JPS61108589A - Optical information recording medium - Google Patents

Abstract

PURPOSE:To improve not only storage stability to heat and light but also that to reproduction light, by providing a recording layer based on a specific compound and a transition metal complex or a cationic salt thereof onto an acrylic polymer layer having a guide groove provided to the surface thereof. CONSTITUTION:A compound represented by general formula has 1-4 halogen atoms present on its indole and indolenine rings but has no halogen ion present thereon as a counter ion. An anion Y is selected from a pherchlorite ion and benzenesulfonate ion. As a metal complex, bis-dithio-2-diketones and bisphenyl thiols are especially pref. An acrylic polymer layer 2 having guide grooves provided thereto is provided on a substrate 1 and a recording layer 3 is provided thereon to constitute the titled recording medium and, in a sandwich structure, the recording medium is constituted so that the recording layer 3 is opposed to the substrate 1 so as to be brought to the inside, and sealed and integrated by using a spacer 4.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an optical information recording medium suitable for writing and recording using a laser, particularly a semiconductor laser.

[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 rotating disc-shaped information recording apparatus with a laser beam. As an information/information recording medium for use in this type of information recording device, one in which a recording magnetic layer made of a low melting point metal and a dielectric is provided on a substrate has been proposed. However, these have drawbacks such as poor storage stability, low resolution, low recording density, and high cost.

As a result of various studies, the inventors of the present invention have found that when a thin dye film is provided on the substrate, a recording medium with improved writing sensitivity and reflectance and a high reading SA ratio can be obtained, and has already proposed the same. . However, at present, such recording media still lack sufficient stability against light and heat, and storage stability against reproduction light after recording.

〔the purpose〕

The present invention has been made in view of the above problems, and its main purpose is to provide an optical information recording medium with improved storage properties against heat and light, and storage performance against reproduction light.

〔composition〕

As a result of various studies for the above-mentioned purpose, the present inventor found that improving the storage stability of optical information recording media requires not only the material of the substrate on which the recording layer is provided and the composition of the recording layer; The present invention was developed by focusing on the influence of interaction with Therefore, one object of the present invention is to use an acrylic polymer layer as a substrate on which a recording layer is provided, to provide a guide groove in the polymer layer, and to use a compound represented by the following general formula and a transition metal complex or This can be achieved by using a salt of the complex and a cation. Here, the "acrylic polymer" as used in the present invention means a polymer of acrylic ester or methacrylic ester.

In the general formula, X represents a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine, and m and n are 1 to 4
and Y represents an anion selected from the group consisting of perchlorate, benzenesulfonate, P-)luenesulfonate, methylsulfate, and ethylsulfate.

The optical information recording medium of the present invention is basically guided on the surface *t-
A recording layer containing the compound of general formula [0 and a transition metal complex or a cation salt thereof as main components] is provided on the acrylic polymer layer. Furthermore, a protective layer may be provided on the recording layer if necessary. Further, the recording medium thus constructed can also be used in a sandwich structure.

The heat resistance of the recording medium is improved when the compound of the above general formula is used, and this tendency is particularly noticeable when compared with compounds having no halogen atom (3). The reason for this has not yet been fully elucidated, but it is thought to be due to the electron-withdrawing effect of the halogen atom (3) on the indole ring and indolenine ring and the large ionic radius of the counter io 7 (YO). Furthermore, it has been found that when this specific compound is combined with a transition metal complex or its cation salt, the light resistance of the recording medium and the storage stability for the playback source are further improved.

The compound of the above general formula of the present invention is characterized in that 1 to 4 halogen atoms are present on the indole and indolenine rings, and no halogen ion is present as a counter ion. Note that those in which halogen ions are present as counter ions are not suitable because their decomposition rate is fast and, when used as a recording medium, the heat resistance tends to be low. Representative examples of the compounds of the above general formula are as follows, but the invention is not limited to these.

In addition, typical examples of transition metal complexes or cation salts thereof used in combination with the compound of the above general formula in the present invention are listed below, but the present invention is not limited thereto.

1) Acetylacetonatoquizito series (C-1)
N1(II) Acrylacetonate (C-2) Cu(
II) Acetylacetonate (C-3) Mn(III
) Acetylacetonate (C-4) Co (II) Acetylacetonate 2) Bisdithio α-diketone system (C-5) Bis(dithiobenzyl)nickel (C-6)
Bis(dithiobiacetyl)nickel(C-7)bis(4)
-Dimethylaminobenzyldithione nickel (C-83 bis(4-dimethylaminobenzyldithione nickel 3)) Bisphenyldithiol series (C-93 bis(1,2-dithio 7-erun nickel (
C-10) Bis(1,2-dithio-3,6-dimethylphenyl)nickel (C-11) Bis(1,2-dithio-5,4,6-
trimethylphenyl)nickel (C!-12) bis(1,2-dithio-5,4,5
-trimethylphenyl)nickel (C-13) bis(1,2-dithio-5,4,5,
6-titramethylphenyl)nickel (C-14) bis(1,2-dithio-5,4,5,
6-teto2chlorophenyl)nickel (C-15) Bis(1,2-dithio-3,6-dichlorophenyl)nickel (C-163bis(1,2-dithio-@-benzophenyl)nickel (C-17) Bis(1,2-dithio-3,6-methyl-■-benzophenyl)nickel (C-18) Bis(1,2-dithio-3-methyl7
enyl) nickel (C-19) bis(1,2-dithio-3,4,5+
, )lichlorophenyl)nickel(C-20) bis(1,2-dithio-5,4,6-
trichlorophenyl) nickel (c-21) bis(1,2-dithiophenyl) cobalt (c-22) bis(1,2-dithiophenyl) platinum (c-23) bis(1,2-dithio-5-chloro 722]nickel (C-24) bis(1,2-dithio-4-methylphenyl)nickel These metal complexes may also form salts with cations, such as the following quaternary ammonium 1 I can give you some lamb salt.

(C-25) Bis(1,2-diteo-6-methylphenyl)nickel tetrabutylammonium (C-26
) Bis(1,2-dithio-4-methyl7enyl)nickeltetrabutylammonium (C-27) Bis(1,2-dithio-3-methyl7enyl)nickeltetra(t-butyl)ammonium (C-283 bis(1,2-dithio-4-methylphenyl)nickeltetra(t-butyl)ammonium (C-29) bis(1,2-dithio-3,4,6-
) nickeltetra(t-butyl)ammonium (C-50) bis(1,2-dithio-5,4,5-
trimethylphenyl)nickeltetra(t-butyl)ammonium (C-51) bis(1,2-dithio-3,4,6-
) nickeltetra(4-k: troxybutyl)ammonium (C-323bis(1,2-dithio-3,4,5-)limethylphenyl)nickeltetra(4-h)'roxybutyl]ammonium( C-333 Bis(1,2-dithio-5,4,6-)lichlorophenyl)nickeltetra(4-hydroxybutyl)ammonium (C-34) Bis(1,2-dithio-3,4,5-
) Lichlorophenyl) Nickel tetra(4-hydroxybutyl) ammonium (C-35) Bis(1,2-dithiophenyl cobalt tetraprobylammonium (C-36) Bis(1,2-dithiophenyl) platinum dipropyl dibutyl Ammonium (C-37) bis(1,2-dithio-3,4,6-
Dolichlorophenyl]nickelte)(t-)aF-l)ammonium(C-38) bis(1,2-dithio-3,4,5-
trichlorophenyl)nickeltetra(t,-phthyl)
Ammonium 4) Salicylaldehyde oxime system where R1 and R2 represent an alkyl group and M is
Represents a transition metal atom such as N1, CO1Cu, Pd, Pj+.

(C-39) N1(If)o -(N-isopropylformimidoyl)phenol (C-40) N1(If)o -(N-dodecylformimidoylphenol (C-41) Co(If)o - (N-dodecylformimidoyl)phenol (C-42) Cu(If)o -(N-dodecylformimidoyl)phenol (C-43) Nt(t) 2.2'-1: Trilomethe in ethylene bis Lysine]-diphenol (c-44) Co(If) 2.2'-C ethylene bis trilomethylidine)]-diphenol (C-45) Co(■) 2.2'-(1,8-naphthylene bis ° trilomethylidine)]-diphenol (
C-46) Co(II) -(N-phenylformimidoyl)phenol (C-47) Co(II) -(N-phenylformimidoyl)phenol (C-48) Cu(If) -(N- phenylformimidoyl) phenol (C-49) Ni (...) salicylaldehyde phenylhydrazone (C-50) Ni (II) salicylaldehyde oxime 5) Thiobisferrate chelate system, where M is the same as above. , R5 and Aki represent an alkyl group. Further, M has a single charge and may form a salt with a cation.

(C-51) N1(If)n-butylamino(2,
2'-thiobis(4-tert-octyl)-phenolate] (Cyaaorb-Uv-1084 (American Cyanamid Company Limited)) (C-52) Co (n) n-butylamino (2,
2'-thiobis(4-tart-octyl)-7yl-
](C-53) N1(n) -2,2'-thiobis(4-tert-octyl)phenolate
Hydrazine-8-methyldithiocarboxylate General formula % Formula % Among the above metal complexes, bisdithio-2-diketones and bisphenyldithiols are particularly preferred. In addition, the transition metal complex has a weight ratio of 1/100 to the compound with the general formula symbol.
The weight ratio is preferably 1/20 to 1/6, although about 1/2 to 1/2 is added.

Various methods can be applied to form the recording layer according to the present invention, but since the compound represented by the general formula itself has low sublimability, methods such as vapor deposition and sputtering are not preferred, and a goating method using an organic solvent is usually applied. is preferred. When a coating method is applied, the recording layer in the present invention is formed by coating a solution of the compound of the general formula [0] and a transition metal complex or its cation salt dissolved in an organic solvent on an acrylic polymer layer having guide grooves. In addition, stabilizers, antioxidants, flame retardants, surfactants, dispersants, etc. may be included in the formation of the recording layer, but binders reduce reflectance. Examples of organic solvents used for coating include methanol, methylene dichloride, 1,2-dichloroethane, etc. Conventional methods such as coating hasply coach ink, spin coating, roller coating, dipping, etc. This is done by the ;-ting method.

The thickness of the recording layer (dry) is 20 mm at the convex part of the guide groove.
A range of 0λ to 2000X, preferably 250 to 800^ is suitable. If the film thickness is less than 200λ, the absorption is too small to record, and if it is more than 2000λ, the recording sensitivity decreases and noise increases.

It is necessary that guide grooves be formed in advance on the substrate on which the recording layer according to the present invention is provided.

Information is recorded in a spiral or concentric pattern, but for high-density recording it is necessary to reduce this pitch.

However, if there is no guide groove, there will be an inconvenience that the recording tracks will intersect due to shaft vibration or the like. The guide groove usually has a structure in which convex portions located at a high level and concave portions located at a low level exist alternately, and the height of the concave and convex portions is usually adjusted to λ/12 to λ/4. In addition, the width of the concave portion is approximately 0.3 μm to 1.2 μm, and the pitch thereof is 1.6 μm.
It is about pm to 2.4 μm. At the same time, information such as track addresses and sector addresses is also stored when creating the master disc.

Since coating with an organic solvent is usually used to form the recording layer in the present invention, the guide grooves must be insoluble in the solvent and the material constituting the guide grooves must not interact with the components constituting the recording layer. Therefore, it is necessary that the guide groove is made of an acrylic ester polymer and a methacrylic ester polymer, and it is particularly preferable that the guide groove is made of an acrylic ester polymer and a methacrylic ester polymer, and a photocurable amount is particularly preferable.

Further, as the substrate on which the guide grooves are formed, the acrylic polymer layer may be used as it is, or a layer on which guide grooves are formed on another substrate may be used. Plastic, glass, metal, ceramic, etc. can be used as such a substrate, but plastic is preferable because it is lightweight and hard to break.

Representative examples of the acrylic polymer used in the present invention include ethyl acrylate, n-butyl acrylate, 1-butyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, and octadecyl acrylate. , ethoxyethyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfuryl acrylate, stearyl acrylate, lauryl acrylate, N,N-diethylaminoethyl acrylate, N,N - Dimethylaminoethyl acrylate, glycidyl acrylate, benzyl acrylate, cyclohexyl acrylate, dicyclo is tenyl acrylate and the corresponding methacrylate; diacrylate and dimethacrylate are 1,3-propanediol diacrylate. , 1,6-butanediol diacrylate, 1,6-hexanediol diacrylate, 1.10
-Decanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxypiparic acid ester, neointhyl glycol diacrylate acrylate, trimethylolpropane diacrylate, bisoxyethylated bisphenol A diacrylate 1 bisdi(oxyethylenated) hisphenol A diacrylate, bisoxybutypyrenated bisphenol A diacrylate, bis(,t-?
'/propylenation) bisphenol A diazyryle-[
triacrylates, 3-methylbentanediol diacrylate, bis(acryloxymethyl)tricyclodecane, and make acrylates corresponding to each of the above acrylates. Examples of triacrylates and trimethacrylates include trimethylolpropane triacrylate and intererythritol. Mention may be made of triacrylates and the respective methacrylates as well as tris(2-hydroxyethyl)isocyanate. Examples of acrylates and methacrylates having four or more functional groups include diintaerythritol hexaacrylate, tetramethylolmethanetetraacrylate, hantaerythritol tetraacrylate, and the corresponding methacrylates. Among the above esters, diacrylic acid esters are preferred from the viewpoint of crosslinking properties, and bis(acryloxy)tricyclodecane is particularly preferred because of its small interaction with the recording layer.

In addition, K forming the acrylic polymer layer in the present invention
In addition to the above esters, Aku may contain known photopolymerization initiators (e.g. benzoin ethers) and sensitizers (
For example, amines), storage stabilizers (for example, quaternary ammonium chloride), etc. can be used. The photopolymerization initiator is used in an amount of 0.05 to 10 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of the acrylic ester or methacrylic ester monomer. The amount of sensitizer is 0.01 per 100 parts by weight of monomer.
It is preferable to contain it in a range of 5 parts by weight. In addition, the storage stabilizer is 0.001 to 100 parts by weight of the monomer.
It is preferable to contain it in a range of 2 MEk parts.

The optical information recording medium of the present invention basically has a recording layer provided on a substrate having guide grooves, but depending on the purpose, a preservation layer can be further provided on the recording layer. The protective layer is provided for the purpose of protecting the recording layer from scratches, dust, dirt, etc. and improving the chemical stability of the recording layer, and the film thickness is suitably at least α1 μm, preferably at least 50 μm. Examples of materials for the protective layer include polymeric materials such as ionomer resins, polyamide resins, vinyl resins, natural polymers, silicones, and liquid rubber, and inorganic compounds such as 5102, M
gF2, sio, TiO2, ZnO, TiN.

SiH, metals or metalloids such as ZnSCu, S
.

N1, Cr, Ge, Ss, CdlAg, At, etc. can be used.

Further, the recording layer in the present invention may be provided on one side or both sides of the substrate, and the recording layer may be provided in a so-called sand inch structure in which a pair of recording media are arranged with the recording layer on the inside to prevent dust and scratches. You can also avoid it. Further, in the sandwich structure, a material used for the substrate can be used as a protection plate on the opposite side of the recording surface. However, this protective plate needs to be transparent if the substrate on the recording layer side is opaque.

Next, the configuration of the optical information recording medium of the present invention will be illustrated with reference to the drawings.

As shown in FIG. 1, one example of the recording medium of the present invention is one in which an acrylic polymer layer 2 having guide grooves is provided on a substrate 1, and a recording layer 3 is further provided thereon. be.

An anchor coat 4 or the like may be present between the substrate 1 and the polymer layer 2.

FIG. 2 shows a so-called sand inch structure, which is the most preferred structure of the recording medium according to the present invention. This is a recording medium having the structure shown in FIG. 1, which is placed facing a substrate 1 so that the recording layer 3 is on the inside, and is enclosed and integrated using a spacer 4. The opposing substrate 1° may be a simple substrate or may have a recording layer provided thereon.

Alternatively, instead of using the air sandwich structure as shown in FIG. 2, it is also possible to use a single-plate structure in which a protective plate is provided to cover the recording layer 6 of the structure shown in FIG.

Conventional injection methods can be applied to form the guide grooves in the present invention, but in order to form guide grooves on the substrate that allow accurate writing and reading of information, it is preferable to use the method described below. .

First, as shown in FIG.
Prepare 2. The material of this type is generally nickel, chromium, or an alloy thereof, and is subjected to surface hardening or other treatment as necessary, but quartz glass, which is transparent to ultraviolet light, is preferable. Next, as shown in FIG. 4, a polymerizable composition 13 containing the above esters of the present invention as a main component is applied onto the mold 12, and after the substrate 1 is placed on top of the polymerizable composition 13, actinic radiation is irradiated. The polymerizable composition 13 is photocured. As a light source for active rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a carbon arc, an ultraviolet light lamp, etc. are used. After irradiation with actinic radiation, mold 12 is peeled off as shown in FIG.
A polymer layer 13' on which the guide grooves (concavo-convex pattern) 11 of No. 2 are accurately transferred remains on the substrate 1.

〔Example〕

EXAMPLES The present invention will be further explained below using Examples together with Comparative Examples, but the present invention is not limited by these Examples.

Example 1 1,6-hexanethiol acrylate)97. ! A polymerizable composition consisting of 5% by weight and 3% by weight of benzoin isopropyl ether is dropped onto a quartz stamper, and an acrylic coat (Fuji) 1 is applied thereon as an anchor coat layer.
After overlapping the acrylic substrates coated with 878-Fujikura Kasei), a high-pressure mercury lamp (80 W/
m ) for 2 minutes from a distance of 26 strokes for photocuring. Next, when the acrylic substrate was slowly pulled away from the stamper, guide grooves were formed on the substrate.

On the guide groove thus formed, a 1,2-dichloroethane solution of 0.7% by weight of the above-mentioned exemplified compound (D-1) and 1% by weight of the above-mentioned exemplified complex (C-7) was added. After coating and drying, a recording layer with a thickness of 500 mm was provided. Next, this recording layer was placed opposite the acrylic plate, and a 1n thick layer was placed -
An air sandwich structure as shown in FIG. 3 was formed using a thermosetting epoxy adhesive and a thermosetting epoxy adhesive.

This recording medium uses a semiconductor laser with a wavelength of 790 nm, a linear velocity of 1.24 m1sec, and a beam diameter of 1.6 ttm.
A signal of 0.7■2 was recorded. When this was reproduced, a C/N of 54 dB was obtained.

Next, this recording medium was exposed to 500W tungsten light for 2 hours.
When I played the signal again after leaving it for 4 hours, it was 55 dB.
A C/N of . Separately, this recording medium was stored in a constant temperature and humidity chamber at 60° C. and 90% for 3,000 hours, and then the signal was reproduced again, yielding 516B OC/N.

Examples 2 to 33 Each recording medium was produced and evaluated in the same manner as in Example 1 according to the formulations shown in the table below, and the results are summarized in the table below.

Comparative Examples 1 to 10 Each recording medium was produced and evaluated in the same manner as in Example 1 according to the formulations shown in the table below, and the results are summarized in the table below. A-1, A-2 and A-3 in the table
The compound is represented by the following general formula.

! (A) -T6 Heheheroro to Sun Tsuri LO sentry Sunono's dumb son's mouth (A) Rumor Ro He He Ro Sun
to 6 inches to LI'lLl')
The dumb pus
Hit your knees! (b) F
sentry sentry dumb sentry sentry
Incredible pain
ri mute h mute's mute
Chlorororo lolololololololololoro lol1. n mute Rororo +0 to mute 'OVo! Dimension Sentou (A) Dimension Sentoku I Roro Rororo Low CN Mouth P Example - 1 - Hehe = 6 mouths (l O. (1 (5d d cl cIOF% W
K to PCO-NG.

Rumors and rumors to rumors and rumors (JCJ (J (J (JC)ωQC) Q (J CJ
0 lo lo lo lo lo lo lo lo lo lo lo lo Ln %ONaQ
Wound - Heme! The dumb-semi v-v-c%4C'4hehehehehe 2B, D-10C-
52α3029 D-11C
-55α2530 D-9C
-70,2031D-90-80,20 32D-9C-351llL30 s3 o-9C-350,15
-G2 No D-2 - 3 No D-3 - 4D-4 none - 5D-5 none - 6D-6 none - 7A-I C-80,15 8A-20-370,15 9A-30-70, 15 1OA-I C-70,15 Comparative Example 11 On a substrate provided with a flat base layer made of acrylic polymer,
A recording layer was formed in the same manner as in Example 1. Although information was recorded on this at a pitch of 2 μm, track crossing occurred and the signal could not be read out.

〔effect〕

The optical information recording medium of the present invention does not have high recording sensitivity and is extremely stable against heat and light, so it has high storage stability, and therefore the written information does not change much over time, so there is no change in the written information (accurate). It has the advantage of being able to read the information and being easy to manufacture.

[Brief explanation of the drawing]

FIGS. 1 and 2 are cross-sectional views showing an example of the structure of an optical information recording medium of the present invention, and FIGS. 3 to 5 are explanatory views showing an example of a method for forming guide grooves. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Polymer layer provided with guide grooves, 3...
... Recording layer, 4... Spacer, 11... Guide groove, 1
2... Stamper-113... Polymerizable composition, 13'
...1 combined layer. Patent applicant: Rihito Rico Co., Ltd.
Patent attorney Haku Yamashita. -I. Procedural amendment January 21, 1985 Manabu Shiga, Commissioner of the Japan Patent Office1, Indication of the case, Patent Order No. 230300 of 19812, Name of the invention Optical information recording medium3, Case of person who makes M correction Relationship with Patent applicant address 1-3-6 Nakamagome, Ota-ku, Tokyo Name (
6741 Ricoh Co., Ltd. Contents of 76 Amendment to 14 Agents 1) The scope of claims will be amended as shown in the attached sheet. 2) General formula (1) on page 4, line 10: t - Correct as follows. 5) Add the following statement between the second and third lines of page 14. "(C-Ml) bis(1,2-dithio-3,4,6
4) In the formula on page 65, the following description of Example 64 is added next to Example 33. 1 Above 2, Claims On the acrylic polymer layer having guide grooves ft on the surface, a compound having the general formula (in the formula, or representing a halogen/atom selected from the group consisting of fluorine, , m and n are 1 to
4, and Y represents an anion selected from the group consisting of per@mate ion, benzenesulfone [[ ion, p-toluenesulfonate ion, methyl sulfate ion, and ethyl sulfate ion. An optical information recording medium, characterized in that the compound represented by /'f: represents) and the transition metal complex 19 have a recording layer containing a salt of the complex and a cation.

Claims (1)

[Claims] On the acrylic polymer layer having guide grooves on the surface, there is a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein X is selected from the group consisting of fluorine, chlorine, bromine, and iodine) represents a halogen atom, m and n are 1 to 4
and Y represents an anion selected from the group consisting of perchlorate ion, benzenesulfonate ion, p-toluenesulfonate ion, methylsulfate ion and ethylsulfate ion). 1. An optical information recording medium comprising a recording layer containing a transition metal complex, or a salt of the complex and a cation.