anion and R1 and R2
each represents a substituted or unsubstituted aryl group) Next, the structure of the optical information recording medium according to the present invention will be explained with reference to one drawing.

As shown in FIG. 1, the optical information recording medium of the present invention basically comprises a substrate 1 and a recording layer 2 containing the above-mentioned polymeric substance and organic dye.

Further, the recording layer can also have a two-layer structure in which a light-reflecting layer and a light-absorbing layer are combined in any order.

The recording layer can be formed by conventional means such as vapor deposition, sputtering, CVD or solution coating. When using a solution coating method, the recording material is dissolved in an organic solvent and subjected to delta spraying, roller coating, dipping and spinning. This can be done by conventional coating methods such as blade coating and curtain coating. Organic solvents generally include alcohols such as methanol, ethanol, and impropatol, acetone, and methyl ethyl ketone.

Ketones such as cyclohexanone, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, sulfoxides such as dimethylsulfoxide,
Ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate, ethyl acetate, aliphatic heloquine hydrocarbons such as chloroform, methylene chloride, dichloroethane, carbon tetrachloride, trichloroethane, etc. Aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorobenzene, etc. can be used.

The thickness of the recording layer is preferably 100A to 10μm and 200A.
~2 μm is appropriate.

When writing and recording from the substrate side, the substrate 1 must be transparent to the laser beam used.

Furthermore, when performing from the recording layer side, it does not need to be transparent.

As the substrate, glass, plastics such as polyester, polyamide, polyolefin, polycarbonate, epoxy, polyimide, and polymethyl methacrylate, metals, and ceramics are usually used, but any other materials used for recording media may be used.

Furthermore, as shown in FIGS. 2 to 4, the structure shown in FIG. 1 may be further provided with an undercoat layer 3 and/or a protective layer 4.

At this time, the above-mentioned polymeric substance of the present invention may be contained in the undercoat layer and/or the protective layer.

In addition, stabilizer 1 dispersant is used in the undercoat layer or protective layer.

Flame retardants, lubricants, antistatic agents, surfactants, plasticizers, etc. may also be contained.

The subbing layer 3 (a) improves adhesiveness, (b) serves as a barrier against water or gas, and (C) improves storage stability of the recording layer.

It is used for the purposes of (d) improving reflectance, (e) protecting the substrate from solvents, and (f) forming pregrooves. For the purpose of (a), various substances such as the above polymer materials and silane coupling agents can be used, and for the purposes of (b) and (c), materials other than the above polymer materials can be used. Inorganic compounds such as 5io2°MgF2. Si
O, TiO2, ZnO, TiN, SiN, etc., metals or semimetals such as Zn, Cu, S, Ni, Cr,
Ge, Se.

Cd, Ag, AA, etc. can be used. For the purpose of (a), metals such as At, Ag, etc. or organic thin films having metallic luster such as methine dyes, xanthine dyes, etc. can be used, and (e).

For the purpose (f), ultraviolet curing resins, thermosetting resins, thermoplastic resins, etc. can be used.

Undercoat layer thickness α1-30 μm, preferably 0.2-10
μm is appropriate. The protective layer 4 is provided for the purpose of protecting against scratches, dust, dirt, etc., improving the storage stability of the record 1i, and improving the reflectance, and is made of the same material as the undercoat I-. be able to. The thickness of the protective layer is suitably 0.1 μm or more, preferably 50 μm or more.

Furthermore, as another configuration of the optical information recording medium according to the present invention, two recording media having the same configuration as shown in FIGS. It may be arranged in a so-called air sandwich structure in which it is placed inside and sealed, or it may be in a so-called close-contact sandwich structure (bonded structure) in which it is adhered with a protective layer 4 interposed therebetween.

Note that if a semiconductor laser with a wavelength of 750 to 850 nm is used as the laser light source, the device can be made smaller.

〔Example〕

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 Polymethyl methacrylate (hereinafter referred to as
The dye of the following formula and the above-mentioned exemplary compound A-1 (average molecular weight 30,000) were placed on a substrate (abbreviated as PMMA J).
A recording medium was prepared by coating a solution dissolved in 1,2-dichloroethane at a weight ratio of :2 using a spinner to form a recording layer having a thickness of 700 mm.

Example 2 A recording medium was produced in the same manner as in Example 1 except that a dye of the following formula was used instead of the dye in Example 1.

Example 3 A recording medium was produced in the same manner as in Example 1 except that a dye of the following formula was used instead of the dye in Example 1.

Example 4 A recording medium was produced in the same manner as in Example 2, except that Kn-listed exemplary compound A-4 (average molecular weight: 1t10,000) was used instead of the polymeric substance (A-1) in Example 2.

Example 5 A recording medium was produced in the same manner as in Example 4 except that a dye of the following formula was used instead of the dye in Example 4.

Example 6 A 100' thick Te film was deposited on a 1.2 mm thick PMMA substrate.
was vacuum-deposited, and the recording layer of Example 5 was further provided thereon to produce a recording medium.

Example 7 A recording medium was produced in the same manner as in Example 2 except that the above-mentioned exemplified compound A-6 (average molecular weight 20,000) was used instead of the polymeric substance (A-1) in Example 2.

Implementation II 8 Instead of the polymeric substance (A-1) in Example 2, the above-mentioned 5
A recording medium was produced in the same manner as in Example 2 except that 1J Compound A-7 (average molecule=ioooo) was used.

Example 9 A recording medium was produced in the same manner as in Example 2 except that the above-mentioned exemplary compound A-8 (average molecular weight 20,000) was used in place of the polymeric substance (A-1) in Example 2.

Comparative Example 1 A recording medium was produced using only the dye in Example 1.

Comparative Example 2 A recording medium was produced using only the dye in Example 2.

Comparative Example 3 A recording medium was produced using only the dye in Example 3.

Each recording medium produced in the above Examples and Comparative Examples had a wavelength of 7.
Information was written and reproduced from the substrate side using a 90 nm semiconductor laser beam at a recording frequency of 0.5 MHz and a linear velocity of 1.5 m/se, and the reproduced waveform was subjected to distortion analysis (scanning filter, bandwidth 30 KHz). ) l, C/N was measured. Next, the reflectance and C after irradiating the same recording medium with 54,000 lux tungsten light for 50 hours
/N was measured.

Note that the reflectance was measured from the substrate side. The results are summarized in the table below.

Example 1 26.8 2.5 56 19.1
2.7 512 26.5 2.5 56
22.7 2.5 545 24.2 2.
5 53 19.8 2.7 514 26
．． 7 2.5 55 25 3 2.5 53
5 22.7 2.7 54 21.1 2
．． 7 526 32.3 i 52
31.1 50 467 2 & 5 2.
5 56 19.6 2.7 518 2
5.9 2.5 55 20.7 2.5
509 27.1 2.5 56 1&4
2.7 48 Comparative Example 1 2a3 2.3 5
7 10.9 Measurement impossible Distance measurement impossible 2 27.9
2.3 58 12.1 13 254
2.3 56 15.4 50 53
[Effects] The optical information recording medium of the present invention configured as described above can have the following effects.

1. High sensitivity recording is possible even when using a long wavelength laser (#-thick conductor, -za).

2. It is possible to form pits with a good shape.

High C/N can be obtained.

5. High stability against heat and light, excellent storage stability,
A recording medium with little reproduction deterioration can be obtained.

[Brief explanation of the drawing]

1 to 4 are cross-sectional views showing the structure of the optical information recording medium of the present invention. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Organic thin film recording layer, 5... Undercoat layer, 4... Protective layer.

Claims (1)

[Claims] An optical information recording medium in which a recording layer is provided on a substrate directly or via an undercoat layer, and further a protective layer is provided thereon as required, wherein the recording layer contains an organic dye and a formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, M represents Ni, Pd, or Pt, X and Y represent 0 or S, and φ represents the atomic group necessary to form a conjugated system.) An optical information recording medium characterized by containing a polymer substance having repeating units.