JPH0742365B2 - Cyclic olefin-based random copolymer composition and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has excellent performance such as transparency, heat resistance, moisture resistance and chemical resistance, excellent precision moldability, and excellent adhesion to an information recording film. And a cyclic olefin polymer composition and an information recording substrate comprising the cyclic olefin polymer composition.

[Conventional technology]

Polycarbonate, poly (methyl methacrylate), polyethylene terephthalate, and the like are known as synthetic resins having excellent transparency. For example, polycarbonate is a resin that is excellent in transparency, heat resistance, heat aging resistance, and impact resistance. However, there is a problem that it is easily attacked by a strong alkali and has poor chemical resistance. Polymethylmethacrylate is easily attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has a problem of low heat resistance. Further, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it has a problem that it is weak against strong acids and alkalis and is easily hydrolyzed.

On the other hand, polyolefin, which is widely used as a general-purpose resin, has excellent chemical resistance, solvent resistance, and many excellent mechanical properties, but many have poor heat resistance and are crystalline resins. Because of this, it is inferior in transparency. In general, in order to improve the transparency of polyolefin, a method of adding a nucleating agent to refine the crystal structure or quenching to stop the crystal growth is used, but the effect cannot be said to be sufficient. Rather, the addition of a third component such as a nucleating agent may impair the excellent properties inherent to polyolefin, and the quenching method requires a large amount of equipment and reduces the crystallinity. As a result, heat resistance and rigidity may be reduced.

For a copolymer of ethylene and a bulky comonomer,
For example, U.S. Pat.No. 2,883,372 describes ethylene and 2,3-
Copolymers with dihydroxydicyclopentadiene are disclosed. However, although this copolymer has an excellent balance of rigidity and transparency, it has a glass transition temperature of around 100 ° C. and is poor in heat resistance. Further, a copolymer of ethylene and 5-ethylidene-2-norbornene has the same drawback.

Also, Japanese Patent Publication No. 46-14910 proposes a homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a, -octahydronaphthalene. However, the polymer is inferior in heat resistance and heat aging resistance. Further, in Japanese Patent Laid-Open No. 68-127728, 1,
Although a homopolymer of 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene or a copolymer of the cyclic olefin and a norbornene type comonomer has been proposed, It is clear from the description in the above publication that all the polymers are ring-opening polymers. Since such a ring-opening polymer has an unsaturated bond in the polymer main chain, it has the drawback of being poor in heat resistance and heat aging resistance.

Further, the present applicant is a heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, while a cyclic olefin-based random copolymer consisting of ethylene and a specific bulky cyclic olefin has transparency, It has been found that it is a synthetic resin having well-balanced mechanical properties and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers, and it has already been disclosed in JP-A-60-168708. 59−
220550, Japanese Patent Application No. 59-236828, Japanese Patent Application No. 59-236829, and Japanese Patent Application No. 59-242336. Despite being an olefin polymer, the cyclic olefin-based random copolymers proposed by these proposals have excellent adhesiveness with various materials, but when used for molding an information recording substrate, they are harsh. Under the conditions, the adhesion to the information recording film may be insufficient.

On the other hand, conventionally, polymethyl methacrylate, polycarbonate, polystyrene, hard polyvinyl chloride, epoxy resin and the like have been used as a resin material forming an information recording substrate (which may be abbreviated as an optical disk). However, the optical disks molded from these resin materials all have some drawbacks. For example, polymethylmethacrylate has poor heat resistance at a heat distortion temperature of around 100 ° C., and has a high water absorption rate of 0.4%, which tends to cause dimensional changes due to moisture absorption and warpage. Although polycarbonate has excellent heat resistance, it has a large photoelastic constant and a large birefringence. Moreover, although the surface temperature is low and it is easily scratched, and the water absorption rate is 0.15%, which is smaller than that of polymethylmethacrylate, the problem of moisture resistance still remains. Polystyrene is inferior in heat resistance, impact resistance, and surface hardness, and since it has a large birefringence after molding, it cannot be practically used as an optical disk. Polyvinyl chloride is also very poor in heat resistance and has poor workability and durability, so that it is difficult to use it as an optical disc. Epoxy resin is very excellent in heat resistance, but has poor moldability and has a problem in mass production. Moreover, the photoelastic constant is large, and there is a problem of birefringence due to residual stress during molding. Although glass is excellent in heat resistance, moisture resistance, surface hardness, etc., it is inferior in handling and productivity because it is brittle, easily broken, and heavy.

[Problems to be solved by the invention]

The inventors of the present invention have excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, excellent precision moldability, and excellent adhesion to the information recording film. As a result of diligent study on the resin composition for optical disk, a composition comprising two specific types of cyclic olefin-based random copolymers having different softening temperatures (TMA) achieves the above performance,
It was found that such a cyclic olefin-based random copolymer composition is excellent as a resin material for optical disk molding,
The present invention has been reached.

[Means for Solving Problems] and [Operation] According to the present invention, (A) an ethylene component and the following general formula [I] or [I]
I] consisting of a cyclic olefin component and having an intrinsic viscosity [η] measured in decalin of 135 ° C. of 0.05 to 10 dl
/ g, and the cyclic olefin-based random copolymer having a softening temperature (TMA) of 70 ° C. or higher, and (B) an ethylene component and the following general formula [I] or [I]
I) consisting of a cyclic olefin component and having an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 5 dl /
a cyclic olefin-based random copolymer having a softening temperature (TMA) of less than 70 ° C. in the range of g, and the weight ratio of the following (A) component / (B) component is
Provided is a cyclic olefin-based random copolymer composition characterized by being in the range of 100 / 0.1 to 100/10, and an information recording substrate molded from the cyclic olefin-based random copolymer composition is a use invention. Provided as.

General formula [In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group].

The cyclic olefin-based random copolymers [A] and [B] constituting the composition of the present invention are cyclic olefin-based random copolymers composed of an ethylene component and a specific cyclic olefin component. The cyclic olefin component is a cyclic olefin component represented by the following general formula [I] or general formula [II], and in the cyclic olefin-based random copolymer of the present invention, the cyclic olefin component is the general formula [II].
I] or a structure represented by the general formula [IV] is formed.

General formula [In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group].

General formula [In the formula, n, m, l and R ¹ to R ¹⁰ are the same as defined above. The cyclic olefin, which is a constituent component of the cyclic olefin-based random copolymer that constitutes the composition of the present invention, is selected from the group consisting of unsaturated monomers represented by the general formula [I] and the general formula [II]. It is at least one cyclic olefin.
The cyclic olefin represented by the general formula [I] can be easily produced by condensing cyclopentadiene and the corresponding olefin by the Diels-Alder reaction, and the cyclic olefin represented by the general formula [II] can also be prepared. Similarly, it can be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction. General formula [I]
Specific examples of the cyclic olefin represented by the following are compounds listed in Table 1, or 1,4,5,8-dimethano-1,2,3,
In addition to 4,4a, 5,8,8a-octahydronaphthalene, 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, 3,4,4a5,8,8a-octahydronaphthalene, 2,
3-dimethyl-1,4,5,8-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-
1,45,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 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,
Examples include octahydronaphthalene such as 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, and the compounds shown in Table 2.

Specific examples of the cyclic olefin represented by the general formula [II] include the compounds shown in Tables 3 and 4.

The cyclic olefin-based random copolymers [A] and [B] constituting the composition of the present invention each have an ethylene component and the cyclic olefin component as essential components. In addition, other copolymerizable unsaturated monomer components may be contained, if necessary, within a range that does not impair the object of the present invention. Specific examples of the unsaturated monomer which may be optionally copolymerized include, for example, propylene, 1-butene, and 4-methyl-in a range of less than equimolar to the ethylene component unit in the random copolymer to be produced. The number of carbon atoms such as 1-pentene, 1-hexene, 1-octene, 1-decene, -dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene is 3 or more.
Examples include 20 α-olefins and the like.

In the cyclic olefin-based random copolymer [A] that constitutes the composition of the present invention, the repeating unit (a) derived from the ethylene component is 40 to 85 mol%, preferably 50 to 50 mol%.
The repeating unit (b) derived from the cyclic olefin is in the range of 15 to 65 mol%, preferably 25 to 50 mol%, and the repeating unit (a) derived from the ethylene component and the The repeating (b) derived from the cyclic olefin component forms a substantially aligned cyclic olefin-based random copolymer randomly arranged. The fact that the cyclic olefin-based random copolymer of the present invention is substantially linear and does not have a gel-like crosslinked structure is confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C. it can.

The cyclic olefin-based random copolymer [A] constituting the composition of the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.05 to 10 dl / g, preferably 0.08 to 5 dl / g.
It is in the range of g.

The softening temperature (TMA) of the cyclic olefin derivative random copolymer [A] constituting the composition of the present invention measured by a thermal mechanical analyzer is 70 ° C or higher, preferably 90 to 250 ° C, more preferably 100 to 200. It is in the range of ° C. The glass transition temperature (Tg) of the cyclic olefin-based random copolymer [A] is usually 50 to 230 ° C.,
It is preferably in the range of 70 to 210 ° C.

The degree of crystallinity of the cyclic olefin-based random copolymer [A] constituting the composition of the present invention is 0 to 10%, preferably 0 to 7%, particularly preferably 0. To 5%.

In the cyclic olefin-based random copolymer [B] constituting the composition of the present invention, the repeating unit (a) derived from the ethylene component is 60 to 98 mol%, preferably 60 to 98 mol%.
The repeating unit (b) derived from the cyclic olefin is in the range of 2 to 40 mol%, preferably 5 to 40 mol%, and the repeating unit (a) derived from the ethylene component and the repeating unit (a) The repeating unit (b) derived from the cyclic olefin component forms a substantially linear cyclic olefin-based random copolymer that is randomly arranged.
The fact that the cyclic olefin-based random copolymer of the present invention is substantially linear and does not have a gel-like crosslinked structure is confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C. it can.

The cyclic olefin-based random copolymer [B] constituting the composition of the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 5 dl / g, preferably 0.08 to 3 dl / g.
Is in the range.

The cyclic olefin based random copolymer [B] constituting the composition of the present invention has a softening temperature of less than 70 ° C., preferably 60 to −10, as measured by a thermal mechanical analyzer.
C., more preferably 55 to 10 ° C. The softening temperature of the cyclic olefin-based random copolymer [B] is 30 to 250 ° C., preferably 50 to 200 ° C. higher than the softening temperature of the cyclic olefin-based random copolymer [A].
More preferably, the temperature is lowered by 70 to 150 ° C. Further, the cyclic olefin-based random copolymer [B]
Has a glass transition temperature (Tg) in the range of -30 to 60 ° C, preferably -20 to 50 ° C. The glass transition temperature of the cyclic olefin-based random copolymer [B] is lower than that of the cyclic olefin-based random copolymer [A] by 30 to 240 ° C., preferably 50 to 200 ° C. Is.

The crystallinity of the cyclic olefin-based random copolymer [B] constituting the composition of the present invention is 0 to 10%, preferably 0 to 7%, and particularly preferably 0. To 5%.

In the composition of the present invention, the weight ratio of the cyclic olefin-based random copolymer [A] / the cyclic olefin-based random copolymer [B] is 100 / 0.1 to 100/10, preferably 100.
/0.3 to 100/7, particularly preferably 100 / 0.5 to 100 /
It is in the range of 5. The weight ratio of the [A] component / [B] component is 1
If it is less than 00 / 0.1, the effect of improving the precision moldability of the composition and the adhesion of the information recording film under severe conditions is insufficient, and if it is more than 100/10, the transparency of the molded product deteriorates. Or, the smoothness of the surface is deteriorated, so that the performance as an information recording material is deteriorated.

The cyclic olefin-based random copolymers [A] and [B] constituting the cyclic olefin-based random copolymer composition of the present invention are all disclosed in JP-A-60-168708 and JP-A-61708.
-120816, JP 61-115912, JP 61-
115916, Japanese Patent Application No. 61-95905, Japanese Patent Application No. 61-95906
It can be produced by appropriately selecting the conditions in accordance with the method proposed by the present applicant in JP-A Nos. 61-271308 and 61-272216.

As a method for producing the cyclic olefin-based random copolymer composition of the present invention, a known method can be applied, and the cyclic olefin-based random copolymers [A] and [B] are separately produced,
A method for producing by blending [A] and [B] with an extruder,
[A] and [B] in a suitable solvent such as heptane,
Solution blending method which is carried out by sufficiently dissolving in saturated hydrocarbon such as hexane, decane and cyclohexane, aromatic hydrocarbon such as toluene, benzene and xylene, and [A] and [B] are synthesized in separate polymerization vessels. A method for producing a polymer by blending the obtained polymer in another container can be given.

13 of the cyclic olefin-based random copolymer composition of the present invention
The intrinsic viscosity [η] measured in decalin at 5 ° C is 0.05 to 10 dl / g, preferably 0.08 to 5 dl / g,
The softening temperature (TMA) measured by a thermal mechanical analyzer is 80 to 250 ° C, preferably 100 to 200 ° C, and the glass transition temperature (Tg) is 70 to 230 ° C, preferably 90 to 210 ° C. Is in the range.

The cyclic olefin-based random copolymer composition of the present invention contains the cyclic olefin-based random copolymer [A] and the cyclic olefin-based random copolymer [B] as essential components. Agent, weathering stabilizer,
Antistatic agents, slip agents, anti-blocking agents, anti-fog agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes and the like can be added, and the mixing ratio is an appropriate amount.
For example, as a stabilizer to be added as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di- -T-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamide bis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate and other phenolic antioxidants Agents, zinc stearate, calcium stearate, fatty acid metal salts such as calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tritate Polyhydric alcohol fatty acid such as stearate Examples include stealth. These may be blended alone or in combination, for example, tetrakis [methylene-3
Examples include a combination of (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane with zinc stearate and glycerin monostearate.

An information recording substrate is formed from the cyclic olefin-based random copolymer composition of the present invention according to a conventional method, and an information recording film is laminated on the information recording substrate according to a conventional method.

The information recording substrate of the present invention can be applied to any type of conventionally known structure for information recording substrates, specifically, optical discs, flexible optical discs, optical cards, optical fibers, optical tapes. , Optical halo,
A structure such as a magnetic disk can be adopted.

A conventionally known information recording film can be laminated on the information recording substrate of the present invention. For example, as the information recording film, specifically, TeSe, TePb, Se, a tellurium alloy such as TeSeSb, a film in which a metal is dispersed in an organic Mac such as Te-carbon, a metal oxide such as TeO ₂ , AuPd, , AuPt
Examples thereof include gold alloys, terbium-based alloys such as TbFe, TbFeCo, and TbGdFe, cyanine-based and naphthoxy-based organic dye films, and magnetic materials such as ferrite. Further, as the reflection, metals and alloys such as Al, Cr, Au and Co can be mentioned. Furthermore, as a protective film or an enhance film, Si ₃ N ₄ , SiO ₂ , ZnO, TiO, ZnS
Examples thereof include e and CdS. As a method for laminating the information recording film, all conventionally known methods such as a vapor deposition method, a sputtering method, an ion plating method, a spin coating method and a coater method can be adopted.

〔Example〕

Next, the present invention will be specifically described with reference to examples. In addition, the measuring method and evaluation method of various physical-property values in this invention are shown next.

(1) Softening temperature (TMA): Thermo mechan manufactured by Deyupon
It was measured by the thermal deformation behavior of a 1 mm thick sheet using a ical analyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, the temperature was raised at 5 ° C./min, and the temperature at which the needle penetrated 0.635 mm was defined as TMA.

(2) Adhesion of the information recording film: The resin substrate with the information recording film was placed in a thermo-hygrostat (PL-3G manufactured by Tabai Co., Ltd.)
It was treated at 85 ° C and 85% relative humidity for one week. Immediately after the treatment, the surface condition of the recording film and the adhesion between the recording film and the resin substrate were observed with a metallurgical microscope (magnification: 100 to 400 times).

〔The invention's effect〕

The cyclic olefin-based random copolymer composition of the present invention is excellent in transparency, heat resistance, heat aging resistance, solvent resistance, dielectric properties and mechanical properties, and is excellent in precision moldability. The information recording substrate molded from the random copolymer composition has excellent adhesion to the information recording film.

Polymerization Example 1 (Synthesis of copolymer (A) having a softening temperature of 70 ° C. or higher) Ethylene and 1,4,5,8-dimethano- were continuously added using a 2 glass polymerization vessel equipped with a stirring blade. 1,2,3,4,4a, 5,8,8a
-Octahydronaphthalene (structural formula: (Hereinafter abbreviated as DMON)). That is, from the top of the polymerization vessel, a cyclohexane solution of DMON was added, and the concentration of DMON in the polymerization vessel was 60 g / VO (OC ₂ H ₅ ) Cl ₂
Solution of vanadium in the polymerization vessel of 0.9 mmol /, ethylaluminum sesquichloride (Al
A cyclohexane solution of (C ₂ H ₅ ) _1.5 Cl _1.5 ) was continuously fed into each of the polymerization reactors so that the aluminum concentration in the polymerization reactor was 7.2 mmol / min.
It is continuously withdrawn so that the polymerization liquid in the polymerization vessel becomes 1. From the top of the polymerization vessel, ethylene is fed at a rate of 85 / hr, hydrogen is fed at a rate of 6 / hr, and nitrogen is fed at a rate of 45 / hr. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization.

When the copolymerization is carried out under the above reaction conditions, a polymerization reaction mixture containing an ethylene / DMON random copolymer is obtained. A small amount of isopropyl alcohol was added to the polymerization liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction. Then, the polymerization solution was charged into a household mixer containing about 3 times the amount of acetone with respect to the polymerization solution while rotating the mixer to precipitate the produced copolymer. The precipitated copolymer was collected by filtration, dispersed in acetone so that the polymer concentration became about 50 g /, and treated with the boiling point of acetone for about 2 hours. After the treatment described above, the copolymer was collected by filtration and dried under reduced pressure at 120 ° C. for 24 hours.

The ethylene composition of the ethylene / DMON random copolymer (A) thus obtained was 59 mol% as measured by ¹³ C-NMR analysis, and the intrinsic viscosity [η] was measured in decalin at 135 ° C. Was 0.42dl / g and the softening temperature (TMA) was 154 ℃.

Polymerization Example 2 (Synthesis of Copolymer (B) with Softening Temperature Below 70 ° C.) In Polymerization Example 1, the concentrations of DMON, VO (OC ₂ H ₅ ) cl ₂ and ethylaluminum sesquichloride in the polymerization vessel were 23, respectively.
g /, 0.7 mmol / and 5.6 mmol / are continuously fed, and ethylene is fed from the upper part of the polymerization vessel at 140 / hour.
Hydrogen is supplied at 13 / h, nitrogen is supplied at 25 / h, and the polymerization temperature is 10 ℃.
Polymerization was continuously carried out in the same manner except that After completion of the polymerization, the produced copolymer was allowed to project in the same manner as in Polymerization Example 1, and the projected copolymer was collected and dried at 180 ° C. under reduced pressure for 12 hours.

The ethylene composition of the ethylene / DMON copolymer (B) obtained as described above was 89 mol% as measured by ¹³ C-NMR analysis, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was The softening temperature (TMA) was 0.44 dl / g and 39 ° C.

Example 1 400 g and 4 g of copolymers (A) and (B) synthesized in Polymerization Examples 1 and 2 (weight ratio: (A) / (B) =
100/1) was put into cyclohexane 8 and dissolved at about 50 ° C. with sufficient stirring. The obtained homogeneous solution is acetone
It was thrown in at 24 and the (A) / (B) blend product was made to come out. The resulting blend was dried at 120 ° C. under reduced pressure overnight.

Tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate, glycerin monostearate as a stabilizer to the obtained (A) / (B) blend. Resin [A],
0.5%, 0.05% and 0.5%, respectively, of the total amount of [B], pelletized at 23 ° C using a 20 mmφ extruder (L / D = 20), and then injection molding machine IS manufactured by Toshiba Machine Co., Ltd. -50,
A disk plate with a thickness of 1 mm and a diameter of 80 mm (both sides are mirror surfaces) was molded. The obtained disk plate was ultrasonically cleaned with Freon TE (manufactured by Mitsui Dupont Fluorochemical Co., Ltd.), and then Si ₃ N ₄ / TbFeCo as an information recording film was formed by a sputtering method.
A / Si ₃ N ₄ 3 layer film (without pretreatment such as press patterning, the film thickness of the core layer was 500 A) was formed. The film formation condition observed by a microscope was good. The film-coated 80 mmφ disk plate obtained above was placed in a constant temperature and humidity layer at a humidity of 85% RH and a temperature of 85 ° C for 170 hrs.
I left it. When the state of the film after the test was observed with a microscope, the appearance of the recording film did not change as compared with that before the test, and the film adhesion was good.

Comparative Example 1 The copolymer (A) obtained in Polymerization Example 1 was blended with a stabilizer in the same manner as in Example 1, and after pelletizing, a disk plate of 80 mmφ was formed to form a film, and the same evaluation as in Example 1 was performed. Ivy. As a result of observing the surface of the film after the environmental test with a microscope, as shown in Table 5, peeling of the recording film was observed at the place where foreign substances exist near the surface of the substrate and at the liquid dripping part at the time of cleaning the substrate.

Comparative Example 2 A blended product was prepared in the same manner as in Example 1 except that the blend ratio of the copolymers (A) and (B) was 100/15, and the same evaluation as in Example 1 was performed. As a result, the condition of the film was good before and after the environmental test. However, the transparency of the disk plate was poor and it was difficult to use it as an information recording plate.

Examples 2 to 7 Copolymers (A) synthesized in the same manner as in Polymerization Examples 1 and 2,
Evaluation was performed in the same manner as in Example 1 using (B). The results are shown in Table 5.

With 80φ disc plate prepared in Example 8-10 Example 1,3,5 (after Freon TE wash), Si was used in Example 1, 3 and 5 as an information recording film ₃ N ₄ / TbFeCo / Instead of the Si ₃ N ₄ 3 layer, a SiO ₂ 1-layer film (film thickness 500A) was prepared. After carrying out the same environmental test as in Examples 1 to 7, the surface of the recording film was observed with a microscope and as a result, the film adhesion was good.

Examples 11 to 12 Al was formed as an information recording film on the 80φ disk substrate after cleaning prepared in Examples 3 and 6 by an evaporation method (thickness 100
A). After performing an environmental test under the same conditions as in Examples 1 to 10, the surface of the recording film was observed with a microscope. As a result, the adhesiveness between the recording film Al and the substrate was good.

Claims (2)

[Claims] 1. An intrinsic viscosity [η] comprising (A) an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II] and measured in decalin at 135 ° C.
Is in the range of 0.05 to 10 dl / g and has a softening temperature (TMA) of 7
A cyclic olefin-based random copolymer having a temperature of 0 ° C. or higher, and (B) an ethylene component and the following general formula [I] or [I
I) consisting of a cyclic olefin component and having an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 5 dl /
a cyclic olefin-based random copolymer having a softening temperature (TMA) of less than 70 ° C. in the range of g, and the weight ratio of the following (A) component / (B) component is
A cyclic olefin-based random copolymer composition characterized by being in the range of 100 / 0.1 to 100/10. General formula [In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group]. 2. An intrinsic viscosity [η] comprising (A) an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II] and measured in decalin at 135 ° C.
Is in the range of 0.05 to 10 dl / g and has a softening temperature (TMA) of 7
A cyclic olefin-based random copolymer having a temperature of 0 ° C. or higher, and (B) an ethylene component and the following general formula [I] or [I
I) consisting of a cyclic olefin component and having an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 5 dl /
a cyclic olefin-based random copolymer having a softening temperature (TMA) of less than 70 ° C. in the range of g, and the weight ratio of the following (A) component / (B) component is
An information recording substrate molded from a cyclic olefin-based random copolymer composition in the range of 100 / 0.1 to 100/10. General formula [In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group].