JPH02277689A - Optical data recording medium - Google Patents

Abstract

PURPOSE:To enhance the productivity and to simplify the constitution and a process to achieve the cost reduction by laminating a protective film to a recording film composed of a membrane of a mixture containing at least one of metal oxide and metal nitride fine particles as the first component, org., matter as the second component and metal fine particles as the third component. CONSTITUTION:This optical data recording medium 10 is constituted of a recording film 12 and a protective film 13 and the first component 1 in the recording film 12 is composed of fine particles of oxide or nitride of either one of metals of the Groups IIB - VIB of the Periodic Table or fine particles of both of them. The second component 122 is org. matter and the third component 123 is fine particles of at least one of metals of the Groups IIB - VIB. Next, the protective film 13 is a membrane composed of a mixture containing at least one of metal oxide, metal nitride, metal carbide, metal silicide and metal boride as the first component 131 and org. matter as the second component 132. When this recording film 12 is irradiated with recording laser beam, a protruding deformation part called a bubble is formed and, even when the protective film is laminated to this bubble mode recording medium, the deterioration of recording reproducing characteristics, especially, a lowering of a reproduction signal contrast ratio is reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to an optical information recording medium in which information is optically recorded and reproduced by laser beam irradiation.

(Prior Art) Two types of optical information recording media have been put into practical use. The first optical information recording medium 100 has an air gap structure, and the second optical information recording medium 200 has a so-called solid structure. The schematic cross-sectional diagram of each
2(a) and (b), FIG. 12(a) is the air space configuration,
(b) shows a solid structure. In FIG. 12(a), 101 and 111 are substrates, 102 and 112 are spacers,
103 and 113 are recording films, and 104 is a space.

In the air gap configuration, the substrate 1 on which the recording film 103 is deposited
01 and the substrate 111 on which the recording film 113 is deposited are arranged so as to face each other. The solid structure is characterized in that recording films 202 and 212 deposited on two substrates 201 and 211 are opposed to each other and integrated with each other via an adhesive layer 203.

A drawback of the spaced configuration is that the two substrates 101, 111 are bonded together only at the spacers 102, 112, so the substrates 101, 111 are easily deformed. Furthermore, since prevention of deformation requires advanced technology and complicated processes, it is difficult to reduce costs. Despite these drawbacks, optical information recording media with a solid structure are used because a hole-forming type recording film that has a solid structure causes a significant decrease in recording sensitivity. In other words, the space configuration can be said to be a configuration dedicated to recording media that use hole-forming type recording films.

In the solid structure, since the substrates 201 and 211 are bonded and integrated over the entire surface, there is an advantage that the substrates are less deformed. However, the disadvantage of a recording medium with a solid structure is that, although it does not have an air gap structure, it still requires many manufacturing steps, making it difficult to reduce costs.

The increase in the number of steps and the accompanying decrease in yield are mainly caused by the adoption of the bonding step. The adhesion process consists of three steps: coating, curing, and aging.

The coating process is a wet process. On the other hand, in almost all cases, the recording film is formed by a dry process such as vacuum deposition or sputtering. Therefore, there is no consistency between the two. That is, continuous processes, which are essential for improving productivity, are not possible. It must be carried out as two completely independent steps. Curing and aging of adhesives is a dry process. However, these steps usually require a long time, ranging from several hours to 24 hours, and have low productivity.

That is, it is strongly desired to realize an optical information recording medium that has a simple manufacturing process and can be manufactured at low cost.

(Problems to be Solved by the Invention) An object of the present invention is to provide an optical information recording medium that uses only a dry process, that is, has high productivity, has a simple structure and process, and can therefore achieve low cost. There is a particular thing.

[Structure of the invention]

(Means for Solving the Problems) In order to obtain an optical information recording medium that has excellent recording and reproducing characteristics, can be reduced in cost, and is highly practical, the following three means are used in the present invention.

The first is that the overcoat structure is simpler than the solid layer structure. FIG. 1 is a schematic diagram showing a cross section of an optical information recording medium 10 that is one of the embodiments of the present invention. In FIG. 1, 11 is a substrate, 12 is a recording film,
13 is an overcoated protective film.

The second is to use a bubble mode recording medium as the recording film 12, in which when irradiated with a recording laser beam, raised deformed parts called bubbles are formed instead of holes called holes. . The characteristics of bubble mode recording media are:
Unlike a hole mode recording medium, even when a protective film is laminated, there is little deterioration in recording/reproducing characteristics, particularly in reproduction signal contrast ratio.

The third method is to use a thin film as the protective film 13, which can be formed by the same dry process as the recording film 12 and has characteristics that are satisfactory as a protective film.

That is, it is necessary to use a new protective film that has high mechanical strength and hardness, has a rich protective function for the recording film, and has good adhesion to the recording film.

Hereinafter, the recording film and protective film of the recording medium according to the present invention will be explained in more detail.

FIG. 2 shows a recording film 1 of an optical information recording medium 10 according to the present invention.
2 is a schematic diagram showing each cross section of the protective film 13 and the protective film 13. FIG.

In FIG. 2, 121 in the recording film 12 is a metal of group IIB of the periodic table, a metal of group IIIB, I
At least one of, or both of, oxide fine particles of any of the VB group metals, VB group metals, and VIB group metals, or nitride fine particles of any of the above metals. Hereinafter, regarding the notation of metals, for example, "metal of group XA of the periodic table" will be abbreviated as "rXA metal". Further, 121 fine particles made of metal oxide or metal nitride form a matrix of the recording film 12 and form the skeleton of the recording film. Also.

122 in the recording film 12 is an organic substance which is a second component.

This organic substance 122 is dispersed within the matrix 121. Furthermore, 123 in the recording film 12 is a fine particle of at least one of IIB gold metal IIIB metal, ■B gold metal VB metal, and VIB metal, which are the third components.

Next, 131 in the protective film 13 in FIG. 2 indicates ITB metal, IIIB gold metal IVBVB metal B, which is the first component.
metal, VIB metal, IIIA metal, IVA metal,
VA Gold Metal VIA Metal, VIIA Gold Metal and VIII
A fine particles of oxide of any gold metal, IIIB gold metal rV
BVB metal [l metal, ■ A gold metal VA gold metal and VI
Any nitride fine particles of A metal, IIIB metal, IV
BVB Metal VA Metal, VA Gold Metal VIA Metal, VIIA
Carbide fine particles of either gold metal or VIIIA gold metal, IVA metal.

Silicide fine particles of either VA gold metal or VIA metal, BIB metal, mA gold metal IVA metal, VA gold metal VI
At least one of boride fine particles of A metal, VIIA gold metal, and VIIIA gold metal. The fine particles 131 form a matrix of the protective film 13 and form the skeleton of the thin film. Further, 132 in the protective film 13 is a second component, an organic substance, which is dispersed in the matrix 13].

(Function) FIG. 3 is a schematic diagram showing a cross section of the recording medium of the present invention in which bubbles are formed. In FIG. 3, the protuberance indicated by 14 is a bubble. A void 15 is formed between the recording film 12 and the substrate 11 in the bubble forming portion 14 .

As shown in FIG. 2, the recording film 12 contains at least metal oxide or nitride fine particles, metal fine particles, and organic matter. Therefore, when such a recording film is irradiated with a recording laser beam, the bubble 1 is created through the following four steps.
4 is formed. That is, the first step is absorption of the laser beam by the metal particles, and as a result of the absorption, the temperature of the metal particles increases.

The second step is to raise the temperature of the metal oxide, nitride fine particle matrix, and dispersed organic matter by thermal diffusion from the metal fine particles. The third step is the decomposition and evaporation of the dispersed organic matter.6 The fourth step is the deformation of the metal oxide and nitride fine particle matrix induced by the evaporation of the organic matter acting as gas pressure. At this time, the protective film 1 on the recording film
3 is also raised similarly to the recording film 12. Through the above process, bubbles 14 can be formed on the recording medium IO.

The writing principle is as described above, but reading is performed as follows. That is, when this raised deformation portion is irradiated with a reading laser beam, the beam is diffracted. Therefore,
By detecting the reflected light of the readout beam, it is possible to detect the presence or absence of a deformed portion or the position of the deformed portion as a change in the amount of reflected light. The contrast ratio of the readout signal increases as the amount of deformation increases. Furthermore, in a recording medium that has a high contrast ratio, it is easy to perform signal processing with a low error rate. The shape of the bubble is
As described later, this can be controlled by optimizing the chemical composition of the recording film and the protective film.

As mentioned above, the protective film should have three satisfactory characteristics: high hardness, good adhesion to the recording film, and ability to be formed by the same dry process as the recording film.

The first property, high hardness of the protective film, is achieved by using at least one of metal oxides, metal nitrides, metal carbides, metal silicides, and metal borides as constituent components of the protective film, which are inherently highly hard. This is achieved by

The second satisfactory property, the increase in the adhesion of the protective film to the recording film, depends on the chemical properties of the protective film, such as its components and composition, and its physical properties, such as its coefficient of thermal expansion and internal stress. This is achieved by making the characteristics of each recording film similar. Specifically, since the recording film is composed of metal oxide, nitride fine particles, metal fine particles, and organic matter,
High adhesion to the recording film can be obtained by forming the protective film with an organic material added to the above six types of high hardness components. The adhesion of the protective film of the present invention is the adhesion of a thin film composed of the above six types of high hardness compounds alone, or
The adhesion strength is greater than that of a thin film composed of organic matter alone.

Furthermore, regarding the similarity of the formation process with the recording film, which is the third characteristic of the protective film.

Although it will be explained in more detail later, it can be easily agreed that it is possible due to the similarity of its structure to that of a recording film.

One advantage of forming the protective film after forming the recording film is that it can reduce costs as mentioned above, but another advantage is that there are fewer pinholes and foreign substances. Since a protective film can be formed, it is easy to obtain a recording medium with a low error rate.

(Example) As the metal oxide or metal nitride 121 which is the first component of the recording film 12 of the optical information recording medium of the present invention, any metal oxide or metal nitride may be used as long as it is stable when stored in the atmosphere. is also available. The following are particularly desirable. As a metal oxide, periodic table mu gold metal oxide A
Q□○1, Ga, O,.

I n, O,, IVB *Gold oxide Sio,, Ge
O□, SnO2, VB metal oxide sb, ○1.5b2
o, , Bi201, VIB metal oxide Tea can be used.

These can be used alone or in combination. As a metal nitride, I[[B metal nitride B
N, AQN, GaN, InN, IVBVB metallization S
i, N4, Ga, N can be used. Similar to the metal oxides described above, a plurality of these can be used in combination. Furthermore, metal oxides and nitrides may not be used independently, but may be used as a mixture, or as a quaternary system of multiple metals, oxygen, and nitrogen, such as 5i-AQ-〇-N. can not use.

Organic matter 1 in the recording film 12 which is the second constituent component of the recording film
22 is carbon, hydrogen, and oxygen.

Alternatively, any organic material can be used as long as it contains at least nitrogen, or both, and fluorine.

As the metal fine particles 123 in the recording film 12, which is the third component of the recording film, any material can be used as long as it is stable when stored in the atmosphere.

The following can be used as particularly desirable:

That is, IIB gold metal Zn of the periodic table, [AQ of 8 metals.

In, ■8 metals Si, Ge, Sn, and VB metal Sb.

Bi, VIB metal Te can be used. These can be used alone or in combination.

It can also be used as an alloy or as an intermetallic compound.

The metal oxides, metal nitrides, metal carbides, metal silicides, and metal borides 131 that are the first constituent components of the protective film 13 of the recording medium of the present invention are also stable when stored in the atmosphere. Anything can be used. The following are particularly desirable. As a metal oxide, periodic table IB gold metal oxide CuO2, IIB
Metal oxide Zn○, IffB m group oxide AQ2
0. , Ga2O,, In201, IVBVB metal oxide Si○2, GaO2, SnO,, VB metal oxide 5b
2o,, 5b2o,, Bi, 03, VIB metal oxide T e O2, HA gold metal oxide Y, Off, rare earth metal oxide, IVA metal oxide Tie,, Z r O
,,HfO2,VA gold metal oxide V,03. Nb2O,
, Ta, O,, VIA metal oxide Cr201, M
O203, WO2, ■ Metal oxide MnO, M, 2
0. ．． Mn, O,, ReO2, VIIIA gold metal oxide Fe, O,, Fe50. , RuO2, CoO, Ni○, etc. can be used. As metal nitrides, periodic table I [[B
Metal nitride BN, AQN, GaN, InN, ■B
Gold metal nitrides Si, N, Ge, N, VB metal nitrides SbN, and IVA metal nitrides TiN, ZrN, H
fN, VA gold metal nitride VC, NbC3T a C1V
IA metal nitrides Cr N , M o N , W
N etc. can be used.

As carbides, carbides of IIIB metals of the periodic table B4C3
■8 Metal carbide 5iC1 and MC type T i C3
ZrC, HfC, VC, NbC, TaC, MoC1WC
1 Furthermore, MC2 type VC2, TaC2, M o C2,
WC2, and M3C type Mn, C, Fe, C, Go,
C1Ni3C etc. can be used. As metal silicides, silicides of IVA metals of the periodic table TiSi2, Z r Si
,,HfSi, VA gold metal silicide VSi2, Nb5Si
,, TaSi, , VIA metal silicide CrSi2, Mo
Si2, WSi2. VIIIA Gold Metal MnSi, VII
IA gold metals such as Fe, Si, CoSi, and Ni52 can be used. Examples of metal borides include Periodic Table I [IA gold metal borides Yb4, Yb1□, IIIB metal borides Al
Borides of rare earth metals such as 2B2, LaB, IV
A metal boride TiB, TiB2, ZrB, ZrB2,
ZrB, , HfB, , VA gold metal boride V B , N
b B, T a B z, Ta3B, , VIA metal boride CrB, CrB2, Cr, B4. Cr2
B, Cr, B.

VIIA gold metal borides MnB, MnB, VIIIA gold metal borides FeB, Fe, B, Co3B, Ni, B, etc. can be used.

As the organic substance 132 which is the second component in the protective film 13, the same organic substance as the recording film 12 can be used.

That is, any organic substance can be used as long as it contains at least carbon, hydrogen, oxygen, nitrogen, or both, and fluorine.

A recording film and a protective film having such a structure can be manufactured by various methods as described below. The first method is to simultaneously perform reactive sputtering and plasma polymerization. The second method is to perform multi-target sputtering and plasma polymerization simultaneously. Third
is a method in which plasma polymerization and multi-source deposition are performed simultaneously. The fourth method is a method using only multi-target spattering. The fifth method is a method using only multi-source evaporation. The sixth method is a plasma CVD method using organic metals, metal halides, hydrocarbons, and the like as raw materials.

A detailed example of manufacturing the recording film and protective film of the present invention by the first method will be shown below. For example, in order to form a recording film containing at least metal oxide fine particles, metal fine particles of the metal oxide, and an organic substance, the metal target may be heated using at least hydrocarbon, oxygen, or further argon or carbon fluoride. It is best to subvert it with a mixed gas that contains it. Similarly, in order to fabricate a thin film containing at least metal nitride particles, metal nitride particles, and an organic substance, the metal target may be heated using hydrocarbon, nitrogen, or at least argon or carbon fluoride. Sputtering may be performed using a mixed gas containing the above. Here, the hydrocarbon is CH4
, C, H methane hydrocarbons such as C, H, Cz H
4. Ethylene hydrocarbons such as Ca Hi, C, H2,
Acetylenic hydrocarbons such as C, H4, C, H,, C
, H, -CH,, C, I-(□2) and other cyclic hydrocarbons can be used.

As carbon fluoride, CF4. CHF,,C,FiC,F
, methane-based fluorocarbons such as C, F4. C3F1C2H
, F, etc., and cyclic fluorocarbons such as C4F, C, F, C, F1□, etc. can be used.

In addition, in order to form a protective film containing at least metal oxide fine particles and organic matter, the metal target may be a hydrocarbon,
Sputtering may be performed using oxygen or a mixed gas containing at least carbon fluoride. As the hydrocarbon and carbon fluoride used for forming the protective film, any of the hydrocarbons and carbon fluoride used for forming the recording film can be used.

Here, although the structures of the recording film and the protective film are different, the reason why both can be manufactured using substantially the same manufacturing method as described above is as follows. That is, in the discharge in a sputtering device, the parameter that can usually be changed is the gas composition.

There are five types: discharge pressure, applied power, discharge time, and average residence time of gas. In the case of forming the recording film and protective film disclosed in the present invention, reactive sputtering and plasma polymerization proceed simultaneously as described above. Gas composition, discharge time,
When the average residence time of the gas is kept constant, plasma polymerization is promoted as the discharge pressure increases and applied power decreases, and conversely, reactive sputtering is promoted as the discharge pressure decreases and the applied power increases. There is a tendency to Therefore, the chemical composition of the formed thin film can be controlled by changing the discharge pressure and applied power.

How the chemical composition of the thin film changes depending on the discharge pressure when the applied power is constant will be explained using FIG. 4. FIG. 4 shows the first example according to the present invention under a certain applied power.
This is the relationship between the deposition rate of a thin film such as a recording film and the discharge pressure according to the manufacturing method.

As shown by curve A, the thin film deposition rate increases gradually as the discharge pressure increases. However, this thin film is composed of both components incorporated into the thin film by reactive sputtering and components incorporated by plasma polymerization. The deposition rate of the former component is as represented by curve B.

It shows an extreme value at a certain discharge pressure, and rapidly decreases at a discharge pressure higher than that pressure. On the other hand, the deposition rate of the latter component increases almost monotonically as the discharge pressure increases, as represented by curve mC.

Next, how the chemical composition of the thin film changes depending on the applied voltage when the discharge pressure is constant will be explained using FIG. FIG. 5 shows the relationship between the thin film deposition rate and applied power under a certain discharge pressure. The deposition rate of the thin film increases as the applied power increases, as represented by curve A. here.

This increase in deposition rate is primarily due to an increase in the deposition rate B of components incorporated into the thin film by reactive sputtering. The components taken in by plasma polymerization show extreme values in the region where the applied power is low.

Furthermore, even if the discharge pressure and applied voltage are constant, the chemical composition of the thin film to be formed can be controlled by changing the gas composition. That is, in the case of sputtering using a mixed gas containing a reactive gas, the thin film formed is: (1) composed of only a metal component, (2) a mixture of a metal component and metal oxide or nitride fine particles. If ■
When it is composed only of metal oxide and nitride fine particles that are reaction products, it can be classified into three types. Changes in the constituents of this thin film primarily depend on the partial pressure of the reactive gas. In other words, PM is the partial pressure at which a thin film is formed from only metal components.
, P is the partial pressure at which a thin film is formed from metal components, metal oxides, and nitride particles. , when the partial pressure at which a thin film is formed only from metal oxide and nitride fine particles is P, these three
Under certain conditions such as appropriate applied power and discharge pressure, the following relationship holds between the two.

Therefore, in the case of forming the recording film of the present invention, the relationship between the partial pressure of the reactive gas and the deposition rate of the product by reactive sputtering and the organic matter by plasma polymerization under a certain applied power and discharge pressure is shown in Figure 6. It becomes like this. In Figure 6,
B-1 is the deposition rate of metal components among the products of reactive sputtering, and B-2 is the deposition rate of metal oxide and nitride fine particles. In addition, C is the deposition rate of organic matter, A
is the total thin film deposition rate. Here, the minimum partial pressure of the responsive gas at which the metal oxide or nitride fine particles are incorporated into the recording film is P, and the maximum partial pressure of the responsive gas at which the metal component is incorporated into the recording film is P2.

Next, the decomposition temperature of organic matter can also be controlled by controlling the average residence time of the gas. This is because by increasing the average residence time of the gas, the plasma polymerization reaction is promoted, and a more dense three-dimensional structure, or in other words, a more highly cross-linked organic substance, can be formed. 6 Finally, the discharge time is directly related to the thinness of the thin film.

The above describes the type of recording film that can be formed by changing the five parameters, and the method used to produce the desired recording film. By appropriately selecting these parameters, the recording/reproducing characteristics, spectral characteristics, lifetime characteristics, etc. of the recording film can be controlled to suit the purpose.

The second manufacturing method of the recording medium of the present invention is a method in which simultaneous multi-target sputtering and plasma polymerization are performed at the same time, and in particular, protection is made of constituents that are difficult to form by reactive sputtering, such as silicides and borides. This is an effective method for forming films. Specifically, the recording film is formed by plasma polymerization of stearic acid and hydrocarbon of any of the above metal targets and any of the above metal oxide or metal nitride targets, and similarly, the protective film is formed by plasma polymerization of stearic acid and hydrocarbons. Hydrocarbons, which serve as raw materials for plasma polymerization, are formed by sputtering a compound target such as any of the metal oxides described above and plasma polymerization of hydrocarbons, etc.;
As the carbon fluoride, any of those listed in the first manufacturing method can be used.

A third method for manufacturing a recording medium of the present invention is a recording film.

Another method is to incorporate components other than organic substances in the protective film into the thin film by a method such as electron beam evaporation.

Specifically, the recording film is formed by a process in which any of the metal raw materials described above and any of the metal oxide or nitride raw materials described above are placed in different crucibles and evaporated by alternately irradiating them with electron beams. This is done by plasma polymerization of hydrocarbons, etc.

The protective film can be formed by simultaneous evaporation of compound materials such as metal oxides by electron beam irradiation and plasma polymerization of hydrocarbons, etc., or by reactive vapor deposition by introducing oxygen, nitrogen, etc. into the plasma. It is formed by a method in which a process of plasma polymerization of hydrocarbons, etc. is carried out simultaneously. In this production method as well, any of the hydrocarbons and hydrogen fluoride listed in the first production method can be used as raw materials for plasma polymerization.

A fourth method for manufacturing a recording medium of the present invention is a method using only simultaneous multi-target sputtering. The recording film is formed by simultaneously stearic acid of any of the metal targets described above, any of the metal oxides described above, a nitride target, and an organic target. Organic targets include PTFE, PFA, FEP, EPE, and ET.
Fluorine-containing polymers such as FE, PCTFE% PVDF and PVF, nitrogen-containing polymers such as polyimide and polyetherimide, and oxygen-containing polymers such as polyetherketone and polyetheretherketone can be used. Svater ring is performed using a rare gas such as argon, but depending on the type of organic target, hydrocarbon gas may be used.

Adding carbon fluoride or the like is also an effective method for improving the recording and reproducing characteristics of a recording medium. The protective film is formed by simultaneous sputtering of the above compound target and the above organic target. The sputtering is performed by adding a rare gas such as argon, or a hydrocarbon, carbon fluoride, or the like. The additive gas is used to improve adhesion and scratch resistance.

A fifth method for manufacturing the recording medium of the present invention is a method using multi-source vapor deposition. recording membrane, and.

The protective film can be formed by vacuum evaporation of any of the above-mentioned metal raw materials by resistance heating in a boat made of high melting point metals such as tungsten, molybdenum, tantalum, etc., or by electron beam evaporation and any of the above-mentioned metal oxides, metal nitrides, or metals. It is formed by simultaneous electron beam evaporation of carbide, metal silicide, and metal boride raw materials and vacuum evaporation of organic material by resistance heating of a metal boat. The following various materials can be used as organic raw materials. Namely, stearic acid.

These include carboxylic acids such as palmitic acid, myristic acid, and sulfanilic acid, nylon, polyvinyl alcohol, methylcellulose, polymethacrylic acid, and polyethylene.

Further, dyes such as phthalocyanine and cyanine are also preferred organic substances.

A sixth method for producing a recording medium of the present invention is a plasma CVD method using highly volatile organic metal compounds, hydrides, halides, carbonyl compounds, hydrocarbons, and the like as raw materials. Organometallic compounds are mainly found in IB of the periodic table,
IIB, IIIB, IVB.

VB, VIB, ■B Can be used as a gold metal raw material.

For example, organometallic compounds include AQ(CH3), , Ga(CH
,),,In(CH3),,5i(CH,)4,Ga(
CH,)4.5n(CHx)4.5b(CHa)a,B
i(CH,), etc., and the hydride is SiH4,G
aH4, SbH, etc. can be used. Halides and carbonyl compounds are mainly HA and r in the periodic table.
VA, VA, VIA, VIIIA.

VIIIA gold metal can be used as a raw material for rare earth metals.

For example, YF3. LaF, ,MnF, ,FeF, ,Ni
F.

Fluorides such as Ti(4, CrC et al., NbCQ, C
r(Co)s, TaC1, CrCQ3, MoCQs,
Chlorides such as WCQ, or M o (G O)
−, W (GO) s, Fe (CO) s,
Go, (Go),, N1 (C○),, Rh, (C○)1
It is a carbonyl compound such as 1. Also, (CzHs
LTiC: et al. (C, H,), ZrCQ, , (C, H,
)2Hf(1,.

Metal complexes such as (C,H,)2MoC, (c2Hs)awct, etc., as well as Y(OC5H7)3, Ti(OC,H
,),,Z r (OC3H7) a, Nb(QC,H
,),,Ta(QC,H,),.

Cu(OCH-)a, Al2(OC3H1), Si
(QC2Hg)4゜5n(QC,H,), 5b(QC
, H, )a, and metal alkoxides such as Bi(OC2H5)3 can also be used. these are.

After being subjected to treatment such as heating if necessary, it is introduced into a CVD reaction vessel. In addition, Ha, Ne, and Xe are used as carrier gas.
, Ar, N, etc. are used, and in addition, reactive gases such as 02, C01Go, , N, O, N, , NH,, N2H
ICH C, H4, C, H,, C, H C, H,, CF
C, F, C2F, C, H, etc. are used.

The basic structure and manufacturing method of the recording film and protective film of the present invention are as described above, but in addition to the basic structure, various characteristics that the recording film and protective film should satisfy are described below.

The first characteristic that a recording film should satisfy is that its spectral absorption should be 10 to 60% and its spectral reflectance should be 30% or more in a film thickness range of 20 to 200 nm, which is suitable for a bubble-forming type recording film. It is to show. The spectral characteristics of a recording film mainly depend on the properties of metal particles in the recording film, that is,
It depends on the type, particle size, and content. In the case of the recording film of the present invention, if the recording film contains about 5 to 15% by weight of metal fine particles, the spectral absorption rate and spectral reflectance fall within the above range.

The second characteristic that should be satisfied is that the reproduced signal contrast ratio is 0.
．． It is possible to form bubbles with a good shape and sufficient protrusion height that can take a large value of 6 or more. As described above, bubble formation occurs as a result of evaporation of organic matter in the recording film acting as gas pressure on the interface between the recording film and the substrate.

In the case of the recording film of the present invention, if the amount of organic matter in the recording film is 0.5 or more and 4% by weight or less, the above-mentioned good reproduced signal contrast ratio can be obtained.6 Evaporation temperature of organic matter from the recording film of the present invention That is, the decomposition temperature of the film B varies depending on the nature, type, molecular structure, molecular weight, etc. of the organic substance, but the decomposition temperature is 100%.
The temperature range is above 250°C. The particle size of metal oxide and nitride fine particles in the recording film is preferably 10 nm or less, and the number of fine particles in the film thickness direction is at least 15.
A grain size or more is required. It is also desirable that the particle size of the metal fine particles in the recording film is 10n+++ or less.

In addition, from the viewpoint of improving corrosion resistance, it is desirable that the metal fine particles be amorphous.The above-mentioned characteristics of the recording film and protective film, namely composition, evaporation temperature, spectroscopic characteristics, particle size, and crystallinity, are A desired value can be achieved by controlling the film formation parameters during formation of the recording film to predetermined values.

The first characteristic that the protective film should satisfy is that it should have sufficient protection against damage to the recording film due to scratches, etc., at a film thickness of 5000 mm or less, which is easily achieved by the normal dry process method. It is to have. This protective function increases as the mechanical hardness of the protective film increases. In the case of the protective film of the present invention, fine particles of compounds such as metal oxides, which are originally characterized by high hardness, are included as one of its constituent components. This gives it sufficient mechanical hardness. As a result of various experiments, the hardness value of the protective film was 4H based on the pencil hardness specified in JIS K5400.
With the above, the protective function of the recording film was sufficient. The second characteristic that the protective film should satisfy is that it has high adhesion to the recording film. In the case of a protective film composed only of compounds such as the metal oxides mentioned above, the internal stress is often high, and cracks may occur in the protective film during the lamination process or for a period of time after lamination. In the case of the protective film of the present invention, since it contains an organic substance that is effective in reducing internal stress as a constituent component, there are almost no problems with cracking or peeling caused by internal stress. There wasn't. The amount of organic matter in the protective film is suitably 0.4 or more and 6% by weight or less. It is desirable that the particle size of the fine particles of a compound such as a metal oxide in the protective film be as fine as Ionm or less.

This is because internal stress is relaxed, and as a result, the effect of improving adhesion is increased. The number of grains in the film thickness direction is required to be at least about 20 grains or more. The various properties of the protective film described above, such as composition and particle size, can be set to desired values by controlling the film forming parameters at the time of forming the protective film to predetermined values. Furthermore, it is desirable that the protective film be dense and free from pinholes and voids. Densification of the protective film, that is, high density, can be achieved by optimizing film formation parameters as well as various properties. Although it is difficult to quantitatively evaluate the adhesion of the protective film to the recording film, the occurrence of peeling problems in the optical memory manufacturing process after film formation can be practically ignored if the amount of organic matter in the protective film is within the above range. I got as few results as I could.

Furthermore, when the recording/reproducing laser beam is irradiated from the protective film side, the third characteristic that the protective film must satisfy is that it has high spectral transmittance. This is to enable the laser beam to reach the recording film effectively and perform recording with high efficiency, or to perform reproduction with a low error rate. In the case of the protective film of the present invention, the spectral transmittance is preferably 60% or more. Since the constituent components are compound particles such as metal oxides and organic substances, they do not inherently exhibit high light absorption.

In addition, even if metal particles are included in the protective film due to the formation conditions of the protective film, the spectral transmittance will be 60%.
There is no problem as long as the protective function and adhesion do not decrease to below 100%, and other protective functions and adhesion do not decrease.

Various types of substrates can be used for the optical information recording medium of the present invention. That is, the shape and material of the substrate change depending on what kind of recording/reproducing device the recording medium is used for. However, this is because the main characteristics of a recording medium exhibit unique characteristics regardless of the type of substrate. for example,
The recording medium of the present invention can be used in any form of an optical memory disk, an optical memory card, or an optical memory tape.

Any of a metal substrate, an organic substrate, and a glass substrate can be used as the optical memory disk. Metal substrates include AQ and A1 alloy substrates; organic substrates include acrylic, polycarbonate, epoxy, polyolefin, polyarylate, polyetherketone, polyetherimide, Polyetherketone, polyetheretherketone, polyphenylsalline, etc. can be used. Applicable shapes include φ14', φ12', φ8', φ518'', φ318'', and φ2'.

Any substrate thickness such as 1.5t or 1.2t is applicable. The configuration shown in FIG. 1 is suitable for the optical memory disk. As an optical memory card, any of metal-based and organic-based substrates can be applied, except for glass substrates. IS with outer diameter of 86x54nn+
It is applicable to O standard and other types. The thickness of the substrate may be 1.2t, 0.7t, 0.4t, etc. The substrate for the optical memory tape has a thickness of 25 mm. Any material can be used as long as it can be formed into a tape shape of about 100 ml, has heat resistance to withstand the temperature rise during film formation, and mechanical strength to withstand harsh operating conditions.0 For example, polyethylene terephthalate , polyetherketone, polyimide, polyetheretherketone, polyetherimide, polysulfone, polyarylate, etc. can be used.

It is desirable that the various substrates described above have groups for tracking guides formed on their surfaces. The groups may be formed directly on the surface of the substrate, or may be formed by laminating a group forming layer made of an ultraviolet curing resin, for example.

Further, suitable group patterns are spiral or concentric circles for an optical disk, stripes or arcs for an optical card, and stripes for an optical tape. Further, a substrate on which formatting and tracking patterns are arranged is desirable.

(Example-1) Six types of optical information recording media with recording films and protective films as shown below (
(See Table 1). That is, the recording film\protective film is (A et O, +AQ ten organic substances)\(AQ, 03+
organic matter), (In, O, +In+organic matter)\(In
, 03 + organic matter), (S n O, + S n 10 organic matter) \ (SnO, 10 organic matter), (SbO, + Sb + organic matter) \ (sb, ○, 10 organic matter), (Bi, O, + Bi + organic matter) \ ( Bizoa + organic matter), (T e O, +
There are 6 types: Te+organic matter)\(Tea, 10 organic matter). The recording film and the protective film were formed using an RF magnetron sputtering device (model CFS-8ERF, manufactured by Tsude Seisakusho Co., Ltd.) each equipped with a target made of the metal.

The shape of the target (purity 4N, high purity chemical layer) is φ1
It is 25X4t. The board has a shape of φ130 x 1.2t and is made of polycarbonate resin (Idemitsu Petrochemical Exhibition M8A25
1-^, with continuous servo group) was used. The discharge involved in forming the recording film and the protective film, that is, reactive sputtering and plasma polymerization, are CH, O, CF.
The experiment was carried out using a mixed gas consisting of . The composition of the mixed gas is CH110□/CF, = 64.4/27.6/8
．． It was unified to 0 (volume%).

The gas flow rate is Qco*/Qo*/QCF4=1
4.0/6.0/1.7 SCCM. The recording film was formed using an applied power of 600 W and a discharge pressure of 6 mTorr (N
z conversion value), the discharge time is when the recording film thickness is 80n+++
Adjustments were made within the range of 2 to 3 minutes so that The protective film was formed using the same sputtering device as the recording film was formed. The conditions for forming the protective film were the same as those for forming the recording film, such as the same gas type, gas composition, and
Gas flow rate. The thickness of the protective film thus formed was 170 to 210 nm.

The chemical compositions of the recording film and protective film were determined as follows.

That is, a recording film deposited on a silicon substrate under the same conditions,
The amount of organic matter determined from thermogravimetric analysis of the protective film is about 2 to about 4% by weight and about 3 to about 5% by weight, respectively.
Met. Further, the amount of metal components determined by differential scanning calorimetry for samples produced in the same manner was about 8 to about 20% by weight in the recording film, and about 1% by weight in the protective film. Further, the evaporation temperature of the recording film determined from thermogravimetric analysis was about 120 to about 170°C, and the evaporation temperature of the protective film was about 180 to about 210°C.

The adhesion of the recording film and the protective film was evaluated by an adhesive tape peeling test on the following three types of samples. The first and second samples are samples in which a single layer of a recording film and a protective film are respectively formed on a polycarbonate resin substrate, and the third sample is a sample in which a recording film and a protective film are laminated in this order on a polycarbonate resin substrate. Next, adhesion was examined using the method specified in JIS DO202 (cross-over test method), and no peeling was observed in any of the samples. Regarding the protective film formed on the glass substrate under the same conditions, ASTM 3363
, JIS K5400. When the pencil scratch hardness was determined by the method specified in K5401, all of the six types of protective films showed large hardness values of 4H to 6H.

Next, the life characteristics of these six types of optical discs were evaluated as follows. That is, the spectral reflectance ('
This is an evaluation based on a change in ljA (measured at a constant wavelength of 830 nm, Cary-17). The spectral reflectance before standing is Ro, and after standing is R1, the value of R1/RO is 0.95 or more for all of the 6 types of optical discs, indicating good life characteristics.

The spectral reflectance R6 of these six types of optical disks before the life evaluation was all 40% or more. This value is at a level sufficient to process the reproduced signal with a high SN ratio.

Further, the adhesion of the recording film and the protective film and the hardness of the protective film were measured and evaluated even after being left under the above environmental conditions, and both the adhesion and hardness were found to be the same as before being left.

The recording and reproducing characteristics of six types of optical discs manufactured in this manner were measured. Measurement is at rotation speed 1800rpm+*
, at a radius of 55 m (slow speed 10.4 m/5ec). The wavelength of the laser beam is 830r+s+, and the NA of the objective lens is 0.6. Recording was performed with a write power of 10 to 18 mW and a pulse width of 150 nsec. For reproduction, the laser output is 0. This was done with a continuous beam of F+++W. Table 1 shows the relationship between the saturation value of the reproduced signal contrast ratio obtained by varying the writing power, the existing writing power necessary to obtain the contrast ratio, and the configuration of the optical disc.

(Left below) The playback signal contrast ratio of all 6 types of optical discs is 0.
．． The value was 5 or more, which was large enough for practical use. Here, the reproduced signal contrast ratio is calculated by dividing the amount of light reflected from the written portion by R, and the amount of reflected light from the red written portion by R.
The value obtained from R, -R)/(R, +R,) was assigned.

(Example 2) Ten types of optical discs were manufactured with the same protective film and different recording films. The composition of the recording film of type 10 (see Table 2) is [(In, 3Zn1.), O, +In, 3Zn1. +
Organic matter, [(r n 71 Ag24) 203 +
I nts A et al., Ten Organic Matter], [(I nys S
1ts) z 03 + I null S iz2+
organic matter].

[(IntsGes2)io, +IntsGe
z2+organic matter, [(In so S n1Ji 0
3 + In@4 S n1@10 organic matter], [(In
tsSbzJiOa+In7,5b34+organic matter], [
(I nts B 1s4)z○3 + I nts
8124+organic matter], [(I n ** Txts)
i o, tenI n@4 Ti1. 10 organic matter], [(I
n**Crts)zoa+In@4Crxg+organic matter]
, [(Ins, Co1.), O, + In, 4Co□,
10 organic matter], the protective film is [In, ○, 10 organic matter]
This is the structure.

The recording film is formed using an In target and the metal target (Zn, AQ, Si, Ge, Sn, Sb).
, Bi, Ti, Cr, and Co, purity 4N, and high purity chemical layer) were simultaneously discharged (the sputtering device was CFS-SEP-55 model manufactured by Billion Seisakusho Co., Ltd.). The board is
A polycarbonate resin material (C-89SV manufactured by Idemitsu Petrochemical Co., Ltd., with a continuous servo group) having a diameter of φ89 x 1.2 t was used. Discharge, that is, sputtering and plasma polymerization are: C, H, C-C4F, 0□.

This was carried out using a mixed gas consisting of Ar. The composition of the mixed gas is +c2HG/CC4F110x/Ar=40.
The ratio was unified to 8/9.2/25.0/25.0 (volume%).

The gas flow rate is QC-H-/QC-C4F-/QO
-/QAr=9.8/2.2/6.0/6. OSCC
It is M. The recording film was formed at an applied power of 600 W and a discharge pressure of 4 mTorr (N2 equivalent value), and the discharge time was controlled to be between 1.5 and 2.5 minutes so that the film thickness was 80 to 90 sm.

Next, the protective film was formed following the formation of the recording film. Using an In target as a target and C, Ho2, C, and F4 as mixed gases, reactive sputtering and plasma polymerization were performed, and a protective film was laminated on the recording film. The mixed gas composition is C, H, 10, /C, F4 = 57
．． The ratio was unified to 0/24.8/18.2 (volume%). The gas flow rate is Qc-14s/Qo-/QC2F
4” 13.8/ 6.0/ 4,43CCM.

The conditions for forming the protective film were that the applied power was 400 W, the discharge pressure was 15 wTorr (N, converted value), and the discharge time was 5 minutes. The thickness of the protective film formed in this way is approximately 3
It was 00 nm.

The chemical compositions of the recording film and protective film were as follows. That is, the amount of organic matter determined from thermogravimetric analysis of the recording film and the protective film deposited on the silicon substrate under the same conditions as when forming the recording medium was about 3 to about 4% by weight, respectively.
It was about 4 to about 5% by weight. Further, the evaporation temperature was about 130 to about 170°C for the recording film, and about 210°C for the protective film. Furthermore, the content of metal components determined for samples produced in the same manner was about 11 to about 14% by weight in the recording film, and less than 1% by weight in the protective film.

Examples of adhesion and pencil scratch hardness of recording film and protective film
Evaluation was made in the same manner as in 1. The adhesion of the protective film to the polycarbonate resin substrate and the recording film was good, and the number of peelings in the cross-cut test was zero. The pencil scratch hardness of the protective film was 5H. Recording and reproducing characteristics of the 10 types of optical discs produced were measured under the same conditions as in the examples. Table 2 shows the relationship between the structure of the optical disc, the saturation value of the reproduced signal contrast ratio, and the write power required to obtain it.

(The following is a blank space) As shown in Table 2, all of the 10 types of optical discs had a large reproduced signal contrast ratio of 0.6 or more.

(Example 3) Three types of optical discs were manufactured with the same protective film and different recording films. The composition of the three types of recording film (see Table 3) is (G
a, O, +In+organic substance), (SiO2+In+organic substance), (Gang +InIn-like substance).

The protective film has a structure of (Y2O, ten organic substances).

The recording film is formed by using the metal oxide (Ga, O3, 5i
n2, Gem, and In targets were simultaneously discharged (the sputtering device was the same as that of Example-2).
(the same four-element simultaneous sputtering device as that used in ), and the gas used for discharge was a mixed gas of Ar, CH, and O2. The composition of the mixed gas is Ar/CH4/○, =23154/2
3 (volume%).

The gas flow rate is QAr/QCH4/qo, =
6/14/63CCM. The board is φ130X
A 1.2 t polycarbonate resin servo (for C-130FS sample servo manufactured by Idemitsu Petrochemical) was used. The discharge conditions during recording film formation are as follows. That is, the applied power was 500 W, the discharge pressure was 2 mTorr, and the discharge time was 2
The minutes were set as common.

The protective film was formed by discharging a Y2O3 target with a mixed gas of Ar and CH4°O2. The mixed gas composition is
A r / CH4102 = 23154/23 (volume %), gas flow rate is QAr / QC) + 4 / Qoz
= 6/14/65CCM. The discharge conditions were: applied power 600 W, discharge pressure 35 mTorr, and discharge time 6.
The minutes were set as common.

The metal component content in the recording film determined in the same manner as Examples-1 and -2 was about 17 to about 20% by weight, the amount of organic matter was about 2% by weight, and the metal component content in the protective film was detected. Below the limit, the amount of organic matter was about 5% by weight.

When the adhesion of the recording film and the protective film was evaluated in the same manner as in Examples-1 and -2, the number of peelings of all three types was zero, which was good. The pencil scratch hardness of the protective film was 6H.

Table 3 shows the structure of the recording film and the measurement results of the recording and reproducing characteristics obtained in the same manner as in Examples-1 and -2.

The reproduced signal contrast ratios were all about 0.6, which was a good value.

(Example 4) Sixteen types of optical cards were manufactured with the same recording film and different protective films. The composition of the recording film is (In, O, +In + organic matter) (see Table 4). The composition of the 16 types of protective films is as follows:
(CuO+organic substance), (ZnO+organic substance).

(Ga2o, 10 organic matter), (Sin, 10 organic matter), (G
em.

+ organic matter), ('ri○2+organic matter), (ZrO, 10 organic matter), (Hf○, 10 organic matter), (Nb, O, 10 organic matter), (Ta, O.

+ organic matter), (Cr, O, 10 organic matter), (Red, L+
organic matter), (M n O, 10 organic matter), (Fe203+
organic matter), (Coo organic matter), and (NiO+organic matter). The recording film and the protective film were formed by a plasma blating method in which electron beam evaporation and plasma polymerization are performed simultaneously (TSGD-120 manufactured by Tokuyo Seisakusho). The board is 8
A 6 x 54 x 0.7 t polyarylate resin material (Enblade manufactured by Unitika) was used. A mixed gas consisting of C and H02 was used for plasma polymerization. The mixed gas composition is C2H4102=60/40 (volume %), and the gas flow rate is Qc*o</Qoz=12/8SCCM.

The content of metal components in the recording film determined in the same manner as in Example 1 was about 17% by weight, and the amount of organic substances was about 2% by weight. The amount of organic matter in the protective film was about 3 to about 6% by weight.

The adhesion of the recording film and the protective film, which were evaluated in the same manner as in Example 1, were both good6.Furthermore, the pencil scratch hardness of the protective film was 4H to 6H.

The recording and reproducing characteristics of the 16-type optical card thus manufactured were measured as follows. The linear velocity was kept constant at 50 .mu./5ee, and writing was performed by irradiating a laser beam with a pulse width of 50 .mu.sec and a power of 10 to 20 mW. The wavelength of the laser beam is 780 nm, and the NA of the objective lens is 0.17.
It is. Reproduction was carried out by irradiating a continuous beam of 0.5 ■W. Table 4 shows the relationship between the saturation value of the reproduced signal contrast ratio, the write power required to obtain the contrast ratio, and the configuration of the optical card.

All of the 16 types of optical cards had reproduction signal contrast ratios of around 0.6, which were sufficiently large for practical use.

(Example-5) Fifteen types of optical cards were manufactured in which recording films and protective films were formed using the same film-forming method as in Example-4 (see Table 5).

The substrate used was one made of polyether sulfone resin (4100G manufactured by Susumu Kagaku) measuring 86 x 54 x 0.7 t. The recording film was composed of (BN + In 10 organic materials), (A4N + In 10 organic materials), (GaN 10 In organic materials), (InN + In 10 organic materials), (SL, N, +A9 + organic materials), (Ge3N,
+Sn+organic substances). The protective film is (BN10 organic matter), (AI2N+organic matter), (GaN+organic matter),
(InN + organic matter), (Si, N, 10 organic matter), (G
e, N4 + organic matter), (TiN ten organic matter), (ZrN ten organic matter), (HfN ten organic matter), (VN ten organic matter), (
1 of NbN (10 organic matter), (TaN 10 organic matter), (CrN 10 organic matter), (MoN + organic matter), (WN + organic matter)
There are 5 types.

The saturation value of the reproduced signal contrast ratio obtained in the same manner as in Example-4 and the write power necessary to obtain it,
Table 5 shows the configuration of each optical card. All of the 15 types of optical cards had reproduction signal contrast ratios of 0.4 or more, which were sufficient for practical use.

(Hereinafter, blank space) Furthermore, the adhesion of the 15 types of protective films evaluated in the same manner as in Example-1 was all good. The pencil scratch hardness of the protective film measured in the same manner as in Example-1 was 4H.
It was 6H.

(Example 6) Sixteen types of optical cards with a common recording film and different protective films were manufactured using the same film forming method as in Example 4 (see Table 6).The substrate was 86 x 54 x 0.7 t. A material made of polyetherimide resin (Ultem/Engineering Plastics) was used. The recording film is (Sb, O, +Sb+organic substance). The protective film is made of (SiC+organic material), (Ti
C organic matter), (ZrC + organic matter), (HfC organic matter), (VC ten organic matter), (NbC ten organic matter), (T a
(C10 organic matter), (MoC+organic matter), (WC10 organic matter), (V CZ+organic matter), (TaC, 10 organic matter), (
M o C, 10 organic matter), (WC2 0 organic matter), (Mn
3C+organic matter), (Fe, C+organic matter).

There are 16 types of (Co, C10 organic matter).

Table 6 shows the saturation value of the reproduced signal contrast ratio obtained in the same manner as in Example 4, the write power required to obtain the contrast ratio, and the configuration of each optical card.

(The following is a blank space) As shown in Table 6, all of the 16 types of optical cards exhibited a reproduced signal contrast ratio of 0.5 or more, which was sufficient for practical use.

Furthermore, the adhesion of the 16 types of protective films evaluated in the same manner as in Example-1 was all good. The pencil scratch hardness of the protective film measured in the same manner as in Example-1 was 5H.
This was a high value.

(Comparative Example-1) In order to evaluate the adhesion of the protective film of the present invention, a protective film that lacks some of the constituent elements of the Examples of the present invention, that is, does not contain any organic matter and is made only of metal carbide, was used as an Example. It was manufactured in the same way as -4. In other words, a sample (Sb, O, +Sb+
A sample was prepared in which a recording film made of (organic substance) was formed and a protective film was formed on this recording film. The protective film is SiC, T
There are four types: iC, TaC, and WC. When a cross-cut test was conducted, peeling was observed in the area of about 10% for the sample consisting of only a protective film. Also,
Regarding the sample with the structure of recording film/protective film, peeling was observed in about 20% of the area.

(Example-7) A common recording film was used in the same manner as in Example-4.

Twelve types of optical cards with different protective films were manufactured (see Table 7). The substrates used were 86 x 54 x 0.7 t polysulfone resin (Amoco Chemical P-1700). The recording film has a structure of (SnO, +Sn+organic substance). The protective film is made of (TiSi, organic matter), (Zr
Si2+ organic matter), (HfSi2+ organic matter), (V S
i2+ organic matter), (Nb5Si2+ organic matter), (Ta
Si, 10 organic matter), (CrSi2+ organic matter), (MoS
i, 10 organic matter), (WSi, 10 organic matter), (FeSi,
10 organic matter), (CoS12+ organic matter), (NiSi2+
There are 12 types of organic matter.

Table 7 shows the saturation value of the reproduced signal contrast ratio obtained in the same manner as in Example 4, the write power required to obtain the contrast ratio, and the configuration of each optical card.

(The following is a blank space.) As shown in Table 7, all 12 types of optical cards exhibited reproduction signal contrast ratios of 0.4 or more, which were at a level sufficient for practical use.

Furthermore, the adhesion of the 12 types of protective films evaluated in the same manner as in Example-1 was good. The pencil scratch hardnesses of the protective films measured in the same manner as in Example 1 were all high values of 5H or higher.

(Example 8) In the same manner as in Example 4, 14 types of optical cards were manufactured using a common recording film and different protective films (see Table 8).

The substrate used was one made of polyallylsulfon resin (Amoco Chemical A-400) measuring 86 x 54 x 0.7 t.

The recording film has a structure consisting of (Aff, 03 + An + organic material). The protective film is (YB4 + organic matter)
, (YB engineering 2 + organic matter), (AQB, 10 organic matter), (L
aB, 10 organic matter), (ZrB 10 organic matter), (HfB + organic matter), (VBB + organic matter), (NbB 10 organic matter), (T
There are 14 types: aB2+ organic matter), (CrB10 organic matter), (Fe, B10 organic matter), (Go2B+organic matter), (Co, B10 organic matter), and (Ni2B+organic matter).

Table 8 shows the saturation value of the reproduction signal contrast ratio obtained in the same manner as in Example 4, the write power required to obtain the contrast ratio, and the configuration of each optical card.

As shown in Table 8, all 14 types of optical cards exhibited reproduction signal contrast ratios of 0.4 or more, which were at a level sufficient for practical use.

The adhesion of the 14 types of protective films evaluated in the same manner as in Example-1 was good. Furthermore, the pencil scratch hardness of the protective films measured in the same manner as in Example-1 was all high, 5H or higher.

(Example 9) Three types of optical cards with the same recording film and different protective films were manufactured (see Table 9). The board is 86 x 54xo,
A material made of 7t polymethylpentene resin (Mitsui Petrochemical TPX) was used.

The recording film was formed by simultaneously discharging three types of targets: Al2201, Bi, and PTFE. For sputtering, the same four-element simultaneous sputtering device as that used in Example-2 was used. A mixed gas consisting of Ar and C2F4 was used for the discharge. The composition of the mixed gas is Ar/C2F4=80/
20 (volume %), gas flow rate is QAr/QC2F4
= 16/4 SCCM. The applied power of discharge is 4
00W, discharge pressure was 8 mTorr, and discharge time was 2 minutes.

The protective film was formed by discharging MoSi, WSi2, CoSi, and PTFE targets, respectively. A mixed gas consisting of Ar, C, and F was used for the discharge. The composition of the mixed gas is Ar/C2F4=80/
20 (volume %), gas flow rate is QAr/Q Cz F4=
It was set to 16/45CCM. Discharge (7) Application tIl
Ha: 400W, discharge pressure: 8 mTorr, discharge time: 4
It was set as 1 minute.

Table 9 shows the saturation value of the reproduced signal contrast ratio obtained in the same manner as in Example 4, the write power required to obtain the contrast ratio, and the configuration of each optical card.

(Left below) As you can see from Table 9, all three types of optical cards are 0.
The value reached a practical level of 5 or more.

The adhesion of the 14 types of protective films evaluated in the same manner as in Example-1 was good. In addition, the pencil scratch hardness of the protective film, which was determined in the same manner as in Example-1, was a high value of 5H or more.

(Example 10) Five types of optical cards with the same protective film and different recording films were manufactured (see Table 10). The board is 86X54X O,
A 7t acrylic resin material (M Kasei, stretched methacrylic type, Cosmax) was used. Among the constituent components of the recording film, the metal that disperses the metal oxide at In2O3° was commonly Sb, and the organic matter was varied. That is, there are five types: polyethylene, (polyethylene + hydrogen phthalocyanine), nylon, (nylon + Mg-phthalocyanine), and stearic acid. The protective film is composed of (SiC+nylon).

The recording film and the protective film were formed by electron beam evaporation and vacuum evaporation using resistance heating in a tungsten boat (BHCU-8P-50, manufactured by Tsudushi Seisakusho).

The content of metal components in the recording film determined in the same manner as in Example 1 was about 17% by weight, and the amount of organic substances was about 2% by weight. The amount of organic matter in the protective film was approximately 2% by weight.

The evaporation temperature of the recording film determined in the same manner as in Example-1 was about 120 to about 240°C.

The adhesion of the recording film and protective film was evaluated in the same manner as in Example-1, and both were found to be good. Further, the pencil scratch hardness of the protective film was 4H.

The recording and reproducing characteristics of the thus produced optical card were determined in the same manner as in Example-4. Table 10 shows the saturation value of the reproduced signal contrast ratio, the write power required to obtain the contrast ratio, and the configuration of each optical card.

(The following is a blank space) As can be seen from Table 10, the reproduced signal contrast ratios of the Type 5 optical cards were all 0.5 or more, which was a value sufficient for practical use.

(Example-ti) Six types of optical cards consisting of two types of recording and six types of protective films were manufactured by the plasma CVD method (see Table 11). The board is made of polycarbonate resin, 86 x 54 x O, 7t (Mitsubishi Gas Chemical Kneepilon S-200).
0) was used. One type of recording film is composed of (In, O, +In+organic substance), and the other type is composed of (Nb20.+sb10 organic substance). The protective film combined with the former recording film is (AQ2o, 10 organic matter), (SiO2+i organic matter),
(T i O2 + organic matter). The protective film combined with the latter recording film is made of (Nb20.0 organic matter), (Sn
There are three types: (O, 10 organic matter) and (Ta, O, 10 organic matter).

The recording film made of (In!Off+In+organic substance) is
Discharge a mixed gas consisting of n(CH3), 02, C, H, , H2 (the same plasma C as used in Example-4)
VD equipment). The discharge pressure is 4mTorr,
The applied power is 60W. The recording film consisting of (sb, o, +sb+organic substance) is 5b(CH,),,02,C,H
It was formed by discharging a mixed gas consisting of H2. The discharge pressure was 5 mTorr, and the applied power was 70W.

(AQ20.10 organic matter)
3) It was formed by discharging a mixed gas consisting of -102, C2HG, and Ar.

Below, the composition of the protective film and the type of mixed gas used for formation are as follows:
The protective film made of (Sin2+ organic matter) is Si (○C, H
, ), , CH, , Ar, the protective film consisting of (Ti○2+organic substance) is (C,H,), TiCl2. 02°CH4
, Ar, (Nb, ○, 10 organic substances)
(OCz Hs)s-CH4-Ar, the protective film consisting of (SnO2+organic substance) is Sn(QC3Hv)4,C
The protective film consisting of H4, Ar, (Ta, 03+ organic matter) is a mixed gas consisting of Ta (QC, Hs), CH4, and Ar, respectively. The discharge pressure is 6 mTorr in both cases.
The applied power was 200W in common. The thickness of the recording film was 90 nm in each case, and the thickness of the protective film was 200 to 260 nm.

The content of metal components in the recording film measured in the same manner as in Examples-1 and -2 was about 17 and about 20% by weight, and the amount of organic matter was about 4% by weight in both cases. The amount of organic matter in the overcoat ranged from about 3 to about 5% by weight. Furthermore, the metal content in the protective film was below the detection limit.

The evaporation temperatures of the recording films determined in the same manner as in Example-1 and Example-2 were about 170°C and about 200°C.

Recording film evaluated in the same manner as Example-1 and Example-2,
The adhesion of the protective films was good in all cases.

The pencil scratch hardness of the protective film was 4H to 5H.

The recording and reproducing characteristics of the optical card thus manufactured were measured in the same manner as in Example-4. The relationship between the obtained saturation value of the reproduced signal contrast ratio, the write power required to obtain the contrast ratio, and the configuration of the optical card is shown in the 11th section.
Shown in the table.

(Left below) As you can see from Table 11, all of the six types of optical cards are 0.
It showed a contrast ratio of around 6, which was large enough for practical use.

(Example 12) Three types of optical cards with recording films and protective films as shown below were manufactured by the plasma CVD method in the same manner as in Example 11 (first
(See Table 2). That is, the structure of the recording film\protective film is (AR-
N-0+AQ10 organic matter)\(Affi-N-〇+organic matter), (I n -N -0+I n10 organic matter)\(I
There are three types: (n-N-○+organic substance), (Sb-N-0+Sb+organic substance)\(Sb-N-○+organic substance).

A recording film consisting of CAfl-N-0+AQ+organic matter)
A mixed gas consisting of R(CH3)3, N20, OH,, H, and a protective film consisting of (/1-N-○+organic substance) are Aff.
A mixed gas consisting of (CH3)3, N20, C2H, and Ar was discharged in the same manner as in Example-11.

Similarly, a recording film made of (In-N-0+In+organic substance) is In(CH,)3. N20. A mixed gas consisting of CH4, H, and a protective film consisting of (In-N-○+organic substance) are In(CH,), N20. It was formed by discharging a mixed gas consisting of C2H, Ar. Also, (Sb-N-0
+Sb+organic matter) recording film consists of 5b(CH3)3,
A mixed gas consisting of N20, CH,, H, (Sb-N-
The protective film consisting of ○+organic matter) is 5b(CH,),,N
It was formed by discharging a mixed gas consisting of 20, C2H, and Ar. The discharge pressure was 6 mTorr, and the applied power was 60 W for forming the recording film and 200 W for forming the protective film.

The pencil scratch hardness of the protective film determined in the same manner as in Examples-1 and -2 was 4H to 5H. In addition, Example-1,
The adhesion of the recording film and the protective film was evaluated in the same manner as in Example 2, and both were found to be good.

Table 12 shows the relationship between the saturation value of the reproduced signal contrast ratio measured in the same manner as in Example 4, the write power required to obtain the contrast ratio, and the configuration of the optical card.

(The following is a blank space) Table 12 also shows that the contrast ratio of the Type 3 optical card is good at around 0.6.

(Example-13) The recording film\protective film is (In, O, +In+organic substance)\(I
n20. We created an optical tape with a composition of 10 organic substances. The substrate used was one made of polyetheretherketone resin (ICI Japan, Pictrex) measuring 12.7 x 200 x O.025.

The discharge involved in forming the recording film and the protective film, that is, reactive sputtering and plasma polymerization, are C2H,,02,C-
This was carried out using a mixed gas consisting of C4F. The same sputtering device as that used in Example-1 was used for film formation. The composition of the mixed gas is C2H, /○, /CC
, F, = 64.8/28.6/6.7 (volume %), the gas flow rate is Q C = H-/Q o-/QC-C
4F, = 13.6/6.0/J, 43CCM. The recording film was formed using an applied power of 600 W and a discharge pressure of 6
mTorr and discharge time were 2 minutes. The protective film was formed following the formation of the recording film under the conditions of applied power of 400 W, discharge pressure of 20 mTorr, and discharge time of 4 minutes.

The recording and reproducing characteristics of the optical tape thus produced were measured as follows. That is, the measurement was performed using a semiconductor laser beam with a wavelength of 830 nm as a light source, an apparatus consisting of an optical system equipped with an objective lens of NA = 0.60, and a speed of 11 mm/see. borosilicate glass with a thickness of 1.2 mm was placed on the optical tape (recording film side), and irradiation was applied through the borosilicate glass. The saturation value of the reproduced signal contrast ratio obtained by varying the writing power (pulse width 1 μsec) and the writing power necessary to obtain the contrast ratio were 0.60 and 9 mW, respectively.

(Example 14) When forming a recording film, since the recording/reproducing characteristics vary significantly depending on the composition of the recording film, it is necessary to select appropriate formation conditions. The method for forming a recording film according to the first manufacturing method is simpler in operation than other manufacturing methods, but requires sophisticated techniques. In addition, regarding the formation of the protective film, although it is a similar method to forming the recording film, it is necessary to change the film composition only by changing the film formation parameters and provide the necessary functions as a protective film, so the content is similarly advanced. Contains. In this example.

The results of forming a recording film and a protective film according to the first manufacturing method are shown.

In the same sputtering device as used in Example-1,
Targeting metal indium, CH0 mixed gas
2. A recording film was manufactured as C-C,F. The composition of the mixed gas is CH4/02/C-C4F, =67.
6/29.0/3.4 (volume %), gas flow rate is. Q
C}+4/Qoz/Qc-C4Fl=14
/6/0.7, and the discharge time was 2 minutes.

As described above, when the mixed gas composition is the same, the production of metallic indium in the recording film increases as the discharge pressure decreases and the applied power increases. An increase in the amount of metallic indium provides desirable properties as a recording film, such as an increase in spectral absorption rate and an improvement in recording sensitivity.

FIG. 7 is a formation diagram of a recording film, and the region indicated by triangle ABC in FIG. 7 is the region where a recording film with good characteristics can be obtained. Next, FIG. 8 is a formation diagram of a protective film, and shows an area where a protective film having a pencil scratch hardness of 4H or more can be obtained.

(Example 15) Six types of optical cards were manufactured with the same recording film and different protective films. The composition of the recording film is (In, 03+In+organic substance).・The protective film has the same structure (In20, 10 organic substances), but In20. The respective chemical compositions of the organic matter and the organic matter were changed, that is, the respective fine structures were changed.

The recording film was formed in the same manner as in Example-1. The substrate is 86 x 54 x O. A 7 t polyarylate resin material (Emblade manufactured by Unitika) was used.

The mixed gas used to form the recording film was CH4/02/C
- C4F, =68.0/29.1/2.9 (volume%), gas flow rate Q CH4 / QC2 / QC-C
4F&=14/6/0.6SCCM.

The applied power was 600 W, the discharge pressure was 2 mTorr, and the discharge time was 2 minutes. The chemical composition of the protective film was controlled by changing the film formation conditions. FIG. 9 shows the relationship between the pencil scratch hardness determined for six types of protective films deposited on a glass substrate under the same conditions and the discharge pressure at the time of forming the protective film. The discharge time was 600 W, and the discharge time was 5 minutes in common.

As can be seen from FIG. 9, the pencil scratch hardnesses of the 6 types of protective films were 3B, HB, and 2H13H14H16H.

Next, the recording and reproducing characteristics of the six types of optical cards manufactured in this way were measured in the same manner as in Example-4. The saturation value of the reproduced signal contrast ratio was good at around 0.6 in all cases, and the write power required to obtain this saturation value was around 10 mW. The scratch resistance of these protective films was evaluated according to JIS Ta205. (JI
SK 7205, ASTM D968, D1044). Predetermined amount (10
After dropping an abrasive (#80 5iC) of 0 to 800 ir on the protective film, a haze meter (ASTM D10
03) to improve surface abrasion resistance (haze value JIS K671)
8 K7105, ASTM D1003).

The relationship between the determined haze value and the previously determined pencil scratch hardness was as shown in FIG. 10. It can be seen from FIG. 10 that the decrease in scratch resistance due to the decrease in the pencil hardness of the protective film results in an increase in the number of fine scratches on the surface of the protective film, which manifests as an increase in the diffuse transmittance relative to the total transmittance.

Scratches generated on the surface of the protective film are directly related to an increase in mark error rate in terms of recording/reproducing characteristics. The error rate before and after the surface abrasion resistance test was measured, and the relationship between the rate of increase due to the test, that is, the value obtained by dividing the error rate after the test by the error rate before the test, and the haze value of the protective film was calculated as follows: The results were as shown in Figure 11. It has been found that when the haze value of the retained MW is 2% or less, the increase rate of is substantially approximately 1. Note that the bit error rates before the test were at a level of about 10-' for all six types of optical cards.

(Example 16) Six types of optical cards similar to Example 15 were manufactured, using the same recording film and differing only in the protective film. The configurations and manufacturing methods of the recording film and protective film were all the same as in Example-15.

The adhesion of these protective films to the recording film was determined according to JISK 7.
The investigation was conducted based on the method specified in No. 106. This is a method (based on JIS K711g) in which an optical card is cantilevered and a predetermined load is repeatedly applied to it to perform a fatigue test.

A pendulum type loading device (constant stress amplitude type) was used for loading. The load was 1 kg, and the rotation angle of the pendulum was 5°.

After 107 bending tests, six types of optical cards were visually inspected and found that neither the recording film nor the protective film had peeled off.
was not recognized at all.

If fine ranks occur in the protective film or recording film due to the bending test, the diffused transmittance increases with respect to the total transmittance, the haze value increases, and the bit error rate increases. 1
The increase in haze value due to 07 repeated bending tests is
Among the six types of optical cards, there was a tendency that the higher the pencil scratch hardness of the protective film, the greater the hardness, but the value was as low as less than 10%. Furthermore, the bit error rate before and after the bending test was measured. The rate of increase associated with the test is
All of the six types of optical cards had values of around 10, which are within a practical range.

(Example 17) Six types of optical cards similar to Example 8 were manufactured, using the same recording film and differing only in the protective film. The composition of the recording film is (AQ
, ○, +AQ+organic matter), and the protective film is (YB4+
organic matter), (AQB2+organic matter).

(L a B s + organic matter), (ZrB 10 organic matter),
It is composed of six types: (HfB + organic matter) and (VB + organic matter). The recording film and protective film were manufactured in the same manner as in Example-8.

The adhesion of these six types of protective films was examined in the same manner as in Example-16. That is, a load of 1 kg was applied 10 times with a pendulum rotation angle of 5 degrees, and the haze value and bit error rate before and after the test were measured. No peeling of the recording film or protective film was observed after the test. The increase in haze value for all of the 6 types of optical cards was around 10%, which was at a level sufficient for practical use. Furthermore, the increase in mark error rate was within a practical range of 10 to 20 for all of the 6 types of optical cards.

(Comparative Example-2) In order to evaluate the adhesion of the protective film of the present invention, six types of comparative optical cards similar to Example-17 were manufactured.

The composition of the recording film is CAQ20. +AQ+organic matter), the protective film is YB4. AflB, , LaB, , ZrB, HfB, V
It is composed only of B and does not contain any organic matter.

When repeated bending tests were conducted in the same manner as in Example-Step 7, none of the six types of protective films reached 10' bending test.
Clear peeling of the protective film was observed between 03 and 104 times of bending.

In each of the embodiments described above, a limited kind of metal is applied to each of the recording film and the protective film in an optical information recording medium. Even when a plurality of them were selected and mixed and applied, the properties did not deteriorate and all showed the same remarkable effect.

〔Effect of the invention〕

The optical information recording medium of the present invention has a structure consisting of a recording film on a substrate and a protective film laminated thereon, and the recording film contains at least one of metal oxide fine particles or metal nitride fine particles. The protective film is a thin film of a mixture having one component, an organic substance as a second component, and metal fine particles as a third component; Since the mixture thin film is made of a substance as a first component and an organic substance as a second component, the following effects can be obtained.

■ The manufacturing process is simple because it has a simple structure of a recording film on the substrate and then a protective film.

(2) Since the recording film and the protective film can be formed by a dry process such as a sputtering method, plasma blating method, or plasma CVD method, productivity is high and costs can be reduced.

■ The composition and microstructure of the recording film and protective film have been optimized, resulting in good recording and reproducing characteristics, long life characteristics, excellent explosion resistance, and excellent durability without peeling.

Furthermore, even if a plurality of metals arbitrarily selected from the above-mentioned limited metals are mixed and applied to each of the above-mentioned recording film and protective film,
It showed the same effect as each of the examples.

FIG. 1 is a schematic diagram showing the configuration of one embodiment of the optical information recording medium of the present invention, FIG. 2 is a schematic diagram showing the fine structure of the recording film and protective film of the recording medium of the present invention, and FIG. Schematic diagrams showing cross-sectional structures of bubbles formed by laser beam irradiation, FIGS. 4, 5, 6, 7, and 8 all show the recording film of the optical information recording medium of the present invention, Diagrams for explaining one method of forming a protective film, FIGS. 9, 10, and 1
FIG. 1 is a diagram showing the characteristics of the optical information recording medium of the present invention.

FIG. 12 is a diagram showing the structure of a conventional optical information recording medium.

10...Optical information recording medium ■1...Substrate 12...Recording film +21...Fine particles 122 made of either metal oxide or nitride...Organic substance 123...Fine particles 13 made of metal ...Protective film Made from any of metal nitride, metal carbide, or metal boride 131...Metal oxide, metal silicide, fine particles 132...Organic matter 14...Bubbles 15...Voids 100. 200... Optical information recording medium 101, 111. 201, 211... Substrate 102.1
12... Spacer 103. 113, 202, 212... Recording film 203.
... Adhesive layer 104 ... air gap

Claims (1)

[Claims] In an optical information recording medium in which information is recorded and reproduced by irradiation with a laser beam, the recording medium has a structure consisting of a recording film on a substrate and a protective film laminated thereon. metals, group IVB metals, V
At least one of the oxide particles of Group B metals and Group VIB metals, or the nitride particles of any of the above metals is the first component, and the organic substance is the second component, IIB of the periodic table. Group metals, Group IIIB metals, Group IVB metals, V
It is a mixture thin film containing as a third component fine particles of either a group B metal or a group VIB metal, and the protective film is a mixture thin film containing fine particles of a group IIB metal, a group IIIB metal, or a group IVB metal of the periodic table. , VB group metals, VIB group metals, IIIA group metals, IVA
oxide fine particles of any of Group metals, Group VA metals, Group VIA metals, Group VIIA metals, and Group VIIIA metals;
Nitride fine particles of any of the metals from group IIIB, group IVB, metals from group VB, metals from group IVA, metals from group VA, and metals from group VIA of the periodic table, metals from group IIIB of the periodic table , carbide fine particles of any of the metals of group IVB, metals of group IVA, metals of group VA, metals of group IVA, metals of group VIIA, and metals of group VIIIA, metals of group IVA of the periodic table, metals of group VA metal, and silicide fine particles of any of group VIA metals, metals from group IIIB of the periodic table, metals from group IIIA, metals from group IVA, metals from group VA, metals from group VIA, metals from group VIIA,
An optical information recording medium characterized in that it is a mixture thin film comprising at least one of boride fine particles of any of Group VIIIA metals as a first component and an organic substance as a second component.