JPH04161407A - Cycloolefin random copolymer composition and its use - Google Patents

Abstract

PURPOSE:To provide the subject composition containing plural kinds of copolymer of ethylene and a specific cycloolefin, having excellent moldability, transparency, heat-resistance, thermal aging resistance, chemical resistance, solvent resistance, dielectric characteristics and mechanical characteristics and good pit-transferability and useful for optical material, etc. CONSTITUTION:The objective copolymer composition having an olefin content ratio (Cw/Cn) of >=1.04 (Cw is weight-average cycloolefin content defined by formula III and Cn is number-average cycloolefin content defined by formula IV) can be produced by compounding two or more kinds of copolymer having a softening temperature of >=70 deg.C and produced by the copolymerization of (A) ethylene and (B) a cycloolefin such as unsaturated monomer, etc., expressed by formula I (n is 0 or 1; m is 0 or positive integer; q is 0 or 1; R<1> to R<18>, R<a> and R<b> are H, halogen or hydrocarbon group; R<15> to R<18> may be bonded with each other to form monocyclic or polycyclic group; R<15> and R<16> or R<17> and R<18> may together form alkylidene) or formula II (r is 0 or integer of >=1; s and t are 0, 1 or 2; R<1> to R<15> are H, halogen, hydrocarbon group, alkoxy, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a resin composition having excellent moldability and transferability when molding an optical material such as a substrate for information recording media, and a resin composition formed from this resin composition. The present invention relates to a substrate for an information recording medium and an optical material.

Technical Background of the Invention The present applicant has already made various proposals regarding cyclic olefin random copolymers formed from ethylene and specific cyclic olefins. For example, JP-A-60-1
These include Japanese Patent Application No. 68708, Japanese Patent Application No. 59-220550, Japanese Patent Application No. 59-236828, Japanese Patent Application No. 59-236829, and Japanese Patent Application No. 59-242336. The cyclic olefin random copolymers described in these publications or specifications have excellent transparency, and
It also has excellent properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties. Furthermore, although this cyclic olefin random copolymer is a type of polyolefin, it also has excellent adhesiveness to equipment made of various materials. Therefore, this cyclic olefin random copolymer can be used as a resin for information recording medium substrates,
Alternatively, it has properties that are basically suitable as a resin for forming optical materials such as optical fibers.

The above-mentioned cyclic olefin random copolymers basically have properties suitable as resins for forming optical members. It has been found that when this cyclic olefin random copolymer is used to form a substrate for an information recording medium such as a laser disk, the moldability and recording transferability are not necessarily good. That is, in information recording media such as optical discs, CD discs, and laser discs, that is, read-only optical discs, information is recorded by associating the presence or absence of pits formed on the substrate with "0" and NJ times signals. In order to create a substrate on which information is recorded, a molding method is usually adopted in which a recording master is used and resin is injection molded. The pit diameter is usually extremely small, 1 μm or less, and if the fluidity of the resin is low, the pits may not be transferred properly during transfer from the recording master, causing errors and reducing moldability. On the other hand, when a resin with high fluidity is used, the transferability of pits is improved, but the mechanical properties of the resulting substrate may be deteriorated.

Under these circumstances, the present applicant has proposed that if a cyclic olefin random copolymer composition is composed of at least two types of cyclic olefin random copolymers and the composition satisfies specific requirements, The present invention was completed by discovering that a resin composition having high moldability and good pit transferability can be obtained.

Purpose of the Invention The present invention provides a molding method that has excellent moldability, transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, mechanical properties, etc., and also has excellent pit transferability. The object of the present invention is to provide a novel resin composition capable of forming a body.

A further object of the present invention is to provide a substrate for an information recording medium formed from a resin composition having the above characteristics.

Another object of the present invention is to provide an optical material formed from a resin composition having the above characteristics.

Summary of the Invention The cyclic olefin random copolymer composition according to the present invention comprises: (a) ethylene; , m is 0 or a positive integer, q is 0 or l, R1 to R'' and R6
, Rb each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R+s to R11 may be bonded to each other to form a monocyclic or polycyclic ring. , and the monocyclic ring or polycyclic ring may have a double bond, and R'' and 8-ring or R17 and R'' may form an alkylidene group).

(In the formula [I[], r is 0 or an integer of 1 or more, and S
and t is 0.1 or 2, and R1 to RIs each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group. represents R' (or R'
) and R" (or R7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.) Contains two or more types of cyclic olefin-based random copolymers having a softening temperature (TMA) of 70°C or higher, which are copolymerized with at least one type of cyclic olefin selected from the group consisting of unsaturated monomers. A composition in which the ratio Cw/Cn of the weight average cyclic olefin content (Cw) defined by the following formulas (1) and (2), respectively, and the number average cyclic olefin content (Cn) is 1.04 or more. It is characterized by being

[However, m in formulas (1) and (2) is an integer of 2 or more, and Ci and Wi are the cyclic olefin content (mol%) of component i of the cyclic olefin random copolymer and the composition, respectively. Represents the weight fraction of component i present. ] Further, the information recording medium substrate according to the present invention is characterized by being made of the above-mentioned resin composition.

Furthermore, the optical material according to the present invention is characterized by being made of the above-mentioned resin composition.

The cyclic olefin random copolymer composition according to the present invention satisfies the specific requirements regarding its composition, that is, the cyclic olefin content, as described above, and therefore has the advantages that cyclic olefin resins inherently have. It is possible to improve moldability and information transferability during production of a molded article without impairing transparency.

Therefore, an optical material such as a substrate for an information recording medium formed from the above-mentioned cyclic olefin random copolymer composition has high transparency and excellent reliability of recorded information.

Detailed Description of the Invention The cyclic olefin random copolymer composition according to the present invention will be specifically described below.

The cyclic olefin random copolymer composition of the present invention is
It comprises at least two types of cyclic olefin random copolymers. The physical properties of the cyclic olefin random copolymer constituting the composition are not particularly limited;
Various copolymers can be used as long as the resulting cyclic olefin random copolymer composition satisfies the physical properties described below. It is preferable to use a cyclic olefin random copolymer having an intrinsic viscosity of 0.1 to 5 dl/g, preferably 0.1 to 3 dl/g, as measured in decalin (135°C). . The softening temperature (TMA) of the copolymer preferably ranges from 0 to 250°C, preferably from 8° to 200°C, and particularly preferably from 90 to 180°C.

The softening temperature (TMA) is Therm manufactured by DuPont.

The thermal deformation behavior of a 1 mm thick sheet was measured using a mechanical analyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was heated to 5°C.
The temperature was raised at a rate of 0.635 mm per minute, and the temperature at which the needle penetrated 0.635 mm was defined as TMA. In addition, the glass transition temperature (Tg) of the cyclic olefin random copolymer is usually 60 to 230°.
C1 is preferably in the range of 70-190''c.

The degree of crystallinity of this cyclic olefin random copolymer measured by X-ray diffraction is in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

In the above-mentioned cyclic olefin random copolymer,
The repeating unit derived from ethylene (a) is 40 to 90
The repeating unit derived from the cyclic olefin (b) is present in an amount of 10 to 60 mol%, preferably 15 to 50 mol%.
The repeating units derived from ethylene (a) and the repeating units derived from the cyclic olefin (b) are arranged randomly and substantially linearly. In addition, the ethylene composition and cyclic olefin composition are "C-N
Measured by MR.

The fact that this cyclic olefin random copolymer is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135°C.

The cyclic olefin random copolymer composition according to the present invention is preferably composed of a cyclic olefin random copolymer having the above-mentioned preferable properties. Further, the composition of the present invention contains two or more types of cyclic olefin random copolymers.

The cyclic olefin random copolymer constituting the composition of the present invention has a repeating unit derived from ethylene (a),
It is formed from a repeating unit derived from a cyclic olefin fb) represented by either formula [1] or [II] described below. Here, the cyclic olefin is 2
It is also possible to use a combination of more than one type.

...[I] (where n is 0 or l, m is 0 or a positive integer, q is 0 or l, R1 to RI1 and R1, Rb are each independently, Represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R15 to R'' may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic The ring may have a double bond, and Rl 5 and R16
or RI 7 and R'' may form an alkylidene group).

(Formula III), r is an integer of 0 or 1 or more, and S
and t is 0.1 or 2, and R1 to R15 each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group. table, R5 (or R6
) and Rs (or R7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. ) However, in the above formula [I], n is 0 or l, preferably 0. Moreover, m is 0 or a positive integer, preferably 0 to 3.

And q is 0 or 1.

In the above formula [I[], r is 0 or an integer of 1 or more, preferably an integer of 0 to 3.

and R′−′−R” and Ra and Rb (formula [
I]) or R1-R15 (formula [■]) each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, examples of the hydrocarbon group include, each independently, an alkyl group usually having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms, and specific examples of the alkyl group include: Methyl group, ethyl group, isopropyl group, isobutyl group, and amyl group can be mentioned, and specific examples of cycloalkyl group include cyclohexyl group,
Examples include cyclopropyl group, cyclobutyl group, and cyclopentyl group.

Furthermore, in the above formula [II], R' (or R@) and R
' (or R7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

In addition, in the above formula [I], in the case of q or O, the ring represented using q forms a five-membered ring.

Furthermore, in the above formula [I], R15-R"It may be bonded to each other (together) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring or double bond is Examples of such monocyclic or polycyclic rings include the following monocyclic rings or polycyclic rings.Furthermore,
These rings may have a substituent such as a methyl group.

In addition, in the above formula, the carbon atoms shown with 1 and 2 represent carbon atoms of an alicyclic structure to which groups represented by R'' to RIs in the formula [Il are bonded.

Furthermore, Rl 5 and R16 or R17 and R+a may form an alkylidene group. Such an alkylidene group usually includes an alkylidene group having 2 to 4 carbon atoms, and specific examples thereof include an ethylidene group, a propylidene group, an isopropylidene group, and an isobutylidene group.

The cyclic olefin represented by the formula [Il or [II] above can be easily produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by Diels-Alder reaction.

Specifically, as the cyclic olefin represented by the formula [Il or [II], for example, bicyclo[2,2,
1] Hept-2-ene derivative, tetracyclo[4,4,
0,125,17''] -]3-dodecene derivative hexacyclo[6,6,1,13,6,110,+3.
02.7゜09'43-4-hebutadecene derivative, octacyclo[8,8,O,I'', l 47゜1st In
l 13.1S, Q 1g, Q +2. +7-5-tocosene derivative, pentacyclo[6,6,1,1'', Q27゜09+4-4-hexadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-5-heneicosene derivative, tricyclo[4,3,O,I25 co-3-decene derivative, tricyclo[4,4,0,125 co-3-undecene derivative, pentacyclo[6,5,1,I3', 027°of,
Iff] -4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo[7,4,0,
125,1'''.

0 ” +3] -3-pentadecene derivative, heptacyclo[8,j 0.11=, 110.17°112,
+5.02°7, OIl, I-]-]4-eicosene derivative nonacyclo[10,9,1,1'·7.
1 +3.20°11618.031.02・IQ,
Q12.21. Q 14.19] -5-bentacocene derivative, pentacyclo[8,4,0,125,1”・12°
1. +3]-3-hexadecene derivative, heptacyclo[8,8,0,1'・7.11+, +8゜1131g
, (12,8,0+2.17] -5-heneicosene derivative, nonacyclo[10,10,1,1'', 114°21°116・19.02・11.04・9.013・22.
015.20] -5-hexacosene derivative, 5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-phenyl-bicyclo[2,2,1]hept-2-ene , 5-benzyl-bicyclo[2,2,1]hept-2-ene, 5-tolyl-bicyclo[2,2,1-cohept-2-ene, 5-(ethylphenyl)-bicyclo[2,2,1 ]hept-2-ene, 5-(isopropylphenyl)-bicyclo[2°2.1
]hept-2-ene, 1.4-methano-1,4,4a,9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10゜10a-hexahydroanthracene, cyclopentadiene -acenaphthylene adduct, 5-(α
-naphthyl)-bicyclo[2,2,1]hept-2-ene, 5-(anthracenyl)-bicyclo[2,2,1]hept-2-ene, and the like.

More specific examples of such compounds are shown below.

Vinclo[2,2,1]hept-2-ene derivatives such as.

Tetracyclo[4,4,0,1″l, 17.
l@coco-dodecene derivative: natonohexacyclo[5,6,1,IL= ,]IO,
lff , 02.7°o L +1]-4-heptadecene derivative.

Octacyclo [8, 8, Oll t, @ , 14
．． 7.111.1g 11th o2. I, oll17
] −] Pentacyclo[6 with 5-tococene derivatives
,6,1,B '', 0'', 0'' +4]-4-hexadecene derivative; natonohebutacyclo-5-eicosene derivative or hebutacyclo-5-heneicosene derivative.

Nato's tricyclo[4,3,0,1''s]-3-decene derivative: Nato's tricyclo[4,4,0,1''] -
3-undecene derivative: Nato's pentacyclo[6,5,
1,I'" o2.7, o@IJ-4-pentadecene derivatives: Nato diene compounds: heptacyclo[7,4,0,12',1@",0
''']-]3-pentadecene derivative o2.7, oll, 1@]-, i=emini-eicosene.

OLt, gL IJ, Q1121. Q10.
1-5-bentacocene derivative.

Pentacyclo[8,4,0,1'・jll, +2
．． 61,17-3-hexadecene derivatives: Heptacyclo [8,8,0,1'7.1' Tsuta 1
1.111. H, Off, 1.0+2. I7]-5-heneicosene derivative.

04, @, 013.12.01ime] -]
Mention may be made of 5-hexacosene derivatives and furthermore. (Left below) The cyclic olefin random copolymer composition of the present invention is a cyclic olefin random copolymer obtained by copolymerizing the above specific cyclic olefins alone or in combination with ethylene. Contains two or more types.

The cyclic olefin random copolymer composition according to the present invention can be prepared by separately producing cyclic olefin random copolymers and then blending them, or by using a multistage polymerization method to prepare two types of cyclic olefin random copolymers. Compositions containing the different cyclic olefin random copolymers mentioned above can also be prepared by one continuous process.

The cyclic olefin-based random copolymer is produced, for example, by polymerizing ethylene and the above-mentioned cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. I can do something. This polymerization method itself is well known and has been disclosed in Japanese Patent Application Laid-open No. 1687-1987.
It has been proposed in Publication No. 08, etc.

The cyclic olefin random copolymer which is a copolymer of cyclic olefins and ethylene as described above contains ethylene and the above-mentioned cyclic olefin as essential components, or contains the present invention in addition to the two essential components. If necessary, other copolymerizable unsaturated monomer components may be contained within a range that does not impair the purpose. Specifically, the unsaturated monomer which may be optionally copolymerized includes, for example, propylene, 1-butene, 4-methyl in an amount less than equimolar to the ethylene component unit in the random copolymer to be produced. -1-pentene, 1-hexene, ■-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, ■-
The number of carbon atoms in octadecene and 1-eicosene is 3~
20 α-olefins can be exemplified.

Furthermore, in the present invention, when producing the above-mentioned cyclic olefin-based random copolymer, the cyclic olefin-based random copolymer represented by the above formula [1] or [II] is Cyclic olefins other than olefins can also be polymerized. Such cyclic olefins include, for example, cyclobutene, cyclopentene, cyclohexene, 3.
4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene,
Examples include 3a, 5.6.7a-tetrahydro-4,7-methano-IH-indene, and the like. Such other cyclic olefins can be used alone or in combination, and usually have the formula [I] or [n]
It is used in an amount ranging from 0 to 50 mol% of the cyclic olefin represented by.

Such cyclic olefin random copolymers are disclosed in JP-A-60-168708 and JP-A-61-12081.
Publication No. 6, JP-A-61-115912, JP-A-6
Japanese Patent Application No. 1-115916, Japanese Patent Application No. 1983-95905, Japanese Patent Application No. 1982-95906, Japanese Patent Application No. 1982-27
It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in JP-A No. 1308, JP-A No. 61-272216, and the like.

More specifically, for example, tetracyclo(4,4,0,125゜17. ) using VO(OCH2CH3)C12/AI (CH2CH
.

)15C1,5, reaction temperature 10°C1 reaction time (
It can be produced by adopting conditions in which the copolymerization reaction of ethylene and TCD-3 is carried out for 30 minutes (polymerization reaction residence time).

The cyclic olefin random copolymer composition according to the present invention contains two or more of the above cyclic olefin random copolymers. Such a cyclic olefin random copolymer composition can be produced by mixing a plurality of cyclic olefin random copolymers using various methods.

For example, two or more types of cyclic olefin random copolymers are dissolved in a good solvent such as cyclohexane, the polymers are mixed in a solution state, and then this mixed solution is poured into a poor solvent such as acetone to polymerize. By employing a method of precipitating the combined composition and pelletizing the precipitated polymer composition, the uniformity of the composition is improved.

The cyclic olefin random copolymer composition according to the present invention can also be produced in one continuous process by employing the multistage polymerization method as described above. When adopting a multi-stage polymerization method, it is possible to adopt a method in which two or more types of ethylene/cyclic olefin copolymers with different compositions are polymerized in separate polymerization vessels, and then mixed in one process, or , for example, using TCD-3 as the cyclic olefin and VO(OC
R,CH,)C1,/AI (CH,CH,),,sC
A copolymerization reaction of ethylene and TCD-3 was carried out using 1□, at a reaction temperature of 10°C and a reaction time of 30 minutes, under conditions where the ethylene/TCD-3 supply ratio was smaller than that of the second process below, Producing a copolymer with high cyclic olefin content,
Then, the obtained polymerization solution (containing unreacted ethylene and unreacted cyclic olefin) is supplied to a second polymerization process,
In a cyclohexane medium, the same as above was further supplied as a catalyst, ethylene and TCD-3 were further supplied, reaction temperature was 10°C, reaction time was 30 minutes, and the above-mentioned first
By increasing the ratio of ethylene/TCD-3 from the process described above and producing a copolymer with a low cyclic olefin content in the presence of the copolymer with a high cyclic olefin content, the cyclic olefin random according to the present invention can be obtained. Copolymer compositions can be prepared.

The cyclic olefin random copolymer composition according to the present invention contains two or more types of cyclic olefin random copolymers as described above, and has an intrinsic viscosity [η] measured in decalin at 135°C. ,0. O1 to 5 dl/g1, preferably 0.1 to 3 dl/g, particularly preferably 0.2 to 2.
It is in the range of 5 dl/g.

The softening temperature (TMA) of the cyclic olefin random copolymer composition is 70 to 250°C, preferably 80 to 250°C.
The temperature is 200°C, more preferably in the range of 90 to 180°C. Further, it is desirable that the glass transition temperature (Tg) of the cyclic olefin random copolymer composition is usually in the range of 60 to 230°C, preferably 70 to 190°C.

In addition, the crystallinity of this cyclic olefin random copolymer composition measured by X-ray diffraction method is 0 to 10%,
The range is preferably from 0 to 7%, particularly preferably from 0 to 5%.

In the cyclic olefin random copolymer constituting such a cyclic olefin random copolymer composition, the structural unit derived from the cyclic olefin represented by the formula [1] or [II] is represented by the following formula [I ] or [IV]
It is thought that it forms a repeating unit with the structure represented by

... [■] (In formula [I], m, n, q and R1 to R'' and R
''' and Rb are the same as defined in the above formula [1].

) (Formula [■, r, s, t and R'-R" are the above formula [
II]. ) In the cyclic olefin random copolymer composition as described above, the repeating unit derived from the cyclic olefin (b) is present in an amount of 10 to 60 mol%, preferably 15 to 50 mol%, and ethylene The repeating unit derived from (a) is 40 to
It is present in an amount of 90 mol%, preferably in the range of 50 to 85 mol%.

In the cyclic olefin random copolymer composition of the present invention, the weight average cyclic olefin content (Cw) defined by the following formula (1) and the number average cyclic olefin content (Cn) defined by the formula (2) The ratio Cw/Cn satisfies certain requirements.

Cw=ΣCi Wi =11)i=1 However, in formulas (1) and (2), m represents the number of cyclic olefin random copolymer components constituting the cyclic olefin random copolymer composition, It is an integer of 2 or more, preferably 2 to 5. And Ci is the cyclic olefin random copolymer component i (
Hereinafter, it will be referred to as the i component. ) Cyclic olefin content (mol%)
and Wi represents the weight fraction of component i present in the composition.

In the composition of the present invention, the above Cw/Cn is 1.04 or more, preferably 1.045 to 2.0, particularly preferably 1.05 to 1.3. When the Cw/Cn of the copolymer composition is within the above range, the moldability when the composition is subjected to molding and the transferability of recorded information are improved.

In the present invention, in addition to the above-mentioned cyclic olefin random copolymers, cyclic olefin ring-opened polymers, ring-opened copolymers obtained by ring-opening the same or different cyclic olefin monomers, or their hydrogen Additives can also be used. To explain such cyclic olefin ring-opening polymers, ring-opening copolymers, and hydrogenated products thereof using the cyclic olefin represented by the formula [I] as an example, they react as described below. It is thought that it constitutes a ring-opened (co)polymer and a hydrogenated product thereof. In the case of a hydrogenated product of such a ring-opening polymer, Ci means the content (mol %) of the highest cyclic olefin component structured in component i of the polymer.

↓ Ring-opening ↓ Examples of hydrogenated polymers include ring-opening copolymers of tetrancrotodecene and norbornene and their derivatives, and hydrogenated products thereof.

In addition, in the present invention, the above-mentioned ring-opening polymers, ring-opening copolymers, hydrogenated products thereof, and cyclic olefin-based random copolymers (hereinafter, these are collectively referred to as cyclic olefin-based resins) The - part may be modified with an unsaturated carbonic acid such as maleic anhydride. Such a modified product can be produced by reacting a cyclic olefin resin as described above with an unsaturated carboxylic acid, an anhydride thereof, and a derivative such as an alkyl ester of an unsaturated carboxylic acid. In this case, the content of structural units derived from the modifier in the modified cyclic olefin resin is usually 50 to 10 mol 96 or less. Such a modified cyclic olefin resin can be produced by blending a modifier with a cyclic olefin resin and graft polymerizing it to a desired modification rate, or by preparing a modified product with a high modification rate in advance. However, it can also be produced by then mixing this modified product with an unmodified cyclic olefin resin.

In the present invention, the above ring-opening polymers, ring-opening copolymers, hydrogenated products thereof, cyclic olefin random copolymers, and modified products thereof can be used alone or in combination.

Further, in the present invention, in addition to the above-mentioned cyclic olefin resin, if desired, a softening temperature (TMA) of 70°
Other cyclic olefin resins having less than C may be blended and used.

In addition to the above-mentioned cyclic olefin resin, the cyclic olefin random copolymer composition of the present invention may contain a rubber component for improving impact strength, a heat stabilizer, a weather stabilizer, and an antistatic agent. , a slip agent, an anti-blocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, etc. can be blended, and the blending ratio thereof is an appropriate amount.

For example, as a stabilizer that may be added as an optional component, tetrakis(methylene-3(3,5-di-t-
Butyl-4-hydroxyphenyl)propionate 1methane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate alkyl ester, 2.2'-
Phenolic antioxidants such as oxamide bis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)]propionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate, glycerin monostearate,
Examples include fatty acid esters of polyhydric alcohols such as glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination; for example, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate 1methane and zinc stearate and Examples include combinations with glycerin monostearate.

In the present invention, it is particularly preferable to use a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol in combination; Preferably, it is an esterified polyhydric alcohol fatty acid ester.

Such fatty acid esters of polyhydric alcohols include:
Specifically, glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, and glycerin dilaurate;
Fatty acid esters of pentaerythritol such as pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate are used.

Such a phenolic antioxidant is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and more preferably 0 to 2 parts by weight, based on 100 parts by weight of the cyclic olefin resin. The fatty acid ester is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the cyclic olefin resin.

In addition, in the present invention, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, Magnesium hydroxide, basic magnesium carbonate, dolomite,
Calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass peas, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, carbonized Fillers such as silicon fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

The information recording medium substrate according to the present invention is formed from the cyclic olefin random copolymer composition as described above. Further, there is no particular restriction on the shape of the information recording medium substrate of the present invention, and various forms can be used, such as a so-called air sandwich type in which two substrates are arranged with an air layer in between.

The optical material according to the present invention is formed from a cyclic olefin random copolymer composition as described above. Further, the shape of the optical material of the present invention is not particularly limited, and it can be used, for example, as an optical lens, an optical fiber, etc.

The information recording medium substrate and optical material of the present invention can be obtained by molding the cyclic olefin random copolymer composition of the present invention into a desired shape by employing well-known methods such as extrusion molding and injection moldability. can be manufactured.

Effects of the Invention Since the cyclic olefin random copolymer composition according to the present invention satisfies the specific requirements regarding its composition, that is, the cyclic olefin content, as described above, it essentially contains no cyclic olefin resin. It is possible to improve the moldability during molding and the transferability of information without impairing the excellent transparency, and is suitably used in the production of optical materials such as substrates for information recording media, optical lenses, and optical fibers.

[Example] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

In addition, the measuring method and evaluation method of various physical property values in this invention are shown next.

(1) Melt flow index (MFR) 260°C1 load 2.16 according to ASTM D1238
Measured in kg.

(2) Preparation of test piece A test piece was molded under the following molding conditions using an injection molding machine 1S-55EPN manufactured by Toshiba Machine Corporation and a specified test piece mold.

After molding, the test piece was left at room temperature for 48 hours and then measured.

Molding conditions Niji cylinder temperature 220°C 1 mold temperature 60°C
1 injection pressure car secondary/secondary = 1000/800kg/al
Injection speed (-order) 30 mm/sec, screw rotation speed 15 Orpm (3) Softening temperature (TMA) Thermo Mechanical A manufactured by DuPont
The thermal deformation behavior of a 1 mm thick sheet was measured using a nalyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, the temperature was raised at a rate of 5°C/min, and the temperature at which the needle penetrated 0.635 mm was defined as TMA.

(4) Glass transition temperature (Tg) Measured using DSC-20 manufactured by SEIKO Electronics Co., Ltd. at a heating rate of 10° C./min.

(5) Molecular weight distribution (M w / M n ) Measured by GPC method.

(6) Fluidity evaluation 260°C load 2.16 according to ASTM D-1238
MFRl, measured in kg, and MFR, measured using the same method with a load of 10 kg. The fluidity was evaluated using the following ratio: MF Rr "MF RIQ/MF R2,11. In general, the larger the MF Rr, the better the fluidity and transferability.

(7) Evaluation of groove transferability Using an injection molding machine 15-55EPN manufactured by Toshiba Machine ■, a disk plate with a thickness of 1 mm and a diameter of 80 mm (one side has a mirror surface, the other side has group grooves (interval 1.4 μm, depth 0.09 a) m
, a spiral with a width of 0.5 μm)) was formed, and the groove shape of the obtained disk plate was evaluated using a microscopic microscope.

Example 1 Ethylene and tetracyclo [4,4,0,125°17,
IQ] A random copolymer with -3-dodecene (hereinafter abbreviated as TCD-3), with an ethylene content of 56.0 mo1% as measured by C-NMR, TCD-3
Content: 44.0mo1%, MFR (260°C): 2
0 g/10 m1n, intrinsic viscosity [η] measured in decalin at 135°C is 0.50 d//g, TMA is 178
55% by weight of an ethylene/TCD-3 random copolymer (hereinafter referred to as component A) with a Mw/Mn of 2.8 at 151°C and Tg, and an ethylene content of 72% as measured by C-NMR. 0mo1%, TCD-3 content is 28.0
mo1%, MFR (260°C) or 38g/10m1n
, the intrinsic viscosity [η] measured in decalin at 135°C is 0.54 dl/g, and the TMA is 112°C1Tg or 91
"Ethylene-TCD-3 with C1Mw/Mn of 2.7
After thoroughly mixing 45% by weight of the random copolymer (hereinafter referred to as component C), a twin screw extruder (manufactured by Ikegai Tekko ■, PCM
45) at a cylinder temperature of 220° C. to prepare a cyclic olefin random copolymer composition. The weight average cyclic olefin content (C
w) is 36.8, and the number average cyclic olefin content (C
n) was 35.0, and Cw/Cn was 1.051. The above composition was pelletized using a pelletizer.

Using the obtained pellets, test pieces were prepared by the method described above, and the physical properties were evaluated.

The results are shown in Table 1.

Example 2 Component A is 70% by weight and the ethylene content measured by C-NMR is 81.5 mo
1%, TCD-3 content is 18.5mo1%, MFR (
260°C) is 32g/10m1n, and the intrinsic viscosity [η] measured in decalin at 135°C is 0.51dl/gST.
MA is 71″C1Tg is 48°C, Mw/Mn is 2.8
The same operation as in Example 1 was performed except that 30% by weight of an ethylene-TCD-3 random copolymer (hereinafter referred to as component) was used. The weight average cyclic olefin content (Cw) of the obtained composition was 36.4, the number average cyclic olefin content (Cn) was 31.1, and Cw/Cn was 1.170.

The above composition was pelletized using a pelletizer, a test piece was prepared by the method described above, and the physical properties were evaluated.

The results are shown in Table 1.

Example 3 70% by weight of component A, 5% by weight of component C, 20% by weight of component D, and the ethylene content measured by C-NMR was 62.5 mo
1%, TCD-3 content is 37.5mo1%, MFR (
T
MA is 153°C1Tg month 31°C5Mw/Mn is 2
．． The same operation as in Example 1 was performed except that 5% by weight of the ethylene-TCD-3 random copolymer No. 9 (hereinafter referred to as component B) was used. The weight average cyclic olefin content (Cw) of the obtained composition was 37.8, the number average cyclic olefin content (Cn) was 33.5, and Cw/Cn
was 1.128.

The above composition was pelletized using a pelletizer, a test piece was prepared by the method described above, and the physical properties were evaluated.

The results are shown in Table 1.

Comparative example 1 Component B alone was molded and its physical properties were evaluated.

The results are shown in Table 1.

Comparative Example 2 The same operation as in Example 1 was performed except that 85% by weight of component B and 15% by weight of component C were used. The weight average cyclic olefin content t (Cw) of the obtained composition was 36°1, the number average cyclic olefin content (Cn) was 35.7, and Cw/Cn was 1.011. The above composition was pelletized using a pelletizer, a test piece was prepared by the method described above, and the physical properties were evaluated.

The results are shown in Table 1.

Claims (3)

[Claims] (1) (a) Ethylene (b) The following formula [I] or [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R^1 to R^1^8 and R^a and R^b are each independently a hydrogen atom, a halogen atom, and a hydrocarbon group. R^1^5 to R^1^8 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring represents an atom or group selected from the group It may have a double bond, and R^1^5 and R^1^6 or R^1^7
and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (In formula [II], is an integer of 0 or 1 or more, s and t are 0, 1, or 2, and R^1 ~R^1^5
each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R^5 (or R^6) and R^9 (or R^7) means carbon number 1~
They may be bonded via the alkylene group of 3, or may be bonded directly without any group. ) Two types of cyclic olefin-based random copolymers having a softening temperature (TMA) of 70°C or higher, which are copolymerized with at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by A composition comprising the above, wherein the ratio Cw/Cn of the weight average cyclic olefin content (Cw) and the number average cyclic olefin content (Cn) defined by the following formulas (1) and (2), respectively, is A cyclic olefin random copolymer composition characterized in that it has a molecular weight of 1.04 or more. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) [However, m in formulas (1) and (2) is 2 or more. They are integers, and Ci and Wi represent the cyclic olefin content (mol%) of component i of the cyclic olefin random copolymer and the weight fraction of one component present in the composition, respectively. ] (2) A substrate for an information recording medium, characterized in that it is formed from the composition according to claim 1. (3) An optical material formed from the composition according to claim 1.