CA1310416C - Magnetooptical recording medium - Google Patents

Abstract

Abstract of the Disclosure A magnetooptical recording medium comprises a substrate, a magnetooptical recording film (I) and a reflection film (II), said films being laminated on said substrate in this order. The magnetooptical recording film (I) is a thin film of an amorphous alloy comprising (i) at least one 3d transition metal, (ii) from 5 to 30 atom % of at least one corrosion resistant metal and (iii) at least one rare earth element, and having an easy axis of magnetization perpendicular to the film plane, and the reflection film (ii) comprises a metal or alloy having a conductivity of not higher than 2 J/cm.sec.K. The recording medium described herein has excellent resistance to oxidation in addition to excellent magnetooptical recording characteristics.

Description

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TITL~
~GN~TOOPTICAL R~CORDING M~DIUM

FI~LD OF THE I NVENTION
This invention relates to a magnetooptical recording medium having excellent resistance to oxidation and excellent magnetooptical recording characteristics.
More particularly it relates to a magnetooptical recording medium comprising a substrate, a magnetooptical recording film and a refletion film, said films being laminated on said substrate in this order, having an easy axis of magnetization perp~ndicular to the film as well as excellent resistance to oxida~ion and excellent magnetooptical recording characteristics.

BAC~GROUND OF THE INV~NTION
It is known that magnetooptical recording films comprising at least one transition metal such as iron, cobalt, etc., and at least one rare earth element such as terbium (Tb~, gadolinium ~Gd), etc., have an easy axis of magnetization perpendicular to the film and are capable of forming a small inverse magnetic domain with magnetization anti-parallel to the magnetization of the film. By corresponding the existence or nonexistence of this inverse magnetic domain to "1" or "O", it becomes possible - ~31~6 - 2 ~ 72932-21 to record a digital signal on such magnetooptical recordlng films as mentioned above.
As magnetooptical recording films composed of such transition metals and rare earth elements as mentioned above, there are disclosed those of Tb-Fe series containing 15-30 atom % of Tb, for example, in Japanese Patent Publication No. 20691/1982. There are also used magnetooptical recording fil~s of Tb-Fe series to which a third component metal has been added. Furthermore, magnetooptical recording films of Tb-Co series, Tb-Fe-Co ~eries and the like are known as well.
Though these magnetooptical recording films have excellent recording reproducing characteristics, they still involve such a serious problem from a practical standpoint that they are subject to oxidation in the course of ordinary use thereof and their characteristics tend to change with the lap~e of time.
The mechanism of oxidation deterioration of magnetooptical recording films containing such transition metal~ and rare earth elements as mentioned above is discussed, for example, in Journal of the Society of Applied Magnetism of Japan, Vol.9, No.2, pp.93-96, and this paper reports that this mechanism of oxidative deterioration may be classified into three types as mentioned below.

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a) Pit corrosion By pit corrosion is meant the occurrence of pinholes in the magnetooptical recording film. This corrosion proceeds mainly under the circumstances of high humidity, and it markedly proceeds, for example, in the recording films of such series as Tb-Fe, Tb-Co or the like.
b) Surface oxidation A surface oxide layer is formed on the magnetooptical recording film, whereby the Kerr-rotation angle ~k of the film changes with time and eventually comes to decrease.
c) Selective oxidation of rare earth element Rare earth elements present in the magnetooptical recording film are selectively oxldized, thereby the coercive force Hc of the film comes to largely change with time.
Various attempts have heretofore been made to inhibit such oxidative deterioration of magnetooptical recording films as mentioned above. For instance, there is proposed a procedure in which a magnetooptical recording film is designed to have a three-layer structure wherein the film is sandwitched between anti-oxidi~ing protective layers such as those of Si3N~, SiO, SiO2, AlN, etc. The anti-oxidizing protective layers as proposed above, however, involve such problems that they are relatively expensive and, at the same time, they require much time and labor to be formed on ma~netooptical recording films, and that a sufficient inhibition of oxidative deterioration of the recording films is not always expected even when such anti-oxidizing protective layers are formed on said recording films.
Furthermore, various atte~pts are being made to improve resistance to oxidation of magnetooptical recording films by incorporating a third compon~nt metal into the recording films.
For instance, Journal of the Society of Applied Magnetism of Japan cited above discloses an attempt to improve resistance to oxidation of magnetooptical recording films of Tb-Fe or Tb-Co series by incorporation into the Pilms of such third component metal as Co, Ni, Pt, Al, Cr, Ti and Pd in an amount of up to 3.5 atom %.
In connection with the attempt, said Journal reports that the incorporation of small amounts of Co, Ni and Pt into Tb-Fe or Tb-Co is effective in inhibiting the surface oxidation and pit corrosion of the resulting magnetooptical recording film but has no effect on inhibition of the selective oxldation of Tb contained as a rare earth element in this magnetooptical recording film.
This disclosure means that even if small amounts of Co, Ni 11 3 ~

and Pt are added to Tb-Fe or Tb-Co, Tb which is present in the resul~ing magnetooptical recording film is selectively oxidized, and the coercive force Hc of the film largely changes. Thus, even when small amounts up to 3.5 atom %
of Co, Ni and Pt are added to Tb-Fe or Tb-Co, no sufficient improvement in resistance to oxidation of the resulting magnetooptical recording film is made.
With the view of improving resistance to oxidation of magnetooptical recording films, a teaching on the magnetooptical recording films which are obtained by adding Pt, Al, Cr and Ti in an amount up to 10 atom % to Tb-Fe or Tb-Fe-Co is disclosed on page 209 of the Proceedings of The Nineth Conference of the Society of ~pplied Maynetism of Japan (November 1985). ~ven when Yt, Al, Cr and Ti in an amount up to 10 atom % are added to Tb-Fe or Tb-Fe-Co, however, inhibition of ~elective oxidation of Tb present in the resulting magnetooptical recording films is not sufficient, though the surface oxidation and pit corrosion can be inhibited to a ~airly effective extent. Thus, there has been still left such a problem that the coercive foxce Hc of the resultant magnetooptical recording films will largely change with time, and eventually the coercive force Hc will largely decreases.
Japanese Patent L-0-P Publn. No. 255546/1986 disclo~es a magnetooptical recording film compri~in~ rare ~ 3 ~

earth elements and transition metals which has been improved in resistance to oxidation by adding thereto such noble metal elements as Pt, Au, Ag, Ru, Rh, Pd, Os and Ir, within such a range that a ~err-rotation angle necessary for regeneration of information recorded may be is retained.
Furthermore, Japanese Patent L-0-P Publn. No.
~806/1983 discloses a magnetooptical recording film comprising a polycrystalline thin film having a composition of PtCo in which Pt is contained in an amount of 10-30 atom X.
However, the above-mentioned polycrystalline thin film having this composition of PtCo involves such problems that said polycrystalline thin film as formed require heat treatment such as annealing because it is polycrystalline, that the polyrystalline grain boundaries Prequently put out noise signals, and that it has a high Curie point.
As described above, the prior art magnetooptical recording films comprising Tb-Fe or Tb-Co and further incorporated with such third metal components as Co, Ni, Pt, Al, Cr, Ti and Pd, involve at least one of such problems that they are not sufficient in resistance to oxidation, small in C/N ratio and high in noise level, and that no high C/N ratio can be obtained unless a large bias 9 ~ 3. :~

magnetic field is applied (i.e. they are poor in bias magnetic field dependency).
With the purpose of providing a magnetooptical recording medium which is excellent in resistance to oxidation, usable over a long period of time, high in C/N
ratio and low in noise level and, moreover, excellent in such bias magnetic field dependency that a sufficiently high C/N ratio is obtained even in a small bias field, the present inventors prosecuted extensive researches and eventually have accomplished the present invention on the basis of their finding that the above-mentioned desired properties are possessed by a magnetooptical recording medium comprising (I) a magnetooptical recording film composed of (i) at least one 3d transition metal, ~ii) from 5 to 30 atom % oP at least one corrosion resistant ~etal and (iii) at least one rare ~arth element, and (II) a reflection film composed of a metal or alloy having a ~pecified thermal conductivity, said films being laminated on a substrate.

DISCLOSURB OF THE INVBNTION
The magnetooptical recording medium according to the invention comprises a substrate, a magnetooptical recording Pilm (I) and a reflection film (II), said films being laminated on said substrate in this order, said magnetooptical recording film (I) being a thin film of an amorphous alloy comprising (i) at least one 3d transition metal, (ii) from 5 to 30 atom ~ of at least one corrosion resistant metal and (iii) at least one rare earth element, and having an easy a~is of magnetization perpendicular to the film plane, and said reflection film (ii) comprising a metal or alloy having a thermal conductivity o~ not higher than 2 J~cm.sec.X.
The magnetooptical recording medium set forth above wherein the reflection film (II) comprises a metal or alloy having a thermal conductivity of not higher 2 J/cm.sec.R. and a reflectance of at least 50 % is particularly preferred.
The magnetooptical recording medium according to the invention which comprises a substrate, a magnetooptical recording film (I) comprising a thin film of an amorphous alloy having a composition specified above and à reflection film (II) comprising a metal or alloy having a thermal conductivity of not higher than 2 J~cm.sec.K., said films being laminated on a substrate in this order, has an excellent resistance to oxidation, and in consequence, it is advantageous in that its magnetooptical r~cording film (I) can be thin; a warp of the medium and film crackings are not liable to occur; it r~

has a high C/N ratio; in addition to excellent ~agnetooptical characteristics, its coercive force and Kerr-rotation angle do not substantially change with -time;
and it has an increased re~lectance.

BRIEF D~SCRIPTION OF THE DRAWINGS
Fig. l is a diagrammatic, enlarged cross-sectional view of a magnetooptical recording medium according to one embodiment of the invention;
Fig. 2 is a similar view to Fig.1 illustrating a magnetooptical recording medium according to another embodiment of the invent ion;
Fig. 3 is a similar view to Fig.l illustrating a magnetooptical recording medium according to a further embodiment of the invention;
Fig. 4 is a graph showing a relationship between the CO/(Fe + Co) ratio by atom and the noise level N in dBm of a magnetooptical recording film containing Pt;
Fig. S is a graph showing a relationship between the CO/(Fe + Co) ratio by atom and the noise level N in dBm of a magnetooptical recording film containing Pd;
Fig. 6 is a graph showing a relationship between the CO/(Fe + Co) ratio by atom and the erasion deterioration in terms of the ~ C/N in dB on magnetooptical recording films containing Pt and Pd, L~

- lo - 72932-21 respectively;
Fig. 7 is a graph showing a relationship between the Pt or Pd content in atom % and the resistance to oxidation in terms of the ~ C/N in dB on magnetooptic~l recording films containing Pt and Pd, respectively;
Fig. 8 is a graph showing a relationship between the bias magnetic field in Oe and the C/N ~atio on magnetooptical recording films one containing Pt and the other containing no Pt;
Fig. 9 is a graph showing a relationship between the Pt or Pd content in atom % and the minimum bias magnetic field H sat. in Oe on magnetooptical recording films containing Pt and Pd, respectively;
The results shown in Figs. 4 to 9 were obtained on magnetooptical recording media, each having a structure as shown in Fig.1 and comprising a substrate of an ethylene-cyclotetradodecene, a magnetooptical recording film of a thickness of 300 A and a reflection film of a nic~el alloy having a thickness of 1000 A.
Fig. 10 is a graph showing the C/N ratio (dB) of a magnetooptical recording medium having a Ni Cr alloy reflection film plotted against the Ni content of the reflection film.

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B~ST MOD~ OF PRACTICING THE INV~NTION
As shown in Fig.1, the magnetooptical recording medium 1 according to the invention comprises a substrate, such as a transparent disc, a magnetooptical recording film 3 and a reflection film 4, said films 3 and 4 being la~inated on the substrate 2 in this order.
The magnetooptical recording medium 1 according to the invention may further comprise an enhancing film 5 between the substrate 2 and the magnetooptical recording film 3, as shown in Fig.2.
Further, as shown in Fiy.3 the magnetooptical recording medium 1 according to the invention may comprise two enhancing films 5, one between the substrate 2 and the magnetooptical recording film 3 and the other between the magnetooptical recording film 3 and the reflection film 4.
The substrate 2 is preferably a transparent disc, which may be composed of an inorganic material such as ~lass or aluminium, or an organic material such as polymethyl methacrylate, polycarbonate, a polymer alloy of polycarbonate and polystyrene, amorphous polyolefins as described in US patent No,4,614,7~8, poly(4-methyl-1-pentene), epoxy resins, polyethersulfone, polysulfone, polyetherimide and copolymers of ethylene and tetracyclododecene. Of these, copolymers of ethylene and tetracyclododecenes as described hereinafter are . .

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particularly preferred.
Namely, the substrate 2 is preferably composed of a random copolymer ~A] of ethylene and at least one cycloolefin of the general formula [I] or [II], said copolymer having an intrinsic viscosity ~] of from 0.05 to 10 dl/g as measured in decalin at a temperature of 135 C., and a so~tening temperature (TMA3 of at least ~0C. ~1,3 I R7 o [ I ]

R1)R

wherein n and m each is O or a positive integer,~ is an integer of at least 3, R1 through R12 each represents a hydrogen or halogen atom or a hydrocarbon group.
In the polymer chain of the random copolymer ~A], the component derived from the cycloolefins of the general formulas ~I] and ~II] i5 present in the form of recurring units as represented by the following general formulas ~ ~Q~ ~

[III] and ~IV], respectively.
R3 ~ i` .

[III~

~( R _Rl O )~, wherein n and m each is O or a positi~e integer, Q is an integer of at least 3, R through R . each represents a hydrogen or halogen atom or a hydrocarbon group.
At least one cycloolefin selected from the group consisting of unsaturated monomers represented by the general formulas tI] and ~II] is usable herein to copolymerize with ethylene. The cycloolefins represented by the general formula ~I~ can easily be prepared by condensation of cyclopentadienes with appropriate olefins by Diels-~lder reaction, and similarly the cycloolefins represented by the general formula [II] can easily be prepared by condensation of cyclopentadienes with appropriate cycloolefins by Diels-Alder reaction.

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The cycloolefins represented by the general ~ormula ~I] in the concrete are such compounds as exemplified in Table 1 or, in addition to 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, such octahydronaphthalenes as 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,~,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,~-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2 isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, etc. and such compounds as exemplified in Table 2.

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Table l Chemical formula Compound name Bicyclo[2,2,l]hept-2-ene CH3 6-Methylblcyclo[2,2,l]hept-2-ene CH3 5,6-Dimethylbicyclo[2,2,1]hept-C113 2-ene CH
l-Methylbicyclot2,2,~]hept-2-ene 2H5 6-~thylbicyclot2,2,l]hept-2-ene nC4H9 6-n-Butylbicyclot2,2,l]hept-2-ene IC4H9 6-Isobutylbicyclo[Z,2,l]hept-2-ene CH3 ~-Methylbicyclo~2,2,l]hept-2-ene ~--16- ~ 31~

Table 2 Chemical ~ormula ~ Compound name 5,lO-Dimethyltetracyclo-6 ~ [4 4 0 l2.5 17.lO] 3 dodece~e ~3 ~13 CH3 2,lO-Dimethyltetracyclo-2~s~17~lo]-3-dodecene ll,12-Dimethyltetracyclo-r 4~4~0~l2-5~l7-l~_3_dodeCene ~3 ~13 2,7,9-Trimethyltetracyclo-[4,4,0,l2 5,17 ~]-3-dodecene ~3 al3 H5 9-~thyl-2,7-dimethyltetracyclo-U\~ [4~4~o~l2~5~17~10]_3_dodecene . ~13 2 3 3-I~obutyl-2,7-dimethyltetracyclo~
[4~4~0~l2-5~l7-l~_3_dodeCene ~13 -17- ~310~

Table 2 (continued~

' 9,11,12-trl~ethyltetracyclo-l3 t4,4,,l2 ,1~ 1]-3-dodecene C~ 9-~thyl-11,12-dimethyltetracyclo-13 [4~4~o~l2~5~l7~lo]-3-dodecene ) 2 H3 ~-h 9-I~obutyl-11,12-dlmethyltetra-cyclo[4,4,o~l2 5~17 1]-3-dodecene ~13 CH3 5,8,9,10-Itramethyltetracyclo-[ 4, 4, O, 1~ 5, 17 1 ] -3-dodecene ~ ~ 12 Hexacyclo[6,6,1l,13 6 11-13 4 ~ o2 7,09 14]-4-heptadecene 3 12-Methylhexacyclo[6,6,1,13 6, 10.13 ~l-7;o9 l4]-4-heptadec~ne H~12-~thylhexacyclo~6,6,1,13-6, 13 o2-7 o9 14]_4_heptade ene "~ / 2-Iso utylhexacyclol6,6,1,1 10.13 o2-7 o9~14]_4-heptadecene -18- ~ 3 ~

.
Table 2 ~continued) C~
\~ / ~ ~ ~ ~ (~13) 1,6,10-Trimethyl-12-isobutyl-hexacyclo~6~6 1 13-6 110-13 o2-7 C~13 CH30 ' ~-4-heptadecene octacyclo[g~a~o~l2 9,14 ~ 8, 13.16 03-~ ol 2~17]_s-doco~ene 3 15-Methyloctacyclo~8, a,o,12 , ~V/~14.? lll.lB 113.16 03.s ol2.17~
5-docosene C21~5 15-~thyloctacyclo~8,8,0,12 9,14 7, 113-16,03- a,ol 2 1~]-6-docosene ~ 3 ~

The cycloolefins represented by the general formula [II] in the concrete are, for example, tho~e as exemplified in Tables 3 and 4.

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; Table 3 Chemical formula ~ Compound name 1,3-Dimethylpentacyclo[6,6,1, 13-6 o2-~ O9 14]-4-hexadecene 1 / `\~ ~ 1,6-Dimethylpentacyclo[6,6,1,136, o2 7, 09 .14]-4-hexadecene Q~3 r ~ ~ \ ~ 15,16-Dlmethylpentacyclo[6,6,1, ~ ~J 13 6~o2 7~O9 14]-4-hexadecena 4 ~ 12 Pentacyclo[6.5,1,13'6,O2 7,o9'13]-5~7~ 4-pentadecene 1,3-Dimethylpentacyclo[6,5,.1,1 o2 7, o9 13]-4-pentadecene CH
1,6-Dimethylpentacyclo[6,5,1, 13.6 o2 7 O9 13]-4-pentadecene C~3 , Dimethylpentacyclo~6,5,1, / ~ 1 ,O ,O ]-4-pentadecene ~ .~

~L 31 1~
, Table 3 (contlnued) 12 Pentacyclo[6,6,1,13 6,02'l,09'14 ~4~J 4-he~cadecene 5 ~ 5 H ptacyclo[8,~,0,l3 ~l4~7 8~o~l2-9 14-7 J 03-8,012-17] 5 henelcO~ene 6 10"_~2"_~' 14 1 3~
- Table 4 Chemical formula ~ Compound name ~ g Tricyclo~4,3,0,12'5]-3-decene 4 ~ ~18 C ~ 2-Methyl-tricyclo~4,3,0,1 ]-3 decene 5-Methyl-tricyclo~4,3,0,12'5~-~ I .
3-decene C~13 4 ~ Trlcyclo~4,4,0,1~ 5]-3-undecene 5 C~ `l `
10-Methyl-tricyclo~4,4,0,12-5]-3-undecen~

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While the random copolymer [A] comprises a first component derived from ethylene and a second component derived from at least one cycloolefin of the general formula ~I] or [II], as the essential constituent components, if desired, it may further comprise a third component derived from at least one other copolymerization monomer in an amount of up to an equi~olar to that o~ the first component contained in the copolymer. Monomers which can be used to form the third component include, for example, alpha-olefins having from 3 to 20 carbons atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene.
In the copolymer tA], the recurring units (a) derived from ethylene are present in an amount of from 40 to 85 ~ by mole, preferably from 50 to 75 % by mole, while the recurring units ~b) of the general formula ~III] or ~IV] derived from the cycloolefin or cycloolefins are present in an amount of from 15 to 60 ~ by mole, preferably from 25 to 50 % by mole, and these recurring units (a) and (b~ are arranged in the copolymer ~A]
substantially at random. The molar percentage of the recurring units (a~ and (b) were determined by 13C-NMR.
The fact that the copolymer ~A] is completely soluble in decalin at a temperature of 135C., indicates that it is , ~ .

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substantially linear and free from a gel-forming cr~ss-linked structure.
The copolymer tA] has an intrinsic viscosity ~7, of from 0.05 to 10 dl/g, preferably form 0.08 to 5 dl/g, as measured in decalin at a temperature of 135 C.
The softening temperature (TMA) of the copolymer tA], as measured by a thermal mechanical analyzer is at least 70C., preferably from 90 to 250 C., and more preferably from 100 to 200 C.
The softening temperature (TMA) o~ the copolymer ~A~ was determined by monitoring thermal deformation behavior of a 1 mm sheet of the copolymer [A] using a thermomechanical analyzer supplied by Du pont. More specifically, a quarz needle was vertically placed o~ the sheet under a load of 49 g and the assembly was heated at a rate of 5 C./min. The temperature at which the needle penetrated into the sheet by a depth of 0.635mm was taken as the softening temperature of the copolymer ~A].
The copolymer ~A] has a glass transition temperature (Tg) of normally from 50 to 230C, and preferably from 70 to 210C.
The crystallinity o~ the copolymer [A], as mea~ured by X-ray diffractomery , is normally from 0 to 10 %, preferably from 0 to 7 %, and more preferably from 0 to ~ %.

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The magnetooptical recording film 3 comprises (i) at least one 3d transition metal, (ii) at leas~ one corro~ion resistant metal and ~iii) at least one rare earth element.
As the 3d transition metal (i) use is made of Fe, Co, Ti, V, Cr, Mn, Ni, Cu, and Zn, alone or in combination. Of these, Fe, or Co or both Fe and Co are particularly preferred.
The 3d transition metal is present in the magnetooptical recording film 3 in an amount of preferably from 20 to 90 atom %, more preferably from 30 to 85 atom ~, and the most preferably from 35 to 80 atom %.
The corrosion resistant metal (ii) incorporated into the magnetooptical recording film 3 is effective to enhance the resistance to oxidation of the film. ~s the corrosion resistant metal use is made of Pt,-Pd, Ti, and Zr, alone or in combination. Of these, Pt, Pd and Ti are preferably used alone or in combination. ~specially preferred are Pt and Pd, alone or in combination.
The corrosion resistant metal is present in the magnetooptical recording film 3 in an amount of from 5 to 30 atom ~, preferably from 5 to 25 atom %, more preferably from 10 to 25 atom %, and the most preferably from 10 to 20 atom ~.
With lesc than 5 atom % of the corrosion resistant - 26 ~ ~31~

metal, the resistance of the magnetooptical recording film to oxidation is not appreciably improved, and thus, the coercive ~orce of the film tends to greatly change with time, or the ~err-rotation angle of the film tends to decrease, or the reflectance R of the film tends to be inferior to that of the corresponding film with no added Pt or Pd. On the other hand, if the content of the corrosion resistant metal of the magnetooptical recordingmedium is in excess o~ 30 atom ~, the Curie point oP the film tends to be unduly reduced and frequently becomes lower than ambient temperature.
In addition to the 3d transition metal ti) and the corrosion resistant metal (ii), the magnetooptical recording film 3 contains at least one rare earth element selected from Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, La, Ce, Pr, Nd, Pm, Sm and ~u~ Of these, Gd, Tb, Dy, Ho, Nd, S~ and Pr are preferred.
~ he rare earth element is present in the magnetooptical recording film 3 in an amount of pre~erably from 5 to 50 atom %, more preferably from B to 45 atom %, and the most preferably from 10 to 40 atom %.
The magnetooptical recording film (I~ preferably has the following composition.
(i) 3d Transition metal In the magnetooptical recording film recommended O ~ 3 herein, Fe or Co or both are contained, and Fe and/or Co is preferably present in the magnetooptical recording film in an amount of at least 40 atom % but not more than 80 atom %, preferably at least ~0 atom ~ but less than 75 atom %, and more preferably at least 40 a~om % but not more than 59 atom %.
Further, Fe and/or Co present in the magnetooptical recording film is preferably in such an amount that the Co/(Fe + Co) ratio by atom is from 0 to 0.3, preferably from 0 to 0.2, and more preferably from 0.01 to 0.2.
When the amount of Fe and/or Co is in the range of at least 40 atom ~ but not more than 80 atom %, there iq such an advantage that a magnetooptical recording ~ilm which is excellent in resistance to oxidation and has an easy axis of magnetization perpendicular to the ~ilm is obtained.
In this conneotion, when Co is incorporated into a magnetooptical recording fil~, there are observed such phenomena as (a) the Curie point of the magnetooptical recording film increases and (b) the Kerr-rotation angle (~k) becomes large. As the result, the recording sensitivity of the magnetooptical recording film can be adjusted by the amount of Co to be incorporated and, moreover, a carrier levsl of reproduced signal increases ~ 3 ~

by incorporating Co. In the preferred magnetooptical recording film, the Co/(Fe + Co) ratio by atom is from 0 to 0.3, preferably from 0 to 0.2, and more preferably from 0.01 to 0.2.
Fig. 4 shows a relationship between the Co/(Fe +
Co) ratio by atom and the noise level in dBm on a magnetooptical recording film of PtTbFeCo series, and Fig.
S shows a relationship between the Co/(Fe + Co) ratio by atom and the noise level in dBm on a magnetooptical recording film of PdTbFeCo series.
As we have shown in Fig.4, in a case of a magnetooptical recording film having a composition represented by Pt13Tb28Fe50Cog, as recommended herein, in which the Co/(Fe + Co) ratio by atom is 0.15,the noise level is -56 dBm, whereas in a case of a magnetooptical recording film having a composition represented by Ptl3Tb28Fe36Co23, in which the Co/(Fe ~ Co) ratio by atom is 0.3~, the noise level is as high as -60 dBm, Further, as we have shown in Fig.5, in a case of a magnetooptical redording film having a composition represented by Pd14Tb27Fe52Co~, as recommended herein, in which the Co/(Fe + Co) ratio by atom is 0.12, the noise le~el is -56 d~m, whereas in a case of a magnetooptical recording film having a composition represented by Pd14Tb27Fe41Co1a. in which the Co/(Fe + Co) ratio by atom is 0.31, the noise ~ 3 ~ ;5 level is as high as -51 dBm.
Fi~. 6 shows a relationship between the erasion deterioration in terms of ~ C/N ratio in dB and the Co/(Fe + Co~ ratio by atom on two series of magnetooptical recor~ing films, one of the compostion of PtTbFeCo and the other of the composition of PdTbFeCo.
Specifically, even when a magnetooptical recoxding film having a composition represented by Pt13Tb28Fe50Cog, as recommended herein, in which the Co/(Fe + Co) ratio by atom i3 0.155, has been irradiated with an increased energy at the time of erasing the information once recorded therein, no change in film properties occurs, and new information can be recorded on the erased recording film with the same C/N value as that prior to the erasion.
Furthermore, with a magnetooptical recording film recommended herein no change in film property will occur even when recording and erasing information are repeatedly performed. For instance, no decrease in C/N ratio is observed even when the recording and erasing operations are performed 100,000 times in a magnetooptical recording film having the composition of Pt13Tb28Fe50Cog.
(ii) Corrosion resistant metal Preferred magnetooptical recording films contain Pt or Pd, or both, as a corrosion resistant metal, and the amount of Pt and/or Pd contained in the prefered ~ 3 ~

magnetooptical recording films is from 5 to 30 atom ~, preferably more than 10 atom % but not more than 30 atom ~, more preferably more than 10 atom % but less than 20 atom %, and the most preferably at least 11 atom % but not more than 19 atom ~.
The presence in the magnetooptical recording film of Pt and/or Pd in an amount of at least 5 atom %, particularly in excess of 10 atom % brings about such advantages that resistance to oxidation of said recording film becomes excellent, and even when it is used for a prolonged period of time, no pit corrosion occurs and the C/N ratio does not become low.
Fig. 7 ~hows a relationship between the content of Pt or Pd in the magnetooptical recording film containing Pt or Pd and the decrease of the C/N ratio when said recording film is retained for 1000 hours under the circumstances of 85~ RH and 80 C.
It i~ thus understood from Fig. 7 that when the amount in the magnetooptical recording film of Pt or Pd is at least S atom %, in particular more than 10 atom %, re~istance to oxidation of said recording film improves, no pit corrosion occurs even after a long-term use and also the C/N ratio will not deteriorate.
For instance, a magnetooptical recording film ~ 3 ~

having a composition represented by Pt13Tb28Fe50Co5 or Pd12Tb28Fe53Co7 will not change in the C/N ratio at all even when it is retained under the circumstance of 85~ RH
and 80C ~ox 1000 hours. In contrast thereto, a magnetooptical recording film having a composition represented by Tb25Fe68Co7 containing no Pt or Pd will greatly decrease in the C/N ratio when it is retained for 1000 hours under the circumstances of 85% RH and 80C.
By incorporation into a magnetooptical recording film of Pt and/or Pd in an amount within the range as specified above, a sufficiently high C/N ratio can be obtained even by a small bias magnetic field when information i~ recorded on the magnetooptical recording film or when the information recorded is read out therefrom. If a sufficiently high C/N ratio is obtained by a small bias magnetic field, a magnet for producing a bias magnetic field can be made small in size and, moreover, heat generation from the magnet can be inhibited and hence simplification of a driving device for an optical disc bearing the magnetooptical recording film thereon is made possible. Moreover, because a ~ufficiently large C/N ratio i5 obtained by a small bias magnetic field, it becomes easy to design a magnet for magnetic field modulation recording capable of overwrite.
Fig. 8 shows a relationship between the bias - 32 ~

magnetic field and the C/N ratio (dB) of a ~agnetooptical recording film having a recommended composition of Pt13Tb28Fe50Cog and of a magnetooptical recording film having a composition represented by Tb25Fe68Co7.
It is understood from Fig. 8 that in the conventionally known magnetooptical recording film represented by Tb25Fe68Cog, the C/N ratio is not saturated unless a bias magnetic field of more than 250 Oe is applied, whereas in the magnetooptical recording film recommended herein, represented by Pt13Tb28Fe50Cog, recording can b~ performed even by a small bias magnetic field and the C/N ratio is saturated at a level of 120 Oe or more. In the following examples and comparative examples, a Hsat value of the minimum bias magnetic field of each magnetooptical recording film is shown, at which the C/N ratio is saturated. The smaller is this Hsat value, it follows that the C/N ratio is saturated by a small bias magnetic field.
Fig. 9 shows a relationship between the content of Pt or Pd and the minimum bias magnetic field (Hsat, ~Oe~ ) on a magnetooptical recording film of PtTbFeCo series and on a magnetooptical recording film of PdTbFeCo series.
It is understood from Fig. 9 that the minimum bias magnetic field, Hsat, becomes sufficiently small when the content of Pt and/or Pd exceeds 10 atom %.
(iii) _Rare earth element (R~) In the magnetooptical recording film, at least one rare earth element (RE) is contained, and usable as the rare earth element is Nd, Sm, Pr, Ce, ~u, Gd, Tb, Dy and Ho, alone or in combination.
Of the rare earth elements illustrated above, preferably usable are Nd, Pr, Gd, Tb and Dy, and particularly preferred i5 Tb. The rare earth elements may be used in combination of t~o or more, and in this case the combination preferably contains at least 50 atom % of Tb.
From the standpoint of obtaining an optical magnetism having an easy axis of magneti~ation perpendicular to the film, it i5 pre~erable that this rare earth element is present in a magnetooptical recording film in such an amount as 0.15 < x < 0.45l preferably 0.20 ~ x < 0.4, wherein x represents R~/(RE + FE + Co) ~atomic ratio].
In the present invention, it is also possible to improve Curie temperature, compensation temperature, coexcive force Hc or Kerr-rotation angle ~k, or cheapen the cost of production by incorporating various elements into the ma~netooptical recordin~ films. These elements ~or the purpose intended may be used, for example, in the - ~ 3 ~
- 3~ --proportion of less than 10 atom ~0 based on the to~al number o~ atoms of elements con tituting the recording film.
Ex~mples of useful elements for this purpose other than those constituents of the magnetooptical recording film include such elements as mentioned below.
(I) ~d transition elements other than Fe and Co Concretely, such transition elements include Sc, Ti, V, Cr, Mn, Ni, Cu and Zn.
Of these elements exemplified above, preferably u~ed are Ti, Ni, Cu and Zn.
(II) 4d transition eleme~ts other than Pd Concretely, ~uch transition elements include Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag and Cd.
Of these transition elements exemplified above, preferably used are Zr and Nb.
(III) 5d transition elements other than Pt Concretely, such transition elements include Hf, Ta, W, ~e, Qs, Ir, Au and Hg.
Of these transition elements, preferably used is Ta.
(IV) Group III B elements Concretely, B, Al, Ga, In, and Tl are used.
Of these elements, preferably used are B, Al and Ga.

o ~

(V) Group IV B elements Concretely, C, Si, Ge, Sn and Pb are used.
Of these elements, preferably used are Si, Ge, Sn and Pb.
(VI) Group V B elements Concretely, N, P, As, Sb and Bi are used.
Of these elements, preferably used is Sb.
(VII) Group Vl B elements Concretely, S, Se, Te and Po are used.
Of these elements, preferably used is Te.
It has been confirmed by braod angle X-ray diffractometry that the magnetooptical recording films having a composition described above have an easy axis of magnetization perpendicular to the film plane and that many of them may be an amorphous thin film which exhibits a Kerr hysteresis of a good angular loop, indicating that it is perpendicularly magnetizable and capable of magnetooptical recording.
By the term "Kerr hysteresis of a good angular loop" used herein we mean that the ratio ~k2/9k1 is at least 0.8 wherein ~k1 is a saturated Kerr-rotation angle that is a Berr-rotation angle where the external magnetic field is maximum, and ~k2 is a residual Kerr-rotation angle that is a Kerr-rotation angle where the external magnetic field is zero.

- 36 - ~ 3~ 3 The magnetooptical recording film 3 preferably has such a thic~ness that it has a light transmiqsion of at least 5 % in the absence of the reflection film ~.
Specifically the thickness of the magnetooptical recordi~g film 3 is normally from lO0 to 600 A, preferably from 100 to 400 A, and more preferably from 150 to 300 A.

Reflection film The magnetooptical recording medium 1 according to the invention is provided with a reflection film 4 on the magnetooptical recording film 3. The reflection film 4 is composed of a metal or alloy having a thermal conductivity of not higher than 2 J/cm.sec.K, preferably not higher than 1 J/cm.sec.K. Preferably the reflection film 4 is composed of a metal or alloy having a reflectance of at least 50 ~, preferably at least 70 %, and a thermal conductivity of not higher than 2J/cm.sec.K, preferably not higher than 1 J/cm.sec.K.
Suitable materials for constituting the reflection film 4 include, for example, Pt having a thermal conductivity of 0.~1 J/cm.sec.E., Pd having a thexmal conductivity of 0.76 J/cm.sec.K., Ti having a thermal conductivity of 0.71 J/cm.sec.K., Co having a thermal conductivity of 0.99 J/cm.sec.K., and Zr having a thermal conductivity of 0.23 J,cm.sec.K., and alloys thereof.

_ 3~ _ ~3~

Preferably the reflection film 4 is composed of a nic~el alloy having a reflectance of at least 50 %, preferably at least 70 %, and a thermal conductivity of not ~igher than 2 J/cm.sec.K, preferably not higher than 1 J/cm.sec.K.
Suitable nickel alloys for constituting the reflection film 4 preferably comprise nickel as the primary component and at least one alloying metal selected from the group consisting of silicon, molybdenum, iron, chromium and copper. Such nickel alloys oontain nickel in an amount of from 30 to 9g atom %, preferably from 50 to 90 atom %.
~ xamples of the nickel alloys usable herein to constitute the reflection film include, for example, Ni-Cr alloys ~for example, an alloy of 30-99 atom ~ of Ni and 1-70 atom % of Cr, preferably an alloy of ~0-95 atom ~ of Ni and 5-30 atom % of Cr), Ni-Si alloys (for example, an alloy oP 85 atom %
of Ni, 10 atom X oP Si, 3 atom % oP Cu and 2 atom % of Al).
Ni-Cu alloys (for example, an alloy of 63 atom %
of Ni, 29-30 atom % of Cu, 0.9-2 atom % of Fe, 0.1-4 atom of Si and 0-2.~5 atom % of Al).
Ni-Mo-Fe alloys (for example, an alloy of 60-65 atom ~ of Ni, 25-35 atom % of Mo and 5 atom % of Fe.), $
-- 3~ ~

~ Ni--Mo--Fe--Cr alloys ( for example, an alloy of 55-60 atom ~ of Ni, 15-~0 atom ~ of Mo, 6 atom % of Fe, 12-16 atom ~ of Cr, and 5 atom ~ of W. ), Ni-Mo-Fe-Cr-Cu alloys (for example, an alloy of 60 atom ~ of Ni, 5 atom % of Mo, 8 atom ~ of Fe, 21 atom ~
of Cr, 3 atom % of Cu, 1 atom ~ of Si, 1 atom % of Mn, and 1 atom % o~ W; and an alloy of 44-4~ atom % of Ni, 5.6-~.5 atom ~ of Mo, 21-23 atom % of Cr, 0.15 atom % of Cu, 1 atom ~ of Si, 1-2 atom ~ of Mn, 2.5 atom ~ of Co, 1 atom '~ of W, 1.~-2.5 atom ~ of Nb , and a balance o~ Fe), Ni-Cr-Cu-Mo alloys ( for example, an alloy of 56-5~
atom X of Ni, 23-24 atom ~ of Cr, 8 atom % of Cu, 4 atom %
of Mo, 2 atom ~ of W, and 1 atom % of Si or Mn), Ni-Cr-Fe ailoys (for example, an alloy oP 79.5 atom ~ of Ni, 13 atom ~ of Cu, 6.5 atom ~ of Fe and 0.2 atom ~ of Cu; and an alloy of 30-34 atom % of Ni, 19-22 atom ~ of Cr, 0.5 atom ~ of Cu, 1 atom % of Si, 1.5 atom %
of Mn and a balance of Fe), When compared with a magnetooptical recording film having a reflection film comprising aluminum, copper or gold, a magnetooptical recording film having a reflection film descri~ed herein has an excellent C/N ratio.
In fact, when a magnetooptical recording film having a reflection film composed of a metal such as aluminum having an increased thermal conductivity, is irradiated with a laser beam to form pits in the film, heat energies from the laser beam are conducted to the reflection film and diffused. As a resul~, an increased recording laser power is required; larger and irregular pits are formed in the film; and a dependency of the recording power upon the thickness of the re~lection film become~ larger.
Further, the refleciton ~ilm proposed herein serves to enhance the resistance to oxidation of the magnetooptical recording film, and thus, provides a magnetooptical recording medium capable of maintaining an excellent relisbility for a prolonged period of time.
Preferred reflection films compri~e a ~ickel alloy having a thermal conductivity of not higher than 2J/cm.sec.K, preferaly not higher than lJ/cm.sec.K.
particularly preferred fro~ the view point of a high C/N
ratio are reflection films composed of a Ni-Cr alloy comprising 30-99 atom % of Ni and 1-70 atom % of Cr, in particular 70-95 atom % of Ni and 5-30 atom % of Cr.
When a reflection film composed of a metal or alloy, in particular a nickel alloy having a reduced thermal conductivity and an increased reflectance, is used according to t~e invention, a large Kerr-rotation angle and a higher reflectance can be realized even with a thinner magnetooptical recording film.

~ 3 ~ S

-- ~o The thickness of the relection film 4 may be normally from 100 to 4000 ~, preferably ~rom 200 to 2000 A.
The total thickness of the magnetooptical recording film 3 and the reflection film 4 may be normally o O
form 300 to 4600 A, and preferably from 350 to 2400 A.
The magnetooptical recording medium 1 according to the invention may provided with an enhancing film 5 between the substrate 2 and the magnetooptical recording film 3, and further with another enhancing film 5 between the magnetooptical recording film 3 and the reflection film 4. The enhancing film S serves to enhance the sensitivity of the magnetooptical recording medium 1 according to the invention and also serves to protect the magnetooptical recording film 3. Any transparent film having a refractive index larger than that of the s~b.~trate can be used herein as the enhancing film.
The enhancing film ~ay be composed of ZnS, ZnSe, CdS, Si3N4, SiNx, (0 < x < 4/3), Si and AlN. Of these, Si3N4 and SiNx are preferred from the stand point of anti-crack properties. The thickness of the enhancing film may be normally from 100 to 1000 A and preferably from 300 to 850 ~.
When the enhancing film 5 is used between the substrate 2 and the magnetooptical recording film 3, the -- ~3~

substrate is preferably composed of a copolymer [A] as noted below. Namely, thP ~ubstrate 2 is preferably composed of a random copolymer of ethylene and at least one cycloolefin of the general formula ~I] or ~II], said copolymer having an intrinsic viscosity ~] of from 0.05 to 10 dl/g as measured in decalin at a temperature of 135 C., and a softening temperature (TMA) of at least 1 0 C . ~10 r I ]

~ [II]

wherein n and m each is O or a positive integer, R is an integer of at least 3, R1 through R12 each represents a hydrogen or halogen atom or a hydrocarbon group.
In the polymer chain of the random copolymer ~A], the component derived from the cycloolefins of the general formulas CI] and ~II] is present in the form of recurring units as represented by the following general formulas ... .

- ~2 - 72932-21 tIII] and [ IV], respectively.

~1 0 [ r I I ~

n3 R7 ~ _ 10)~ IV]

wherein n and m each is 0 or a positive integer, ~ i9 an integer of at least 3, R through R 2 each represents a hydrogen or halogen atom or a hydrocarbon group.
While the random copolymer tA] comprises a first component derived from ethylene and a second component derived from at least one cycloolefin of the general formula tI] or tII], as the essential constituent components, if desired, it may further comprise a third component derived from at lea~t one other copolymerizat ~ on monomer in an amount of up to an equimolar to that of the first component contained in the copolymer. Monomers whic~ can be used to form the third component include, for example, alpha-olefins having from 3 to 20 carbons atoms - ~s~

such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, l-octadecene and 1-eicocene.
In the copolymer ~A], the recurring units (a) derived from ethylene are present in an amount of from 40 to 85 ~ by mole, preferably from 50 to ~5 % by mole, while the recurring units (b) of the general formula ~III] or ~IV] derived from the cycloolefin or cycloolefins are present in am amount of from 15 to 60 % by mole, pre~erably from 25 to 50 % by mole, and these recurring units (a) and (b) are arranged in the copolymer ~A]
substantially at random. The fact that the copolymer ~A]
i5 completely soluble in decalin at a temperature of 135 C., indicates that it is substantially linear and free from a gel-forming cross-linked structure.
The copolymer ~A] has an intrinsic viscosity ~]
of ~rom 0.05 to 10 dl/g, preferably form 0.08 to 5 dl/g, as measured in decalin at a temperature of 135 C.
The softening temperature (TMA) of the copolymer ~A], as measured by a thermal mechanical analyzer i~ at least 70 C., preferably from 90 to 250 C., and more preferably from 100 to 200 C.
The copolymer [A] has a glass transition temperature (Tg) of normally from 50 to 230C, and preferably from ~0 to 210C.

~ 3 ~

The crystallinity of the copolymer rA~, as measured by X-ray diffractomery , is normally from O to 10 %, preferably from O to 7 %, and more preferably from O
to 5 ~.
A process ~or preparing the magnetooptical recording medium according to the invention is illustrated hereinafter.
The magnetooptical recording medium may be prepared by depositing a magnetooptical recording ~ilm having a predetermined composition on a substrate by a known sputtering proces~ or electron beam evaporation process, wherein the substrate is maintained at about room temperature, and use is made of a composite target with chips of elements constituting the magnetooptical recordlng film in the predetermined proportions or an alloy target having the predetermined composition. The substrate may be fixed, or may rotates on its axis or may rotates on its axis while revolving. A reflection film is then formed on the so deposited magnetooptical recording film by the similar procedure.
The magnetooptical recording medium as illustrated above may be prepared at room temperature, and the magnetooptical recording film as formed are not always in need of such a heat treatment as annealing for the pupose allowing the magnetooptical recording film to have an easy - ~5 -axis of magnetization perpendicular to the film.
If necessary, in this connection, an amorphous alloy thin film can also be formed on a substrate while heating the substrate to 50-600C, or while cooling the substrate to -50C.
At the time of sputtering, moreover, biasing a substrate is also possible so that the substrate comes to have a negative potential. By doing so, ions o~ an inert gas such as argon accelerated in the electric field will hit not only target substances but also a magnetooptical recording film being formed and consequently a magnetooptical recording film having further enhanced characteristics may be frequently obtained.

EFF~CT OF TH~ INVENTION
The magnetooptical recording medium according to the invention comprising a substrate, a magnetooptical recording film (I) which is a thin film of an amorphous alloy or a specified composition and a reflection film (II) composed of a metal or alloy having a thermal conductivity of not higher than 2 J/cm.sec.K., in which said films are laminated on a substrate in this order, has excellent resistance to oxidation, and in consequence, it is advantageous in that its magnetooptical recording film ~I) can be thin; a warp of the medium and film cracking ~ 3 ~

are not liable to occur; it has a high C/N ratio; in addition to excellent magnetooptical characteristics its coercive force a~d Kerr-rotation angle do not substantially change with time; and it has an increased reflectance.
The invention will be further described by the following examples. It should be appreciated that the invention is not restricted to the example~.
Example 1 A magnetooptical disc was produced by successively laminating on a disc substrate of an ethylene/
tetracyclododecene copolymer having an ethylene content of 60% by mole, a tetracyclododecene content of 40 % by mole, a softeninig temperature (TMA) of 155 C., an intrinsic viscosity ~] of 0.45 dl/g and a crystallinity of 0 % as measured by X-ray diffractometry, according to the sputtering process a film of ZnS having a thickness of 600 A as an enhancement layer, a film of Pt20 Tb32 Fe36 Co12 having a thickness of 200 A as a magnetooptical recording layer, and a film of Ti having a thickness of 200 A as a reflective layer.
Record reproducing characteristics of the disc thus obtained were measured at a recording frequency of 1 MHz (duty ratio 50 %) and a linear velocity of 11 m/sec. As the result, the optimum recording laser ~ 3 ~

power was 3.o mw and C/N was 42 ds (reproducing laser power was l.o mw).
Com~arative Example 1 A magnetooptical disc was produced by successively laminating on the same disc substrate as used in Example 1 accoxding to the sputtering process a film of ZnS having a thickness of 600 A as an enhancement layer, a film of Pt20 Tb32 Fe36 Co12 having a thickness of 200 A as a magnetooptical recording layer, and a film o~ Al (heat conductivity 2.3~ J/cm.sec.K) having a thickness of ~00 A
as a reflective layer.
Evaluation of the disc thus obtained was conducted in the same manner as in Example 1, whereupon the optimum recording laser power was 6.2 mW and C/N was 42 dB.
Making a comparison between Example 1 and Comparative ~xample 1, it is understood that the laser power necessary for recording in the latter example is more than two times that in the former example, ewen though the values of C/N obtained in both examples are at the same level.
Example 2 ~ xample 1 wa~ repeatd except that the film of Ti used had a thickness of 400 A. A~ the result, the optimum laser power was 3.1 mW and C/N was 44 dB.
Comparative Example ~

~ 3 .~

Comparative Exampl~ 1 was r~peatd excep-t that the film of ~1 us~d had a thickness o~ 400 A. As the result, no recording could be performed even when the laser power incréased up to 8.0 mW.
As can be seen ~rom Examples 1 and 2, and Comparative Examples 1 and 2, in the disc~ having a construction falling within the scope of the present invention the power of laser necessary for recording does not practically change depending upon the thickness of the re~lective layer used, whereas in the discs having the film of Al as a reflective layer the power of laser necessary for recording greatly changes depending upon the thickness o~ the reflective layer used.
Example 3 Example 1 was repeatd except that the magnetooptical recording layer used had a composition of Pt20 Tb32 Fe26 C22- As the result, the optimum laser power was 3,9 mW and C/N was 44 dB.
Examp_e 4 Example 1 was repeatd except that the magnetooptical recording layer used had a composition of Pt20 Tb32 Fe22 Co26. As the result, the optimum recording laser power was 5.8 mW, and C/N was 46 dB.
~xamPle 5 Example 1 was repeatd except that a ~ilm of Pt having a thickness of 200 A was used as the reflective layer. As the result, the optimum recording lasex power was 3.5 mW and C/N was 45 dB.
Examl~le 6 Example 1 was repeatd except that a film of Pt having thickness of 400 A was used as the reflective layer.
Example 7 ~ xample 1 was repeatd except that a film of Pd having a thickness of 200 A was used as the reflective layer. As the result, the optimum recording laser power was 3.5 mW and C/N was 45 dB.
Exam~le 8 A magnetooptical disc was produced by successively laminating on the same disc substrate as used in ~xample 1 according to the sputtering process a film o~ SiNx having a thickness of ~00 A as an enhancement layer, a film of Pt1B Tb34 Fe38 Co10 having a thickness of 300 A as a magnetooptical recordin~ layer, and a film of Ni80 Cr20 having a thickness of 700 A as a reflective layer.
Record reproducing characteristics of the disc thus obtained were measured at a recording frequency of 1 MH~ (duty ratio 50 %) and a linear velocity of 5.4 m/sec.
As the result, the optimum recording laser power - 50 - ~ 3~

was 3.5 mW and C/N was 50 dB (reproducing la~er power was 1.0 mW).
~xamples 9-14 and Comparative Example 3-4 Following substantially the same procedure as described in Example 8, there were produced magnetooptical discs, whose magnetooptical layer and reflective layer had the composition and thickness as indicated in Table 5.
The discs thus obtained were evaluated in the same ~anner as in Example a to obtain the results as shown in Table 5.
Example 15 A magnetooptical disc was produced by successively laminating on a disc substrate of the same ethylene/tetracyclododecene copolymer (60 mole ~ of ethylene and 40 mole % tetracyclododecene )as used in Example 1, according to the sputtering process, a film of SiNx (O<x<4/3, n = 2.3 and attenuation constant k=0.014) having a thickness of 600 A as an enhancing layer, a film of Pt13 Tb28 Fe53 Co6 having a thickness of 300 A as a magnetooptical recording layer, and a film of Nig3 Cr7 having a thickness of 2000 A as a reflection layer.
Similar discs were also produced with varied NiCr oomposition in the reflection layer.
The magnetooptical discs so produced were tested for the C/N ratio (dB). The results are shown in Fig.10.

~ 3 ~

Table _ Fagnetooptical Reflective¦Optimum record-¦C/N
recording l~yer layer ing power Example g t Tb Fe Co Ni85Crl5 4.OmW 50dB

xamplelO t8 Tb28Fe53coll Ni80Cr20 5.3 mW 49dB

3xamplell t20Tb35Fe25co2o Ni64Cr36 2.8mW 48dB

3xamplel2 tl2Tb3oFe48colo Ni90CrlO 3.8 mW 48dB

3xamplel3 t25Tb36Fe26col3 Ni80Cr20 6.2mW 49dB

3xamplel4 d7 Tb28Fe54Coll Ni72Cr28 7.2mW 50dB

~omp.Ex 3 tl5Tb30Fe4~Coa Al 6.3 mW 46dB

impos-sible .omp.Ex 4 13 30 49C8 Al 7.8mW to ~ O mea~ ¦
300 A ¦800 A sure I _ ~

- ~ . .. -- ~

- 52 ~3~ 3 Magnetooptical recording media prepared in the following examples were evaluated in the manner mentioned below.
(1) Measurement of optical elasticity constant U~ing a transmission type ellipsometer with a light source of helium neon laser of a wa~elength of 632.8 nm, the birefringence of test specimens, 10 x 10 x 0.5 mm, molded from polymers shown in Table 2 by press molding was measured, wherein no load was placed on the specimen or stress was applied to the specimen by suspending a weight of 50 g, 100 g or 200 g therefrom, and an optical elasticity constant of the specimen was obtained from the relation between the double refractive index obtained and stress applied.
(2) Letterzation ~double path~
Letterzation was obtained from an equation of (birefringence at the time of placing no load x thickness of the test speciment) x 2.
<Referential Example 1>
A photoelasticity constant was measured in an ethylene/tetracyclododecene ( ~ ) copolymer containing 60 mol % of ethylene (by means of C-NMR, it was confirmed that tetracyclododecene in the copolymer had a structure of ~ , polymethyl methacrylate (T10-10, a product of a Kyowa Gas Kagaku Kogyo) and - 53 ~ L/~

polycarbonate (AD-5503, a product of Teijin Kas0i), both of which are starting polymer~ for conventional opticaldiscs.
Furthermore, letterzation (double path) of the test specimens molded into the form of disc was measured at a distance of radius r mm from the center of the specimen at the time when the angle of illumination of laser was shifted diagonally 10 by 10, a~suming the vertical direction as 0.
The results obtained are shown in Table 6.

Table 6 ,....... .
Optical Letterzation Polymer Elasticity (double path) constant r 010 20 30 40 Ethylene/tetracyclo- 27 +18 +18 +19 + 19 + 20 dodecene copolymer -6xlO 7 43 +13 +14 +15 + 15 ~ 17 _ . . 5~ + 7 + ~ + 8 + 9 + 10 As is understood from the results in Table 6, it is expected that because of its small opticalelasticity constant, ethylene/tetracyclodecene copolymer does not practically exhibit optical influences even when the polymer is molded into a substrate under such molding ~ 3 ~

condi~ions as injection molding where residual stress is set up. Further, ~he disc made of thi~ copolymer exhibits a substantially constant birefringence even when the angle of incidence o~ laser beam changes. In addition, when compared with other discs, the disc made of the above-mentioned copolymer exhibits good adhesion to an enhancing film.
<Referential Example 2>
On the ethylene/tetracyclododecene copolymer of Referential ~xample 1 were formed films each containing a compound selected from among various compounds indicated in Table 7 for forming a enhancing layer, and the film-forming speed as measured at that time in each case was as shown in Table 7.

~3.~

Table 7 Film-forming speed (50 W,l min) Reflac-200 400 600 A tive __ _ __ index SiO2 **** 1.45 SiO **** 1.85 ZnO *********** 2.0 ITO ************* 2.0 TiO *** 2.3 Si3N4 *** 2.0 AIN *** 2.25 ZnSe ******************************* 2.58 CdS ***************************** 2.6 As i~ clearly seen from the results in Table 7, it i5 understood that ZnSe and CdS are markedly high in film-forming speed and hence they are particularly excellent from the standpoint of productivety.

Examples 16-21 Disc substrates of 130 mm in diameter were molded respectively from the ethylene/tetracyclododecene copolymer (PO), which were used in Referential ~ 3~

Example 1. On each substrate thus molded was successively formed by the sputtering process a ~ilm of each compound as shown in Table 8 to a thickness of 500 A as an enhancement layer, a magnetooptical recording layer comprising TbFe to a thickness of 1000 A, and an enhancement layer to a thickness of 500 A.
The mangetoopticl recording media thus obtained were allowed to stand for 7 days at 70 C and a5 % RH, subjected to a 7-day heat cycle -test wherein the media were allowed to stand alternately at -20C ~or 2 hours and at ~60 C for 2 hours to measure coercive force (Hc) thereof.
The results obtained are shown in Table 8.

Table 8 Magnetooptical Change in Hc(Koe) Exampl ¦ recording ~edium Substrate Interlayer 70C, 8~% RH Heat cycle 16 PO 3 4 No change No change 1~ PO CdS No change No change 18 PO ZnSe No change No change 19 PO ZnS No change No change PO Si No change No change 21 PO AIN No change No change As is clearly understood from the resul~s in Table 8, the magnetooptical recording media o~ the present invention maintain the initial coercive force quite stably.

Claims (19)

1. A magnetooptical recording medium comprising a substrate, a magnetooptical recording film (I) and a reflection film (II), said films being laminated on said substrate in this order, said magnetooptical recording film (I) being a thin film of an amorphous alloy comprising (i) at least one 3d transition metal, (ii) from 5 to 30 atom % of at least one corrosion resistant metal and (iii) at least one rare earth element, and having an easy axis of magnetization perpendicular to said films, and said reflection film (II) comprising a metal or alloy having a thermal conductivity of not higher than

2 J/cm.sec.K.
2. The magnetooptical recording medium according to claim l wherein said 3d transition metal (i) contained in said magnetooptical recording film (I) is Fe or Co, or both.

3. The magnetooptical recording medium according to claim 1 wherein said corrosion resistant metal (ii) contained in said magnetooptical recording film (I) is Pt or Pd, or both.

4. The magnetooptical recording medium according to claim 1 wherein said rare earth element (iii) contained in said magnetooptical recording film (I) is selected from Nb, Sm, Pr, Ce, Eu, Gd, Tb, Dy and Ho.

5. The magnetooptical recording medium according to claim 1 wherein said magnetooptical recording film (I) contains from 40 to 80 atom % of the 3d transition metal (i) and more than 10 and not more than 30 atom % of the corrosion resistant metal (ii).

6. The magnetooptical recording medium according to claim 1 wherein said reflection film (II) has a thermal conductivity of not higher than 2 J/cm.sec.K. and a reflectance of at least 50%.

7. The magnetooptical recording medium according to claim 6 wherein said reflection film (II) has a thermal conductivity of not higher than 1 J/cm.sec.K. and a reflectance of at least 70%.

8. The magnetooptical recording medium according to claim 1 wherein said reflection film (II) comprises a nickel alloy.

9. The magnetooptical recording medium according to claim 1 wherein said reflection film (II) comprises a nickel-chromium alloy.

10. The magnetooptical recording medium according to claim 9 wherein said nickel-chromium alloy comprises from 70 to 95 atom % of Ni and from 5 to 30 atom % of chromium.

11. The magnetooptical recording medium according to claim 1 wherein said reflection film (II) has a thickness of from 100 to 4000 .ANG., and the total thickness of said magnetooptical recording film (I) and said reflection film (II) is from 300 to 4600 .ANG..

12. The magnetooptical recording medium according to claim 1 wherein it further comprises an enhancing film between said substrate and said magnetooptical recording film (I) and/or between said magnetooptical recording film (I) and said reflection film (II).

13. The magnetooptical recording medium according to claim 12 wherein said ehnancing film comprises Si3N4 or SiNx (0 < x < 4/3).

14. The magnetooptical recording medium according to claim 12 wherein said substrate comprises a random copolymer of ethylene and at least one cycloolefin of the general formula [I] or [II] noted below having an intrinsic viscosity [?] of from 0.05 to 10 dl/g, as measured in decalin at a temperature of 135°C., and a softening temperature of at least 70°C., and said enhancing film comprises ZnS, ZnSe, CdS, Si3N4 SiNx (wherein 0 < x < 4/3) Si3N4, Si or AIN.

[I]

[II]

wherein n and m each is 0 or a positive integer,? is an integer of at least 3, R through R1 each represents a hydrogen or halogen atom or a hydrocarbon group.

15. The magnetooptical recording medium according to claim 1, wherein:
the substrate is a transparent disc made of glass, aluminum or an organic polymer;
the 3d transition metal (i) is Fe, Co, Ti, V, Cr, Mn, Ni, Cu, Zn or a combination of at least two of them and is contained in an amount of 20 to 90 atom % in the magnetooptical recording film (I);
the corrosion resistant metal (ii) is Pk, Pd, Ti or Zr or a combination of at least two of them;
the rare earth element (iii) is Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu or a combination of at least two of them and is contained in an amount of 5 to 50 atom % in the magnetooptical recording film (I);
the magnetooptical recording film (I) has such a thickness that it has a light transmission of at least 5 % in the absence of the reflection film (II);
the reflection film (II) has a reflectance of at least 50 and a thermal conductivity of not higher than 2 J/cm.sec.K, is made of Pt, Pd, Ti, Co, Zr or Ni or an alloy of one of them and has a thickness of 100 to 4000 .ANG.; and the magnetooptical recording medium may contain one or two enhancing films between the substrate and the magnetooptical recording film (I) and between the magnetooptical recording film (I) and the reflection film (II), the enhancing films having a refractive index larger than that of the substrate, enhancing the sensitivity of the magnetooptical recording medium and protecting the magnetooptical recording film (I).

16. The magnetooptical recording medium according to claim 15, wherein:
the 3d transition metal (i) Fe, Co or both of them and is contained in an amount of 40 to 80 atom % in the magnetooptical recording film (I);
the corrosion resistant metal (ii) is Pt, Pd or a combination thereof and is contained in an amount of 10 to 20 atom % in the magnetooptical recording film (I);
the rare earth element (iii) is Gd, Tb, Dy, Ho, Nd, Sm, Pr or a combination of at least two of them and is contained in an amount of 8 to 45 atom % in the magnetooptical recording film (I);
the magnetooptical recording film (I) has a thickness of 100 to 600 .ANG.;
the reflection film (II) is made of an alloy of Ni with one or more alloying metals selected from the group consisting of Si, Mo, Fe, Cr and Cu, containing 30 to 99 atom % of Ni and has such a thickness that the total thickness of the magnetooptical recording film (I) and the reflection film (II) is 300 to 4600 .ANG.; and where the enhancing films are provided, they are composed of ZnS, ZnSe, CdS, Si3N4, SiNX (where x is larger than 0 but is smaller than 4/3), Si or AlN and have a thickness of 100 to 1000 .ANG..

17. The magnetooptical recording medium according to claim 16, wherein:

the 3d transition metal (i) is Fe or a combination of Fe and Co and the amounts of Fe and Co are such that the Co/(Fe + Co) ratio by atom is from 0 to 0.2;
the corrosion resistant metal (ii) is Pt or Pd or a combination thereof;
the rare earth element (iii) is Tb or a combination thereof with at least one of Nd, Pr, Gd and Dy, provided that the combination contains at least 50 atom % of Tb and the rare earth element (iii) is contained in such an amount that x , which is expressed by Re/(Re + Fe + Co) [in which Re, Fe and Co are the amounts of the rare earth element, Fe and Co in terms of atomic percents], is from 0.15 to 0.45; and the reflection film (II) is made of an Ni-Cr, Ni-Si, Ni-Cu, Ni-Mo-Fe, Ni-Mo-Fe-Cr, Ni-Mo-Fe-Cr-Cu, Ni-Cr, Cu-Mo or Ni-Cr-Fe alloy.

18. The magnetooptical recording medium according to claim 16, wherein the amorphous alloy of which the magnetooptical recording film (I) is composed has a formula Pt13 Tb28 Fe50 Co9, Pd14 Th27 Fe52 Co7 Pd12 Tb28 Fe53 Co7; and the reflection film (II) is composed of a Ni-Cr alloy of 30 to 99 atom % of Ni and 1 to 70 atom % of Cr.

19. The magnetooptical recording medium according to any one of claims 15 to 18, wherein the substrate is made of a random copolymer of 40 to 85 mol % of ethylene and 15 to 60 mol % of tetracyclododecene having an intrinsic viscosity of 0.05 to 10 dl/g as measured in decalin at a temperature of 135°C and a softening temperature of at least 70°C.