JP3516022B2 - Optical recording medium - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various optical recording media such as magneto-optical recording disks and phase change type optical recording disks.

[0002]

2. Description of the Related Art Among optical recording media, for example, in magneto-optical recording disks and phase change type optical recording disks, various recording layer constituent materials are formed on a substrate by sputtering or vapor deposition, either directly or through an underlayer. is doing. At this time, resins such as polycarbonate and polymethylmethacrylate are used as the substrate material, but they are not satisfactory in terms of optical characteristics and water absorption.

JP-A-60-26024 and JP-A-3
JP-A-223341 discloses that a norbornene-based cyclic polyolefin such as norbornene or detracyclododecene is used as a substrate material having good optical characteristics and water absorbency.

However, this one is still inadequate in terms of adhesion to the recording layer and the underlayer formed by the vapor phase film forming method, and the recording layer and the like peel off when stored under high temperature and high humidity. It turned out to be inconvenient.

[0005]

SUMMARY OF THE INVENTION A main object of the present invention is to provide an optical recording medium which has a high adhesion between a substrate and a recording layer or an underlayer, a high moisture resistance and a good recording / reproducing characteristic. is there.

[0006]

These objects are achieved by the present invention described in (1) to (5) below. (1) An optical recording medium having a recording layer on a resin substrate directly or via an underlayer, wherein the substrate is a cyclic polyolefin having a repeating structural unit represented by the following chemical formula 3 and an alkylphenol condensate 1 Containing more than one seed,
Content of the alkylphenol condensate is 0.3-2 wt
%, And the substrate has a thermal softening point of 1 on the surface layer portion on the recording layer side.
An optical recording medium having a skin layer of 00 to 140 ° C.

[0007]

[Chemical 3]

(2) The optical recording medium as described in (1) above, wherein the alkylphenol condensate has a structure of the following chemical formula 4.

[0009]

[Chemical 4]

(3) The recording layer and / or the underlayer are formed by a vapor phase film forming method.
Alternatively, the optical recording medium according to (2). (4) The optical recording medium according to any one of (1) to (3), wherein the substrate is formed by injection molding. (5) The light according to any one of (1) to (4), wherein the substrate has a thermal softening point of the skin layer and a second thermal softening point that is 10 to 50 ° C. higher than the thermal softening point. recoding media.

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

In the present invention, 1 is added to the above cyclic polyolefin.
A substrate to which one or more alkylphenol condensates are added is used. As a result, the adhesion between the substrate and the recording layer is significantly improved, and even when used or stored under high temperature and high humidity,
Peeling of the recording layer does not occur.

[0018]

Specific Structure The specific structure of the present invention will be described in detail below.

A preferred example of the optical recording medium 1 of the present invention is shown in FIG. This optical recording medium 1 is a magneto-optical recording disk having a recording layer 3 on a substrate 2.

The substrate 2 includes recording light and reproducing light (600-
It is formed of a resin that is substantially transparent (preferably 80% or more in transmittance) to a semiconductor laser beam having a wavelength of about 900 nm, particularly 700 to 800 nm, particularly 780 nm. This enables recording and reproduction from the back side of the substrate.

As the substrate material, a norbornene-based cyclic polyolefin whose repeating structural unit is the chemical formula 3 is used.

In the above chemical formula 3, R ₁ and R ₂ are preferably hydrocarbon residues, and particularly preferably an unsubstituted alkyl group having 1 to 5 carbon atoms.
The cyclic polyolefin used is preferably a homopolymer consisting of only the same repeating unit of the chemical formula 3, but a copolymer consisting of a plurality of repeating units of the chemical formula 3 having different R ₁ , R ₂ or q. May be In addition, depending on the case, it may be a copolymer containing other structural units such as ethylene. The number average molecular weight is preferably 5,000 to 100,000, and particularly preferably 10,000 to 40,000. In the chemical formula 3, the halogen atom, the ester group, the nitrile group, and the pyridyl group may be referred to as polar groups below.

Such a cyclic polyolefin is used as a monomer, for example, norbornene, and an alkyl- and / or alkylidene-substituted product thereof, for example, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5 -Ethyl-2-norbornene, 5-butyl-2
-Norbornene, 5-ethylidene-2-norbornene, etc .: dicyclopentadiene, 2,3-dihydrodicyclopentadiene, alkyl substitution products thereof such as methyl, ethyl, propyl, butyl, and polar group substitution products such as halogen: di Methanooctahydronaphthalene, alkyl and / or alkylidene substituents thereof, and polar group substituents such as halogen, for example, 6-methyl-1,4: 5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4: 5,8-
Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4: 5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-
Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-cyano-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8, 8a-octahydronaphthalene, 6-pyridyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4:
5,8-Dimethano-1,4,4a, 5,6,7,8,8
a-octahydronaphthalene and the like; cyclopentadiene trimer and tetramer, for example, 4,9: 5,8-dimethano-3.
a, 4,4a, 5,8,8a, 9,9a-octahydro-1H-benzoindene, 4,11: 5,10: 6,9
-Trimethano-3a, 4,4a, 5,5a, 6,9,9
a, 10,10a, 11,11a-dodecahydro-1H
A saturated polymer produced by hydrogenating a ring-opening polymer obtained by polymerizing by a known ring-opening polymerization method using cyclopentaanthracene and the like. Such cyclic polyolefins are described in JP-A-3-223341 and JP-A-60-26024. This cyclic polyolefin is
A commercially available product may be used, for example, Zeonex 2 manufactured by Nippon Zeon Co., Ltd.
A commercially available product such as 80 can be used.

At least one kind of alkylphenol condensate is added to the resin of the substrate 2. As the alkylphenol condensate, the one represented by the above chemical formula 4 is preferable.

In the above, R ¹ is preferably a substituted or unsubstituted linear or branched alkyl group having about 3 to 30 carbon atoms, and when these have a substituent, a hydroxy group or the like is used as the substituent. preferable.

Further, A is particularly preferably a p-phenylene group. Here, the phenylene group represented by A, or bonded to a substituent such as or branched alkyl group having a straight chain of 1 to 10 carbon atoms, or further binding -O-L _n -Y below You may have.

L is preferably an alkyleneoxy group --R ² O--. In this case, R ² is a substituted or unsubstituted linear or branched alkylene group having about 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and when these have a substituent, the substituent is hydroxy. A group and the like are preferable. The number of repetitions n of the alkyloxy group or epoxy group L is 1 to 30.
The degree is an integer of 1 to 20, in particular.

[0028]

Table 1 shows specific examples of such alkylphenol condensates.

[0030]

[Table 1]

In order to obtain these alkylphenol condensates, a polymer such as propylene or butylene may be condensed with phenol and then reacted with ethylene oxide or the like according to a conventional method for producing a nonionic surfactant. At this time, a long-chain olefin can be used instead of propylene, butylene, or the like.

The decomposition temperature of the alkylphenol condensate used in the present invention is 250 ° C to 350 ° C, more preferably 29 ° C.
A temperature of 0 ° C to 340 ° C (DSC) is preferable. The decomposition temperature is
If it is less than this range, a large amount of gas is generated during molding, or the glass transition point of the substrate is lowered. Further, if it exceeds this range, the compatibility tends to deteriorate.

In the present invention, the substrate is preferably injection molded under the conditions described below. Then, the alkylphenol condensate is preferably contained in the resin pellets filled in the injection molding machine used for manufacturing the substrate. Since 96% to 100% of the alkylphenol condensate contained in the resin pellet remains in the substrate when the resin pellet is injection-molded, the physical properties of the substrate can be accurately designed.

In the present invention, the content of the alkylphenol condensate in the substrate resin is 0.3 to 2% by weight, preferably 0.5 to 1.5% by weight. If it is less than this range, the effect of the present invention does not appear, and if it exceeds this range, gas is generated in the substrate during molding, and the quality of the optical recording medium deteriorates.

A skin layer is present on the surface layer portion of the substrate 2 using such a cyclic polyolefin on the side of the recording layer.
The thermal softening point of this skin layer is 100 to 140 ° C.,
Preferably 100 to 135 ° C, more preferably 110
It is preferably ˜135 ° C. Thermal softening point 140 ℃
If it exceeds, the adhesiveness will decrease. On the other hand, when the temperature is lower than 100 ° C., for example, there is a problem in heat resistance when the recording layers are laminated, or dimensional accuracy is deteriorated.

In this case, the heat softening point of the skin layer of the surface layer is the temperature measured as follows. First, a needle is placed on the substrate to be inspected, a load of about 5 g is applied, the temperature is raised from about 30 ° C. at a temperature rising rate of about 2 ° C./min, and the amount of penetration of the needle is measured. The cross section of the needle is a cylinder with a diameter of about 1 mm.

The relationship between the temperature thus measured and the needle entry amount is shown in FIG. As shown in FIG. 1, in the substrate of the present invention, a first bending point and a second bending point occur in the temperature characteristic profile of the needle entry amount.

For example, in a cast substrate or some kind of injection-molded substrate, only one bending point appears in the temperature characteristic of the needle penetration amount, or the first bending point appears only slightly. In addition, the needle entry amount in the first step caused by the first bending point is approximately 200 μm or less. Therefore, it is considered that the first bending point is derived from the softening point of the skin layer on the surface layer of the substrate.

Therefore, in the vicinity of the first bending point of the temperature characteristic profile, the intersection point of the straight line portion before the needle entry and the straight line portion at the time of the first step entry is T _1, and this is the heat softening of the skin layer. It is defined as a point T ₁ . In the present invention, this T ₁ is regulated as described above.

On the other hand, in the second bending point near the intersection of the linear portion of the time of the first stage enters at the second stage enters a T _2, which defines a second heat softening point T ₂ To do. This second thermal softening point T ₂ is considered to be the thermal softening point at the center of the substrate.

The second thermal softening point T ₂ is equal to the first
10 ° C or more from the heat softening point T _{1 of} , more preferably 10
50 ° C higher temperature, 140 ° C or higher, especially 145-1
A temperature of 80 ° C. is preferred. As a result, dimensional accuracy, mechanical characteristics, heat resistance, etc. are excellent.

The skin layer is the SE of the substrate surface layer section.
It can be confirmed from the M image as a layer having a color different from the surroundings, and the thickness thereof is generally 1 to 200 μm, and particularly 10 to 100 μm.
Considered to be degree. The temperature characteristic profile of the needle penetration amount may be measured by various devices commercially available as TMA (thermomechanical analyzer, thermomechanical analyzer), for example, 943 thermomechanical analyzer manufactured by DuPont.

In order to form such a skin layer, it is particularly preferable to form the substrate by injection molding using a cyclic polyolefin.

These are, for example, when cast.
It has the second thermal softening point T ₂ described above.

In order to form the skin layer during injection molding, it is preferable to set the injection pressure to about 250 to 400 kg / cm ² . The melting temperature may be about 300 to 400 ° C., the mold temperature may be about 90 to 120 ° C., and the holding pressure and the mold clamping force may be set under normal conditions.

If necessary, an oxygen barrier film may be formed on the outer surface of the substrate 2, the outer peripheral surface or the like. A tracking groove may be formed on the surface of the substrate 2 on which the recording layer 3 is formed.

In the magneto-optical recording disk shown in FIG. 2, a protective layer 4 as an underlayer and an intermediate layer 5 are provided on a substrate 2.
The recording layer 3 is formed via.

The intermediate layer 5 is provided to improve the C / N ratio, and is preferably made of various dielectric materials, and the layer thickness thereof is preferably about 30 to 150 nm.

Further, the protective layer 6 may be provided on the recording layer 3 together with the protective layer 4. When used in combination, the compositions of the protective layer 4 and the protective layer 6 may be the same or different.

The protective layer 4 and the protective layer 6, which are provided as necessary, are provided to improve the corrosion resistance of the recording layer 3, and it is preferable that at least one of them, and preferably both of them be provided.

These protective layers are preferably composed of an inorganic thin film made of various oxides, carbides, nitrides, sulfides or mixtures thereof. In addition, the protective layers 4 and 6
May be formed of the above intermediate layer material. The thickness of the protective layer is preferably about 30 to 300 nm from the viewpoint of improving corrosion resistance.

The protective layers 4 and 6 and the intermediate layer 5 are preferably formed by various vapor phase film forming methods such as sputtering, vapor deposition and ion plating, and particularly by sputtering.

Information is magnetically recorded on the recording layer 3 by a modulated heat beam or a modulated magnetic field, and the recorded information is magnetic-optically converted and reproduced.

The material of the recording layer 3 is not particularly limited as long as magneto-optical recording can be performed, but an alloy containing a rare earth metal element, particularly an alloy of a rare earth metal and a transition metal, is used.
It is preferably formed as an amorphous film by sputtering, vapor deposition, ion plating, etc., particularly by sputtering.

Rare earth metals include Tb, Dy, Nd,
It is preferable to use one or more of Gd, Sm, and Ce. Fe and Co are preferable as the transition metal.

In this case, the total content of Fe and Co is 65
It is preferably ˜85 at%. And the balance is substantially a rare earth metal.

The composition of the recording layer preferably used is
TbFeCo, DyTbFeCo, NdDyFeCo,
There are NdGdFeCo and the like. In the recording layer, 10
Cr, Al, Ti, Pt, Si, M in the range of at% or less
O, Mn, V, Ni, Cu, Zn, Ge, Au, etc. may be contained. In the range of 10 at% or less, Sc,
Y, La, Ce, Pr, Pm, Sm, Eu, Ho, E
Other rare earth metal elements such as r, Tm, Yb and Lu may be contained.

The layer thickness of the recording layer 3 is usually 10
It is about 1000 nm.

Even if the recording layer 3 and the intermediate layer 5 as an underlayer are formed by a vapor phase film forming method such as sputtering, the film peeling of the recording layer 3 and the intermediate layer 5 from the substrate 2 is effective. Can be prevented.

A protective coat 7 is preferably provided on the protective layer 6. The protective coat 7 is made of various resin materials such as an ultraviolet curable resin, and is usually 0.1 to 100 μm.
The layer may be formed to a thickness of about m. The protective coat 7 may be layered or sheet-shaped. The protective coat 7 is
In particular, a coating film containing a radiation-curable compound and a photopolymerization sensitizer is preferably radiation-cured.

In addition, the present invention can be applied to an optical recording disc having a so-called phase change type recording layer and recording / reproducing by changing the reflectance.

As such a recording layer, for example, Te-Se type alloys described in Japanese Patent Publication No. 54-41902 and Japanese Patent No. 100004835, Te-Ge type alloys described in JP-A No. 62-76035, etc. JP-A-63-56827
Te-In alloys described in Japanese Patent Publication No. 63-160
No. 028, and T described in JP-A No. 63-160029.
e-Sn alloy, JP-A-58-54338, Patent No. 9
74257, Patent 974258, Patent 9742
No. 57 Te oxide type, other various Te, S
e-based chalcogen system, Ge-Sn, Si-Sn
Alloys such as Ag-Zn, Ag which cause an amorphous-crystalline transition
There are alloys such as —Al—Cu and Cu—Al that cause a color change due to a change in crystal structure, and alloys such as In—Sb that cause a change in crystal grain size.

In any of these cases, an underlayer or a protective layer formed by a vapor phase film forming method may be included.

As described above, according to the present invention, the recording layer and the underlayer are provided by the vapor phase film forming method, in particular, the sputtering, and in particular, the phase change type optical recording disk having the metal recording layer and the rare earth metal element. It is suitable for magneto-optical recording having a recording layer containing a metal such as.

[0065]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.

Example 1 As a cyclic polyolefin having the repeating unit of the above chemical formula 3, a commercially available pellet of cyclic polyolefin having a molecular weight of 29,000 of Zeonex 280 manufactured by Nippon Zeon Co., Ltd. was obtained.
The cyclic polyolefin pellets have the following chemical formulas 5 and 6
The two or more kinds of alkylphenol condensates represented by the formulas 5 and 6 were mixed at a weight ratio of 3.2: 1, and the total content thereof was changed as shown in Table 2 to obtain Sample No. 1 to Sample No. 4. .

[0067]

[Chemical 5]

[0068]

[Chemical 6]

This is melted at 350 ° C. and the mold temperature is 10
Injection molding at 0 ℃, injection pressure 350kg / cm ² , 120mm diameter,
Substrate sample No. 1 to sample No. 4 having a thickness of 1.2 mm were obtained. Sample No. 4 having an alkylphenol content of 2.3 wt% had gas unevenness in the substrate.

The thermal softening point of the substrate was measured by TMA as follows. Needle cross section: 1 mm diameter cylinder load: 5 g Temperature rising rate: 2 ° C / min

Under the above conditions, the temperature profile of the needle penetration amount was measured and the first and second thermal softening points T ₁ and T ₂ were calculated. Table 2 shows T ₁ and T ₂ of the substrates used. Also, from the SEM image of this substrate, it was considered that the thickness of the skin layer was about 100 μm or less.

On this substrate, a protective layer made of glass was formed with a layer thickness of 40 nm by high frequency magnetron sputtering.
An intermediate layer made of SiN _x was formed on the protective layer by high frequency magnetron sputtering to have a layer thickness of 80 nm. next,
A recording layer having a composition of Tb ₂₃ Fe ₇₂ Co ₅ was formed on the intermediate layer by sputtering to have a layer thickness of 80 nm.

Further, a protective layer having the same composition as the protective layer was formed on the recording layer by high frequency magnetron sputtering to a layer thickness of 100 nm, and a protective coat was formed on the protective layer. The protective coat was formed by applying an ultraviolet curable resin containing oligoester acrylate and then ultraviolet curing to form a protective film having a thickness of 5 μm.
No. 1 to sample No. 4 were obtained.

A corrosion resistance test was conducted on Sample Nos. 1 to 4 thus produced. That is, sample No. 1 to sample No. 4 are heated at a temperature of 80 ° C and a humidity of 85%
After standing for 2,500 hours under the condition of RH, the state between the substrate and the laminate was observed visually and by an optical microscope.

Among these states, ∘ indicates that there is no abnormality at all, ∘ indicates that slight swelling of about 10 μm to 100 μm occurs, and ◯ indicates that this swelling occurs partially but clearly. Was evaluated as Δ, and the case where peeling occurred also on the entire surface was evaluated as x. The results are shown in Table 2.

Example 2 In Example 1, pellets of Sample No. 1 and Sample No. 3 in which the content of the alkylphenol condensate was 0 wt% and 1.2 wt% were used, and the injection pressure was 370 kg / c.
m ^2, 330 ° C. The melting temperature, except that the mold temperature was 80 ° C. performs injection molding in the same manner, the skin layer thermal softening point 140
Sample No. 5 and sample No. 6 having a temperature of more than 0 ° C. were prepared. The results are also shown in Table 2. From the results shown in Table 2, the effect of the present invention is clear.

[0077]

According to the optical recording medium of the present invention, there is no inconvenience in the adhesion of the recording layer to the substrate even when stored under high temperature and high humidity.

[Brief description of drawings]

FIG. 1 is a graph for explaining a thermal softening point of an optical recording medium of the present invention.

FIG. 2 is a partial cross-sectional view showing an example of an optical recording medium of the present invention.

[Explanation of symbols]

1 Optical recording medium 2 Substrate 3 Recording layer 4 Protective layer 5 Intermediate layer 6 Protective film 7 Protective coat T ₁ First softening point T ₂ Second softening point

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G11B 11/105 G11B 11/105 521D (72) Inventor Setsuko Shibuya 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDK Corporation (72) Inventor Atsuko Jin, 1-13-1, Nihonbashi, Chuo-ku, Tokyo TDK Corporation (56) References JP-A-2-223477 (JP, A) JP-A-60-168708 (JP, A) JP 61-292601 (JP, A) JP 5-39403 (JP, A) JP 4-161408 (JP, A)

Claims (2)

(57) [Claims] 1. An optical recording medium having a recording layer on a resin substrate directly or via an underlayer, the substrate comprising:
A cyclic polyolefin having a repeating structural unit of the following [Chemical formula 1 ] and at least one kind of an alkylphenol condensate represented by the following [Chemical formula 2] are contained, and the content of the alkylphenol condensate is 0.3 to 2 wt%. , The substrate is injection
By being formed by molding, the recording layer side surface portion has a skin layer of the thermal softening point 100 to 140 ° C., the direct setting
The recording layer or underlayer to be formed is formed by a vapor phase film forming method.
Optical recording medium is a disk-shaped substrate being. [Chemical 1] (In the above formula, q is O, 1, 2, 3 or 4, and Rl and R2 are
Each represents a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an ethylidene group, a methoxycarbonyl group, a cyano group or a pyridyl group, and these may be the same or different. Rl and R2 may combine with each other to form a ring. ) [Chemical 2] ( However, R ¹ is an isobutyl group, an isohexyl group,
Sohepuchiru group, an isooctyl group, an isononyl group, 2,4 -
Dimethylheptyl group, decyl group, isododecyl group, tet
Radecyl group, cyclohexyl group, oleyl group, caproy
Le group or lauroyl group, A is, p - phenylene group, o -
Methyl - p - phenylene or o -, m - Jiisopuchiru
- p - phenylene group, L is 2 - hydroxy - n - Puropeno
Xy group, ethenoxy group or 1 -methyl- ethenoxy group
Group, n is an integer of 1 to 30 , Y is hydrogen or carboxyl
Represents a chill group. 2. The substrate has a thermal softening point of the skin layer,
The optical recording disk according to claim 1, which has a first heat softening point which is 10 to 50 ° C. higher than the heat softening point.