JPS58101092A - Optical information recording medium - Google Patents

Abstract

PURPOSE:To provide a titled medium capable of recording with a high energy beam with a recording layer which is composed of 3-layers of a reflecting layer at the side of a substrate, the second light absorbing layer at the surface side and the first light absorbing layer disposed therebetween. CONSTITUTION:Metal compound of silver nitrate or the like is dissolved with colorant in water together with reducing agent such as reduced sucrose or the like. Then, the obtained two resin solutions are sequentially coated on a substrate such as plastic, are heated, dried, are composed at the side of the substrate of a reflecting layer 3 which contains metal particles, at the side of surface of the second light absorbing layer 5 which contains colorant, and of the first light absorbing layer 4 which contains metal particles and/or metal compound therebetween in a recording layer 2, which is beared on the substrate 1, thereby obtaining the objective recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an optical information recording medium in which the recording layer supported on a substrate is composed of three layers: a reflective layer, a first light-absorbing layer and a second light-absorbing layer.

In the past, many optical information recording media for laser writing have been developed. Typical examples include recording media with vapor-deposited films of metals, semimetals, and non-metals, and recording media with reflective films formed by heating a silver dry plate. However, recording media made of vapor-deposited films of metals, semimetals, and non-metals are generally manufactured by vacuum forming in a patch system rather than in a continuous system, making them expensive and requiring a large number of patches. It is difficult to achieve quality uniformity for mass producing products. In addition, exposure is a method of forming a reflective film by heating a silver dry plate.

In addition, since the reflective film is formed on the surface opposite to the substrate, it is prone to scratches and requires a line protection film in practical use.

An object of the present invention is to provide an optical information recording medium in which a reflective layer of metal particles is provided on the substrate side of the recording layer through a short process consisting of coating and heating, and the recording sensitivity is improved.

Another object of the present invention is to provide an optical information recording medium that requires a protective film layer.

According to the present invention, a recording layer supported on a substrate 9 further comprises a reflective layer containing metal particles on the substrate side of the recording layer, and a second light absorption layer containing a dye on the surface side of the recording layer, and Provided is an optical information recording medium capable of recording with a high-energy beam, in which a first light-absorbing layer containing metal particles and/or a metal compound is present between the reflective layer and the second light-absorbing layer. be done.

The basic structure of the optical information recording medium of the present invention will be explained with reference to the accompanying drawings. A recording layer 2 is supported on a substrate 1, and the recording layer 2 includes a reflective layer 3, a reflective layer 3, and a reflective layer 3. Absorbent layer 4
It is composed of three layers: a dielectric layer and a second light absorption layer 5.

The substrate materials used in the present invention are known to those skilled in the art and must be transparent to the high energy beam used.

General recording material substrates such as glass and plastic can be used, and plastic is particularly preferred from the viewpoints of safety, improved recording sensitivity, and flatness. As the plastic, acrylic, polycarbonate, polysulfone, polyimide, etc. are used. Particularly preferred are polysulfones and polyimides. 1+, an undercoat layer using these resins may be provided on the glass substrate. Further, there is no problem even if an undercoat layer is provided on the plastic substrate.

The metal compound used in the present invention has the following metal particles Ag, Au, Cu, PeL,
Pa, Co, Ni, Ti, V, 81, Ge,
Be, Th, Mn.

Pt, Rh, Tc, Re, Ru, Os
, Mo, 'I'a, At, Eng1an, Be1
To, CrXB1, Hf, Y, N, d, Zr,
WSZn.

It can form Mg, BQ, Nb, La, and pr.

Specific examples of the metal compound include steel nitrate, potassium silver cyanide, potassium gold cyanide, silver ammine complex, scissor cyanide complex, gold salt, or gold cyanide complex. As a reducing agent, formalin, tartaric acid, tartrate, reducing sugar,
Hyporite, sodium borohydride, dimethylamine borane, etc. can be used. The reducing agent can be used in an amount of 0.2 to 10 mol, preferably 0.45 to 4 mol, per 1 mol of the metal compound.

It is sufficient that the dye used in the present invention has absorption near the wavelength of the high-energy beam, and it is particularly preferable that the dye has maximum absorption near the wavelength of the high-energy beam.

Examples of these dyes include the following dyes.

(1) Direct dyes Classified based on chemical structure, there are azo, stilbene, thiazole, dioxazine, phthalocyanine, etc. Representative examples of each are listed below.

(a) Azo type C0 work, Dairef+ Yellow 12 (C, L248
95) Orange 29 (' 29155) Red
2 (' 23500) Violet 7 ('
27855) Blue 41 (“ 42700) Green 53 (’ 34270) 59 (’ 5
4040) Brown 25 (' 36030) Black 2
2 (' 35435) 56 (' 34170) (b) Stilbene-based C0 Engineering, Direct Yellow 39 Black 62 (C) Phthalocyanine-based C, 1, Direct Blue 86 (C, Engineering, 7
4180) (2) Acidic dye (a>Azo type C, 1,7 side yellow 36 (c, engineering, 130
s5) Orange 56 (' 22895) Red 9 (' 15635) Violet 7 (' 18055) Blue
29 (' 20460) Green 55C' 13361) Black 26 (' 27070) (b) Anthraquinone C,1,7 violet (C,1,617
10,61800) Blue 23(' 61125
) Green 44 ('61590) Black 4B ('65005) (c) Triphenylmethane type C,1,7)'-Violet 49 (C,1,4
2640) Blue 83 (' 42660) Green 16 (' 44025) (,1) Xanthine-based C, L acid red 92 (c, x, a5410) (
e) Purine C, 1, Acid Red 59 (C, Engineering, 50315
) Black 2 (' 50420) (3) Basic dye (a) Cyanine type C, 1, Bain 7 Ri1 1/7 Do 12 (C, 1,480
70) Violet 7 (' 48020) (b) Azo C, 1, Paysic war plow y1 (C, 1, 2100
0) Black 2 (' 11825) (0) Azine C, 1, Pacific Red 2 (c, x, 5o2
4o) c, r, paysic-L/7 de 1(c, x
, 45160) Violet 10 (' 45170
) Blue 3 (' 51005) Blue 25 (' 52025) (d) Triphenylmethane C,L Basic Red 9 (C', 1.42
500) Violet 3 (' 42555) Blue 1 (' 42025) Green 4 (' 42000) (4) Mordants and acidic mordant dyes (a) Azo-based C0 technology, Moment E r-t'l-1 (C,: [,
14025) Yellow 26 (12288o) Orange 37 ('1873o) Red? (' 16105) Violet 5 ('' 15670) Blue 13 (' 166B0) C, 1, f-Dant Green 11 (C', Engineering, 2Q
440) Black? (' 16500) 佽) Anthraquinone-based Moment Red 3 (C6 engineering, 5 soos) Blue 8 (' 58805) Black 13 (' 63615) (0) Xanthine-based Moment Red 15 (C, engineering, 45305) (d)
Triphenylmethane Moment Violet 1 (C1, 43565) Blue 47 (' 43855) (5) Vat dye b) Anthraquinone C0 ■, Pat Yellow 2 (C, C67ri 00) Yellow 4 (' 59100) Orange 2 (' 59705) Red 10 (' 67000) C, 1, Bat Violet 15Cc, x, 687D
O) Blue 18 (' 59815) Green 8 (' 71050) Black 9 (' 65230) Green D
' 59825) 0:l) Indigoid C, L Pat Orange 5 (c, z, 73335)
Orange 7 ('71105) Red 2 ('75565) Violet 2 ('75385) Blue
1 (' 73000) (6) Disperse dye (&) Azo C, 1, Disper x-I xo-7 (C, 1, 26Q9
0) Orange 5 (' 11100) Red 7 (' 11150) Violet 24 (' 11200) Orange 11 (C, Engineering, 60700) Red 11
(' 62015) Violet 4 (
' 61105) Blue 27 (' 6
0767) (7) Oil-soluble dye (, L) Azo C0■, Solvent Yellow 6 (c, x, 1139
0) Orange 5 (' 18745) Red 27 (' 26125) Brown 5 (' 12020) ■) Anthraquinone Violet 14 (C, 1, 61705) Blue 1
1 (' 61525) Green (' 61
565) (c)7 Talocyanine Solvent Blue 25 (C, 1,74350) cd
) Triphenylmethane type 051 (C, Eng., 21260) The optical information recording medium of the present invention can be manufactured by various methods, and one of the manufacturing examples will be explained next.

First, the metal compound, the reducing agent, and the dye are dissolved in a water-soluble resin using water or a suitable solvent. As the water-soluble resin, for example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, etc. can be used. The weight ratio of the metal compound to the water-soluble resin is 0.1 to 10, preferably 0.5 to 1.5.

The amount of pigment added is 0.002 to 10 in weight ratio to resin.
Preferably it is 0.01 to 1.0. Next, the above resin solution is coated onto a suitable substrate by brush coating, roller coating, flow coating, rotation coating, spray coating, etc. to a film thickness of 0.05.
~10μm, preferably 0.1~2μm, coated with 50~1μm
Dry by heating at 50°C, preferably 60 to 100°C. Thus, a reflective layer of metal particles is formed on the substrate side, while a light absorption layer of metal particles and/or a metal compound is formed on the surface side. After a while, on the first light absorption layer,
A solution in which the dye is dissolved in a resin is coated with a film thickness of [105 to 10μ].
The second light absorbing layer is formed by coating preferably at a thickness of 0.1 to 2 μm. As the resin, known resins can be used, including those that are soluble in a solvent.

Information is recorded by applying a spot of a high-energy beam such as a laser beam from the substrate side, and the absorbed heat creates a hole in the reflective layer and records the information. Since the recording surface is on the substrate side, no protection layer is required.

Furthermore, information can be read by irradiating a low-power laser beam and detecting the information by reducing the amount of reflected light.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 Polyvinyl alcohol 1v Water 9f Silver nitrate
1.5t 28% aqueous ammonia 3-glucose 1.5f A solution with the above composition was applied to an acrylic plate by spin coating and dried at 70°C for 10 minutes to form a reflective layer with a total thickness of 0.6 μm and a third light. Lost the absorption layer.

Furthermore, a solution with a composition similar to that of polyvinylbutylene 0.5F ethanol 5-waterable 9 (manufactured by Orient Chemical Co., Ltd.) 0.1F was applied onto this first light-absorbing layer, dried naturally, and then exposed to a second light-absorbing layer. An absorbent layer was obtained. Reflectance is 30 from visible range to near infrared range
The absorption rate was 65. He-N was added to the recording medium thus obtained.

Using a laser, the irradiation surface energy is 7 mW and the beam diameter is 2.4.
When information was recorded on the substrate surface in μm, a spot with a diameter of 1.4 μm was formed by irradiation for Q, 8 F seconds (writing energy 5.6 nJ/pit).

For comparison, the writing energy was 17.5 nJ/pit when the second light absorption layer was not applied.

Example 2 Polyacrylamide 0.5f Water 9.51 Sulfuric acid steel
1f 28gk aqueous ammonia 3- 5SS formalin α5- A solution with the above composition was applied to an acrylic plate by spin coating and dried at 100°C for 5 minutes to give a total thickness of α5.
A .mu.m reflective layer and a second light absorption layer were obtained. Furthermore, on this first light absorption layer, polyvinyl alcohol
0.5v water
5f Direct Blue 2B (C,
1,22610) 0.2f (manufactured by Sumitomo Chemical Co., Ltd.) was applied to obtain a second light absorption layer.

The reflectance is 351. Absorption rate is 60
It was a fight. He-
When recording was performed using a Ne laser in the same manner as in Example 1, a spot with a diameter of 1.2 μm was formed by irradiation of 1.0 F seconds (writing energy 7 nJ/pit).

For comparison, a sample without the addition of dye was prepared, and the writing energy was 20n, T/pit.

Example 3 The coating liquid for the second light absorbing layer had the same composition as in Example 1, and the dyes and resins shown in the table below were used, and the recording sensitivity shown in the table was obtained.

61200) Mitsui Toatsu Nine Bra #3 98
Tsuku Gt (C, 1, 52015) 10% Example 4 Same composition as Example 1, but the dye in the second light absorption layer was NK-1.
23 (Nippon Kanko Dyes) was used to obtain a 9 recording medium, and a semiconductor laser with a wavelength of 820 nm was used to generate a beam diameter of 15 μm.
When recording was performed from the substrate side with 1 irradiation surface energy of 4 mW, it was found that 1.6 μ' seconds of irradiation (writing energy of 6, 4
nJ/bit), and a spot with a diameter of 0.8 μm was formed.

[Brief explanation of drawings]

The accompanying drawing is a sectional view showing the basic structure of the optical information recording medium of the present invention. DESCRIPTION OF SYMBOLS 1...Substrate, 2...Recording layer, 5...Reflection layer, 4...
... 1st light absorption layer, 5... 2nd light absorption layer. Patent applicant Rico Co., Ltd. −5,・′

Claims (1)

[Claims] The recording layer is supported on a substrate and is composed of a reflective layer containing metal particles on the substrate side, and a second light absorbing layer containing a dye on the surface side of the wrinkled recording layer, and the reflective layer and A high-energy beam recordable optical information recording medium, characterized in that a first light-absorbing layer containing metal particles and/or a metal compound is present between the second light-absorbing layer.