WO1994017128A1

WO1994017128A1 - Pellet of random cycloolefin copolymer and process for producing the same

Info

Publication number: WO1994017128A1
Application number: PCT/JP1994/000088
Authority: WO
Inventors: Masayuki Okabe; Hideki Sakai; Kazuyuki Takimoto; Tetsuji Kasai; Takehiko Kawate; Kenji Wakatsuru
Original assignee: Mitsui Petrochemical Industries, Ltd.
Priority date: 1993-01-29
Filing date: 1994-01-24
Publication date: 1994-08-04

Abstract

A pellet of a random cycloolefin copolymer composed of ethylene and a cyloolefin and having a softening point of 70 °C or above. 30 mg of the pellets contain sixty thousand or less of fine cyclohexane-insoluble particles. The pellet can be produced by the method of feeding the powdery copolymer into an extruder after being heated to 50 °C or above, the method of using an extruder wherein the melting initiating end has the highest temperature that is at least 90 °C higher than the Tg of the copolymer, the method of conducting melt extrusion on a corotating twin-screw extruder, the method of filtering the extruded molten copolymer at a pressure difference of 90 kg/cm2 or less, the method of reducing the amount of the fine powder generated in the step of, for example, drying the pellets below 100 ppm, or a combination of these methods.

Description

Itoda β

Cyclic olefin-based random copolymer pellets and method for producing the same

[Technical field]

The present invention relates to a cyclic olefin-based random copolymer pellet and a method for producing the same. More specifically, the present invention can reduce a reading error caused by a substrate when used as an optical disc substrate, and can be used as a transparent film when used as a transparent film. A cyclic copolymer-based random copolymer belt capable of producing a molded article having particularly excellent optical properties, such as a remarkably improved property, and a polymer having such properties. The present invention relates to a method of manufacturing a pellet having the same.

[Technical background]

The present applicant has already made various proposals for a cyclic olefin-based random copolymer formed from ethylene and a specific cyclic olefin. For example, Japanese Patent Application Laid-Open Nos. Sho 60-168708 and Japanese Patent Application Nos. Sho 59-220550, 59-239368, and 59-23968 No. 29 and No. 59-22432336. The cyclic olefin-based random copolymers described in these publications or in the specification have excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, and dielectric properties. Excellent in various properties such as properties and mechanical properties. Furthermore, this cyclic olefin-based random copolymer is a kind of Despite being a polyolefin, it has excellent adhesion to substrates of various materials. Therefore, this cyclic olefin-based random copolymer is used in the field of optical materials such as optical memories and optical fibers, and in transparent films such as transparent films and transparent containers. Used in the field of container and packaging materials.

In general, such a cyclic-olefin-based random copolymer is generally in the form of a pellet, and the force by which an optical disc substrate or the like is formed from the pellet. The production of optical discs from pellets can result in very few read errors, and the production of transparent films from this copolymer pellet produces very little. Despite this, transparency was sometimes reduced. The present inventor aims to reduce the reading error of an optical disc produced from a cyclic-olefin-based random copolymer pellet, and to improve the transparency of a transparent film. As a result of intensive studies, it has been found that some of these causes are caused by fine particles insoluble in hexahedral hexane contained in the cyclic olefin-based random copolymer pellet.

The cyclohexane-insoluble fine particles contained in such pellets are hardly contained in the cyclic olefin-based random copolymer immediately after polymerization, and the cyclic olefins are not included in the pellets. It is considered to be generated when pellets are produced from the in-based random copolymer.

The present invention has been made in view of the prior art as described above, and is directed to a cyclic olefin system in which the amount of cyclohexane-insoluble cyclic olefin-based random copolymer fine particles is extremely small. It is intended to provide a method for producing a random copolymer pellet. More specifically, the present invention Can reduce reading errors caused by the substrate when used as an optical disk substrate, and can achieve extremely high transparency when used as a transparent film. And a cyclic olefin random copolymer belt capable of producing a molded article having excellent optical properties as described above. Its purpose is to provide a method of manufacturing lett.

[Disclosure of the Invention]

The cyclic olefin-based random copolymer belt according to the present invention comprises:

(a) ethylene,

(b) Cyclic olefin random copolymer having a softening temperature (TMA) of 70 C or more obtained by copolymerization with a cyclic olefin represented by the following formula [I] or [n]: 60,000 cyclohexane-insoluble cyclic olefin-based random copolymer fine particles having a particle diameter of 1 μm or more, which are coalesced pellets and contained in 3 O mg of the pellets It is characterized by the following

A first method for producing a cyclic olefin-based random copolymer pellet according to the present invention comprises:

(a) Ethylene and

(b) The softening temperature (TMA) obtained by copolymerization with at least one type of cyclic olefin represented by the following formula [I] or [H], is 70 ° C or more. When the cyclic cyclic random copolymer is supplied to an extruder, and extruded from the extruder in a molten state, a pellet of the copolymer is produced. It is characterized in that the cyclic orphanic random copolymer is preheated to a temperature of 50 ° C or higher, supplied to an extruder, and formed into a pellet.

In the present invention, the cyclic olefin-based random copolymer supplied to the extruder has a force ⁵ 'which is previously heated to a temperature of 50 ° C. or higher, and the copolymer is a cyclic solvent substantially containing no solvent. The resin may be an olefin-based random copolymer powder, or may contain a solvent in an amount of 20% by weight or less.

A second method for producing the cyclic-olefin-based random polymer pellet according to the present invention comprises:

(a) ethylene,

(b) The softening temperature (TMA) obtained by copolymerization with at least one cyclic olefin represented by the following formula [I] or [または] is 70 ° C or higher. When the cyclic olefin-based random copolymer is supplied to an extruder and extruded from the extruder in a molten state, the copolymer pellet is produced.

The temperature of the cylinder at the beginning of the melting portion of the extruder is 90 ° C. or more higher than the glass transition temperature (Tg) of the copolymer supplied to the extruder, and It is characterized by supplying a cyclic olefin-based random copolymer to an extruder set higher than the other parts and forming it into a pellet.

A third method for producing a cyclic olefin-based random copolymer pellet according to the present invention comprises:

(a) ethylene, (b) The softening temperature (TMA) obtained by copolymerization with at least one type of cyclic olefin represented by the following formula [I] or [D] is 70 ° C or more. When the cyclic olefin-based random copolymer is supplied to a twin-screw extruder and extruded from the twin-screw extruder in a molten state, the copolymer pellet is produced.

It is characterized in that a cyclic olefin-based random copolymer is supplied to a twin-screw extruder in which the screw rotates in the same direction, and is formed into a pellet.

A fourth method for producing the cyclic copolymer random copolymer pellet according to the present invention comprises:

(a) Ethylene and

(b) A cyclic olefin random having a softening temperature (TMA) of 70 ° C or more, obtained by copolymerizing a cyclic olefin represented by the following formula [I] or [D]. In producing the copolymer pellet by supplying the copolymer to an extruder and extruding the molten state from the extruder,

After melt-extrusion from the extruder, the molten cyclic olefin-based random copolymer was adjusted to a pressure difference of 90 kg / Cirf or less by adjusting the pressure difference across the polymer filter to 90 kg / Cirf or less. It is characterized by passing through a filter.

In addition, at this time, the cyclic olefin-based random copolymer was added to 50

It is preferable to heat to a temperature of 'C or higher and feed it to the extruder.

A fifth method for producing a cyclic olefin-based random copolymer pellet according to the present invention comprises:

(a) Ethylene and

(b) at least one kind of ring represented by the following formula [I] or [π]; A cyclic olefin-based random copolymer having a softening temperature (TMA) of 70 ° C or higher obtained by copolymerization with refine is supplied to an extruder, and the extruder is melted. When producing the copolymer pellet by extrusion from

When the pellets extruded from the extruder are dried and / or mixed, the pellets are dried so that the amount of fine powder generated from the cyclic olefin-based random copolymer pellets is 100 ppm or less. And / or mixed.

Further, a sixth method for producing the cyclic olefin-based random copolymer pellet according to the present invention includes:

(a) Ethylene and

(b) The softening temperature (TMA) obtained by copolymerization with at least one kind of cyclic olefin represented by the following formula [I] or [Π] is 70 ° C or more. When the cyclic olefin-based random copolymer is supplied to an extruder, and extruded from the extruder in a molten state, the copolymer pellet is produced.

The cyclic-olefin-based random copolymer previously heated to a temperature of 50 ° C or higher was used. The cylinder temperature at the beginning of the melt was determined by the glass transition temperature (Tg) of the copolymer supplied to the extruder. Temperature is higher than 90 ° C, the temperature at the beginning of the melting part is set higher than the other parts of the extruder, and the rotation directions of the two screws are the same. The copolymer is supplied to a twin-screw extruder and extruded from the extruder in a molten state, and then the copolymer is subjected to a differential pressure of 90 Kg / Crrf or less before and after the polymer filter. After passing through the polymer filter with adjustment to The pellets are dried so that the amount of fine powder generated from the pelletized force of the shaped cyclic olefin-based random copolymer is 100 ppm or less. And / or mixed.

· · · [I] In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ′ to R is and R. And R _b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group;

R ~ R is rather good even if rather good also form a monocyclic or polycyclic bonded to each other, and the monocyclic or polycyclic ring having a double bond and, R ^'5 and R And ¹⁶ or R ¹⁷ and R 18 may form an alkylidene group. R 18

… [Π] In the above formula [Π], p and q are 0 or a positive integer, m and n are 0, 1 or 2,

R ′ to R ′ ⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group,

Via a carbon atom to which Re or R ¹⁰ is attached, an alkylene group having carbon atom or R ^{1 1} is bonded directly or TansoHara child number of carbon atoms. 1 to 3 R ¹³ is bonded May be combined

Further, n = m = 0 Noto-out R ^'5 and R ¹² or R' 5 and may form a monocyclic or polycyclic aromatic ring bonded to each other.

According to the present invention, there is provided a pellet comprising a copolymer of ethylene and cyclic olefin, and the copolymer pellet has a particle diameter of 1 m or more. It contains only a very small amount of the cyclohexane-insoluble cyclic olefin-based random copolymer fine particles, and the molded article produced from this pellet has excellent optical properties. For example, if an optical disk substrate is manufactured from this pellet, read errors due to the substrate can be reduced, and if a transparent film is manufactured, the extremely high level can be achieved. And obtain a film with excellent transparency.

In general, when the resin is supplied to the extruder and brought into a molten state, the supplied resin uses heat transferred from a heated cylinder and a screw that entangles the copolymer. Melting occurs due to both the heat generated by the shearing and the heat generated by the shearing.

However, by pre-heating the copolymer to 50 ° C or higher as described above, the cyclic olefin-based random copolymer is already heated before a shear force is applied. The melt is quickly melted in the extruder, so that even when the screw rotates in the extruder, no excessive shearing force is applied to the cyclic olefin-based random copolymer. .

In addition, by setting the temperature of the cylinder at least 90 C higher than the glass transition temperature of the copolymer and the highest in the molding machine, the cyclic-olefin-based random copolymer can be obtained. Since the melt is mainly brought into a molten state by heat from the heated cylinder, no excessive shearing force is applied to the cyclic olefin-based random copolymer in the extruder.

In addition, when producing a cyclic olefin-based random copolymer pellet using a twin-screw extruder, the rotation directions of the screws are set to the same direction. However, no excessive shear stress is applied to the cyclic olefin-based random copolymer. In addition, a polymer filter (filter for filtering the molten polymer) is placed at the tip of the nozzle of the extruder, and the melted cyclic olefin-based random copolymer is melted into this polymer. In the case of filtration using a mar filter, the difference in pressure (differential pressure) applied to the copolymer before and after the polymer filter in the flow direction is reduced to a certain level or less. Excessive shear is not applied when the copolymer passes through the mar filter.

Furthermore, the cyclohexane-insoluble cyclic olefin-based random copolymer fine particles are used for drying the cyclic olefin-based random copolymer pellets or when such a copolymer-based random copolymer pellet is dried. Often formed by the fine powder generated when mixing the pellets, thus reducing the amount of copolymer microparticles to less than 100 ppm during pellet drying and / or mixing. Follow the steps below.

By performing the above, when producing a copolymer pellet, cyclohexane-insoluble cyclic olefin-based random copolymer fine particles having a particle size of 1 y "m or more are produced. Can be suppressed.

The copolymer pellets thus produced have a very low content of cyclohexane-insoluble cyclic olefin-based random copolymer fine particles having a particle size of 1 μm or more. When optical disc substrates are manufactured from these pellets with excellent optical characteristics, it is possible to reduce reading errors caused by non-uniformity of the substrates and to reduce the need for transparent films. When manufactured, extremely transparent films can be obtained.

[Brief description of drawings]

FIG. 1 shows an example of the steps of the method for producing a copolymer pellet according to the present invention. FIG.

FIG. 2 is a diagram schematically showing an example of an extruder used in the method of the present invention.

FIG. 3 is a diagram schematically illustrating an example of a twin-screw extruder used in the method of the present invention.

FIG. 4 is a diagram showing a combined state of the screen.

Explanation of reference numerals;

1, 1 1 ··· Cylinder 2, 1 2a, 1 2b '.'

3 1 1 3Motor 1 4 1 4

5, 15 '

7 Heating means 7a

8

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the cyclic olefin-based random copolymer belt according to the present invention and a method for producing the same will be specifically described.

The cyclic olefin-based random copolymer pellet according to the present invention comprises a copolymer of a cyclic olefin represented by the following formula [I] or [Π] and ethylene.

Their to, the annular O-les off Lee emissions based random copolymer contained in Bae LESSON preparative 3 0 _m g, hexane-insoluble cyclic O Les off fin system la to particle size 1 / m the following consequent opening The number of random copolymer fine particles is 60,000 or less, preferably 50,000 or less, and more preferably 30,000 or less.

In the present invention, the cyclic olefin-based random copolymer pellet is used in the present invention. The number of fine particles of cyclic olefin-based random copolymers having a pore diameter of 1 m or more contained in a bottle is 1 m or more in 1 Oml. Cyclic hexane-based random copolymer pellets are dissolved in 200 or less cyclohexane in an amount of 3 g / liter, and contained in the resulting polymer solution. It is measured by measuring the number of fine particles having a particle diameter of 1 μm or more with a fine particle force center. In the above measurement, the number of fine particles is measured with a fine particle counter (manufactured by Lion Corporation: KL-01 type) using a KS-60 type sensor.

For such cyclic olefin-based random copolymer pellets, the intrinsic viscosity [] measured in decalin (135 ° C) is usually 0.0 l to 5 dl / g, Preferably it is in the range of 0.1 to 3 dl / g, more preferably 0.2 to 2.5 d1 / g.

The softening temperature (TMA) of the copolymer velvet is 70 ° C or higher, preferably 70 to 250 ° 〇, particularly preferably 80 to 2 ° C. 0 ° C, more preferably 90 ° C: I within the range of 80 ° C. Further, the glass transition temperature (Tg) of the cyclic olefin-based random copolymer pellet is usually from 60 to 230, preferably from 70 to 190. In range.

In addition, the degree of crystallinity were measured me by the X-ray diffraction method for the annular O reflex fin-based random copolymer Perez door is usually 0-1 _00/0, is rather to preferred 0-7%, Particularly preferred is in the range of 0-5%.

Yo I Do annular O reflex fin system random copolymer described above, the repeating units derived ethylene lens power et al, usually 4 0-9 0 mole ^_0/0, preferred and rather 5 0-8 5 mol It has an amount in the range of ^_0/0, also the formula [I] also The [[pi] a repeating unit derived from a cyclic O reflex fin represented by, usually 1 0-6 0 mole ^_0/0, the preferred and rather in the range of 1 5-5 0 mole ^_0/0 Have in quantity. Furthermore, in this copolymer, the repeating units derived from ethylene and the repeating units derived from a specific cyclic olefin are randomly and substantially linearly arranged. . The ethylene composition and cyclic olefin composition can be determined from the values obtained by measuring ' ³ C-ΝR of this cyclic olefin-based random copolymer.

When producing the cyclic olefin-based random copolymer pellets of the present invention as described above, first, the cyclic olefins represented by the following formula [I] or [Π] To produce a copolymer of ethylene and ethylene.

··· [I] In the above formula [I], η is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. If q is 1, R "and R ^B are each independently, represent an atom or a hydrocarbon group described below, and when q is 0, each of the bond to form a 5-membered ring.

In the above formula [I], R ′ to R ¹⁸ and R ^a and R ^B each independently represent a hydrogen atom, a halogen atom or a hydrocarbon

Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the hydrocarbon group usually include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically,

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. be able to. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group and the like.

Examples of the aromatic hydrocarbon group include a fuunyl group and a naphthyl group.

In the formula [I] in is al, R '5 and R' ₆ and power i, and the R '7 and R' _8,

R ^{1 5} and R 1 ⁷ and force ⁵ ', R' 6 and R '8 and the force S, R' 5 and R _'8 and force ί or R,! 6 and RI ⁷ may be bonded to each other (jointly with each other) to form a monocyclic or polycyclic structure, and the monocyclic or polycyclic structure thus formed. May have a double bond. Specific examples of the monocyclic structure or polycyclic structure formed here include the following structures.

In the above examples, the carbon atoms numbered 1 and 2 represent the carbon atoms to which R (R 16) or R ′ 7 (R 18) are bonded in formula [I].

Further, it may also form a R 1 ⁵ and at the R 1 6, or RI ⁷ and R 1 beta and in alkyl Li Den group les. The number of carbon atoms in such an alkylidene group is usually 2 to 20 alkylidene groups, and a specific example of such an alkylidene group is an ethylidene group. And a propylidene group and an isopropylidene group.

· · · [N] In the above formula [Π], p and q are 0 or a positive integer, and m and n are 0, 1 or 2.

R ′ to R each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

Here, the halogen atom is the same as the halogen atom in the above formula [I].

Examples of the hydrocarbon group usually include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms and an aromatic hydrocarbon group. More specifically,

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Can be mentioned. These archi The radical may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group and the like.

Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and the like. Specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenyl group. Enethylethyl group and the like can be mentioned.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Here, the carbon atom to which RQ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R it is bonded are directly or an alkyl group having ¹³ carbon atoms. They may be bonded via a len group. That is, when the two carbon atoms that are bonded via an alkylene Le emissions groups, R ^e and R ^'3 and ^power?, Or R'. And R '' and taken together with each other, methylate down group (- CH ₂ -), ethylene group (one CH _₂ CH ₂ -) or pro Pilet down group _{_{_{(- CH 2 CH 2 CH 2}}} -) of the Any alkylene group is formed.

Further, when n = m = 0, R 5 and R ₁₂ or R ′ ₅ and R ₁₉ may form a monocyclic or polycyclic aromatic ring together with each other. Specifically, the following aromatic rings formed by R and R ′ ² when n = m = 0 can be mentioned.

Here, q is the same as Q in equation [D].

As the cyclic olefin represented by the above formula [I] or [Π], specifically,

Bicyclo-2-heptene derivatives (Bicyclohept-2-ene derivatives), Tricyclo-3-decene derivatives, Tricyclo-3-3-decene derivatives, Tetra Cyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo_3-pentadecene derivative, pentacyclo B-3-Hexadecene derivative, pentacyclo-4-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo- 4-Jacosine derivative, heptacyclo-5-hexaneecocene derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentanecocene derivative, nonacyclo 1-Hexacoxene derivative, cyclopentagen-acenaphthylene addition 1,4-Methanol-1,1,4a, 9a-Tetrahydrofluorene derivative, 1,4-Methanol-1,1,4a, 5,10,10a-Hexahydroa And the like.

Specific examples of the cyclic olefin represented by the above formula [I] or [B] are shown below. Bicyclo [2.2.1] hept-2-ene

CHs 6-methylbicyclo

[2.2. 1] Hept-2-

CHs 5, 6-dimethylbicyclo CH ₃ [2.2.1] hept-2-ene

Trimethylbicyclo

[2.2. 1] Hept-2-

C2H5 6-Ethyl bincro

[2.2.1] Hept 2-ene n C4H9 6-n-butylbicyclo

[2.2. 1] hept-2-ene i C4H9 6-isobutylbicyclo

[2.2. 1] Hept-2-

CHs 7-methylbicyclo

[2.2. 1] hept-2-

Bicyclo [2.2.1] hept-2-ene derivatives Tricyclo

[4.3.0. 1 ² ' ⁵ ] -3-decene

2-methyltricyclo

[4.3.0. I ² · ⁵ ] -3-decene

5-methyltricyclo

[4.3.0. I ² · ⁵ ]-3-Decene

DOO such re cyclo [4.3.1 0.1 ^{^2-5]} - 3 - decene derivatives

Tricyclo

[4.4.0. 1 ² · ⁵ ] -3-Dendene

10-methizoletricyclo

[4.4.0. I ² · ⁵ ] -3- ゥ decene

Tricyclo [4.4. 0. 1 ² · ⁵ ] -3- 3-decene derivative Tetracyclo [4, 4.0.1 ² ^'5.1 ^7, ^10]

-3-dodecene

8-methyltetracyclo

[4.4.0. I ² ' ^5. Γ- ¹⁰ ] -3-dodecene

8-Ethyltetracyclo

C ₂ H ₅ [4.4.0. I ² · ^5. · ^Ι0 ] -3-dodecene

8-Propyltetracyclo

C ₃ H ₇ [4.4.0.1 ² · ^5. · ¹⁰ ] -3-dodecene

8-butyltetracyclo

C ₄ H _S [4.4.0. I ² · ⁵ · Γ ^{] 0} ] -3-dodecene

CH ₃ 8-isobutyltetracyclo

CH ₂ CH [4.4.0. I ² · ⁵ · Γ · ^Ι0 ] -3-dodecene

CH ₃ 8-hexyltetracyclo

[4.4.0. I ² · ^5. Γ · ¹⁰ ] —3—Dodecene

8-cyclohexyltetracycl ο

[4.4.0. I ² · ^5. · ^{, 0} ] -3-dodecene

8-stearyltetracyclo

C _J8 H ₃ 7 [4.4.0. I ² · Γ · ¹⁰ ] -3—Dodecene

5, 10-dimethyltetracyclo

[4.4.0.1 ² · I ⁷ · ^{, 0} ] -3-dodecene

2, 10-dimethinoletetracyclo

[4.4.0.1 ² · ^5. Γ · ^{, 0} ] -3-dodecene

8, 9-dimethyltetracyclo

[4.4.0. I ² · ⁵ · · ¹⁰ ] -3-Dodecene

In

CH ₃ CH:

9, 1 1, 1 2-tri methyl tetracyclo [4.4, 0.1 ² - ^5.1 ⁷ - ^10]

-3-Dodecene 9 - Echino 1 1, 12-dimethyl-tetra: cyclo [.. 4.4.0 1 ^{^2-5} 1 ⁷ ^'10]

- 3 - dodecene CH ₃ 9-Isobuchino 1 1, 12-CH dimethyl tetracyclododecene

CH ₃ [4.4.0. I ² · ^5. Γ · ^{, 0} ] —3—Dodecene

5, 8, 9, 10-tetramethyl

Tetracyclo

[4.4.0. I ² · ^5. Γ · ¹⁰ ] -3-dodecene

8-ethylidenetetracyclo

8 Echiriden-9-methyl-tetracyclo [4.4.0. 1 ² ^'5.1 ^{^7.2, 0]}

-3-dodecene

8 - Echiriden - 9 - Echirutetora cyclo [4.4.0 1 ^{^2-5} 1 ⁷ -.. ^10]

-3-Dodecene

8 - Echiriden - 9 -. I isopropyl tetracyclo [4.4.0 1 ² '. ⁵ 1 ^7']. ]

-3-dodecene

8 Echiriden - 9 - Puchirutetora cyclo [.. 4.4.0 1 ^{^2-5} 1 ^{^7-] 0]}

-3-dodecene

8-n-propylidenetetracyclocyclo [4.4.0. I ² · ^5. Γ · ¹⁰ ] and η and rl2

-3-dodecene

8-n-propylidene

-9-methyltetracyclo

I

[4.4.0. 1 ² · ^5. Γ · ¹⁰ ] —3-dodecene

8-n-propylidene

-9-Ethyltetracyclo

H2 then H3

[4.4.0. I ² · ^5. Γ · ¹⁰ ] —3-dodecene

8-n-propylidene-9-isopropyltetracyclo

[4.4.0. I ² ' ⁵ . 8 - n-propylidene-9 - Puchirutetora cyclo [. 4.4.0 1 ² '. ⁵ 1 ^7' ^10]

-3-dodecene cyclo

8-isopropylidene

-9-methyltetracyclo

[4.4.0. I ² · ⁵ · Γ · ^{, 0} ] —3—Dodecene

8-isopropylidene

-9-ethyltetracyclo

[4.4.0. 1 ² · ^5. · ^{, 0} ] -3-dodecene

8-Isopropylidene-9-Isopropyl tetracyclo

[4.4.0. 1 ² · ⁵ .. 1 ⁷ · ¹⁰ ] -3 -Dodecene

8 - Isopuropiriden - 9 - Buchirutetora cyclo ^{^{[.. 4.4.0 I 2 · 5}} Γ · 10]

-3-dodecene

8-bromotetracyclo

Br [4.4.0. I ² ' ^5. Γ · ^{, 0} ] -3-dodecene

8-fluorotetracyclo

F [4.4.0. I ² · ⁵ · · ¹⁰ ] -3-Dodecene

C £ 8, 9-Dichlorotetracyclo

C £ [4.4.0. I ² ' ^5. · ¹⁰ ] -3-dodecene

Tetracyclo such as [4.4.0. 1 ^{^2-5.} ''. ] -3-Dodecene derivative

^{^{[6.5.1. I 3 · 6 .0}} 2 · 7 .0 8 · 13]

-4- Pen Evening Desen

1,3-Dimethinonone cyclo

^{^{^{[6.5.1.1 3 '6 .0 2'}}} 0 3 · 13]

-4-pentadecene

1,6-Dimethinone cyclo

^{^{[6.5.1. I 3 · 6 .0}} 2 · 7 .0 3 · 13]

-4- Pen Evening Desen

14, 15-dimethyi cyclo

^{^{[6.5.1. I 3 · 6 .0}} 2 '7 .0 9 · 1]

-4- Pen Evening Desen

Pen, such as evening cyclo ^{^{[. 6.5.1 I 3 · 6 .0}} 2 · 7 .0 9 - 13] -4 - Pen evening decene derivatives; pentacyclo

^{^{^{[7.4.0.1 2 · 5. I 9}}} · 12 .0 8 · 13]

-3-Pentadecene 3-methyl

^{^{[7.4.0. I 2 · 5.}} Γ · 12 .0 8 · 13]

One three-pen evening decene

Pen, such as evening cyclo ^{^{[7.4.0. I 2 · 5 ·}} I 3 '12 .0 8 · 13] -3- pen evening decene derivatives

Bentacyclopentadecadiene compounds such as; 1 ⁹ - ^12.0 ⁸ - 'one

In

1 1-Methino pen cyclo

[8.4.0. 1 ^{^2-5.} 1 ³ · ^12.0 ⁸ - ^'3]

-3-hexadecene

1 1-Echino pentacyclo

^{^{[8.4. 0. I 2 · 5}} . I 3 · 12 .0 8 · 13]

-3-hexadecene

10, 1 1-Jimechino pen evening cyclo [8.4.0. 1 ^{^2-5.} 1 ⁹ - ^12.0 ⁸ - ^13]

3 to a pen such as Kisadesen evening cyclo ^{^{[8.4.0. I 2 · 5.}} I s '' 2 .0 8 ·, 3] one 3- to Kisadesen derivatives pen evening cyclo

[6.6. 1.1 ^{^3-6.0} ² 2.0 ⁹ - ^'4] to -4 Kisadesen

1,3-dimethylcyclo

^{^{[6.6. 1. 1 3 · s}} .0 2 · 0 3 · 14] to -4 Kisadesen

1,6-dicyclo

[6.6. 1. 1 ³ · ^6. Ο ² · 0 ⁹ · ' ⁴ ] -4-Hexadecene

CH ₃ CH _; 1 5, 16-Dimethizone cyclo

[6.6.3 1.1 ^{^3-6.0} ² 2.0 ⁹ - ^'4]

- evening pen such Kisadesen to 4 cyclo [6.6 1.1 ³ ^'6.0 ² 2.0 ^{^3-14.]} -4 to Kisadesen derivatives; to Kisashikuro

^{^{[6.6. 1. I 3 · 6}} . ° · 13 .0 2 · 7.

◦ 9 ・ 14] １ 4-Hebeu Desen

0 ² · ⁷ .

0 ^Ζ · ⁷ .

B

0 ² · ⁷ .

1, 6, 10-Trimethyi 12-isobutinoxacyclo [6.6.1

13. 6) 0.I 3 g 2.7 Q S. 1

- 4-heptene evening f Kisashikuro such decene ^{^{[. 6.6 1. I 3 · 6}} .1 10 · ] ^3.0 ^{^2-7.0} ⁹ ^{-, 4]} -4 to single-flop evening decene derivatives Hep Even Cyclo [8.7. 0. 1 ² ' ⁹ .

j 4. 7 j n. n Q 3. 8 G. 16 J

- 5-eicosene Cheb such evening cyclo - 5 - eicosene ^^ body;. Heptene evening cyclo [8.7.0 1 ^{^3.6.}

110.17 I 12.15 Q2.7 g 11.1

-4-eikosen [8.7.

Fart-flop, such as evening cyclo [8.7 0.1 ^{^3.6} 1 ¹⁰ ^'11 1] ² · ¹⁵ 0 ² - ^7.0 ¹¹ ^{-....] 6;} 4-eicosene derivatives;

Trimethyl ^^ Π

^{^{[8. 181.3.01.61 g 4 · 3. 7}} .8 Γ Q 1] · ]

2.

— 5-Hen Eikosen

Heptane cyclo-5-hetaneicosene derivatives such as CH ₃ CH ₃ 42 · ⁷ 1.71 Γ ¹ · ¹⁸

15-methyloctacyclo

[8 1. 3.

138 ..] ^{60. QI 3. 2 -. 8 0} I 1 4 2 · 7 1.7 ^One-18 -5 - docosenoic

15-Echilok Even Cyclo

^{[8 1.138..160. QI 3. 2 ·} 8 3. QII 2. · 7 1.7Ί Γ '· 18

-5-Dosen

Okutashikuro such ^{[.... 8.8.0 I 2} · 9 I 4 · 7 1 · 18 I 13 '16 .0 3' 8 .0 12 - 17] -5 - docosenoic derivatives;

. 1

]

-5-Pen Yu Kosen

5 pen evening Nonashikuro such directrix [10.9 1.1 ^{^4.7} 1 ¹³ -... ²⁰ 1 ¹⁵ ^{-] 8.0} ^{^2-10.0} ^{^{^3-8.0]} 2} -. ²¹ 0 · ^19] Nonacyclo [10.10.

In

Nonashikuro such ^{[1 0. 1 0. 1. 1 5} · 8 1 "· 2 '1 16 -..... 19 ο 2 · η ο · ο 13 · 22 o, s - 20] -6 - to Kisakosen syrup:

And furthermore,

5-phenino bicyclo

[2.2.1] Hept-2-en

5-Metino 5-Feniso

[2.2.1] Hept-2-

5-Penzino bicyclo

[2.2.1] Hept-2-en

5-trino bicyclo

[2.2.1] Hebut-2-en

5- (ethylfurenyl) -bicyclo [2.2.1] hept-2-ene

I

5- (isopropylphenyl)-

Bicyclo [2.2. 1] hept-2-ene 5- (biphenyl) -bicyclo

[2L 1] hept-2-ene

5-Naphtinole) -bicyclo [2 «1] hept-2-ene

5- (Hy-naphthyl) -bicyclo [2 · 1] hept-2-ene

5-(Anthracenyl)-Bisik mouth [2.1] hept-2-ene

5, 6-Dipheniso Bincro

[1] Hept-2-en

Cyclopen Even Gen-acenaphthylene animal

1,4-methano-1,4,4a »9a-tetrahydrofluorene

Ten

1,4-methano-1,4,4a, 5,10,10a

-Hexahydroanthracene

B

2 ' ⁵ .

8- (Echirufuwe sulfonyl) - tetracyclo ^{^{[4 0. 1 2 '. 5}} CH3 Γ', 0] -3- dodecene

8- (isopropyl phenylpropyl) - tetracyclo ^{^{[4 4 0. 1 2 · 5}} Γ '.. ]-3-Dodecene

8, 9 Jifuwenino tetracyclo [440.1 ² ¹⁰ ^'5.'] -3 - dodecene

8- (biphenyl) -tetracyclo [440.1 ² · ⁵ .Γ · ¹⁰ ] -3 -dodecene

8- (yS-naphthyl) -tetracyclo [0.1 ² ' ^5. · ^Ι0 ] -3-dodecene

8- (a-naphthyl) -tetracyclo [440.1 ² · ^5. · ¹⁰ ]-3-dodecene

8-(Rontrathenyl)-Tetracyclo [440.1 ² ' ^5. I ⁷ · ^I0 -Dodecene

Asenaphthylene

Further addition ^ ^

11, 12-benzo - Pen'yu cyclo ^{^{^{[6.5.1.1 3 · 6 .0 2 '}}} 7 .0 9 ·' 3] - 4- pen evening decene

11, 12 - base down zone - pentacyclo ^{^{^{[6.6.1.1 3 · 6 .0 2 '}}} 7 .0 9' 1] to -4 Kisadesen

To 11-Fuenino Kisashikuro ^{^{^{[6.6.1.1 3 · Μ 10 · 13}}} .0 2 · 7

.0 ⁹ · ¹⁴ ] -4-Heptadecene

14, 15-benzo - heptene evening cyclo ^{^{^{[8.7.0.1 2 · Μ 4 · 7}}} .1 17 .0 3 '8

.0 ¹² · ¹⁶ ] -5—Eikosen

The cyclic olefin-based random copolymer is a copolymer of ethylene and the above-mentioned cyclic olefin, for example, in a hydrocarbon medium or at least at a reaction temperature in a liquid cyclic olefin. A catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound (A), or a group IV or lanthanide transition metal compound containing a ligand having a cyclopentagenenyl skeleton and an organoaluminum It can be produced by polymerization in the presence of a catalyst (B) comprising a dimethyloxy compound and, if necessary, an organic aluminum compound.

The yo Ri Specifically, for example, in hexane medium in the consequent b using a continuous polymerization apparatus, Te preparative Rashiku b by an annular O reflex Lee emissions ^{^{_{[4.4.0 I 2 '5, 10}}} ..] - 3 - have use dodecene (hereinafter TCD-3 that there is a this abbreviated), catalyst and to V_〇 _{_{(OCH 2 CH 3) C 1}} 2 / a 1 (CH 2 CH 3) uC l ^ used, reaction Temperature l Ot: Reaction time (polymerization reaction residence time) Ethylene • TCD-3 random copolymer can be produced by polymerizing ethylene and TCD-3 in 30 minutes.

The cyclic olefin-based random copolymer, which is a copolymer of cyclic olefin and ethylene as described above, is a repeating unit derived from ethylene and a cyclic unit derived from the cyclic olefin. The repeating unit to be used is an essential constituent unit. Force derived from ethylene and other monomers copolymerizable with the cyclic olefin as long as the properties of the obtained copolymer are not impaired. May be provided.

Examples of such other monomers include ethylene and other olefins other than the above-mentioned cyclic olefins.

Propylene, 1—butene, 1 pentene, 1-hexene. Ten-, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4 , 4-Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decen, 1-dodecene, 1-tetra Radene, 1-hexadecene, 1-octadecene, and 1-coycosene, etc.

Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene And cycloaffins such as 3a, 5, 6, 7a-tetrahydro—4,7-methano-1H-indene,

2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene, 5-n-butyl-2-norbornene, 5-isobutyl Norbornenes such as i-norbornene, 5, 6-dimethyl-2-norbornene, and 5-octorone 2-norbornene and 5-fluoro-2-norbornene;

1,4-hexagene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentagen, 5-ethylidene Non-conjugated gens such as 2-norbornene and 5-vinyl-2-norbornene.

These other monomers can be used alone or in combination of two or more.

Cyclic olefin-based random copolymers can be used as other monomers as described above.

- a structural unit derived from, usually 2 0 mol% or less, is preferred properly has an amount of 1 0 mole ^_0/0 or less. A polymerization method itself for producing a cyclic olefin-based random copolymer and a catalyst to be used have already been filed, and this copolymer is disclosed in, for example, JP-A-60-168 7 08, 6 1 — 1 2 0 8 16 6, 6 1 — 1 1 5 9 12 2, 6 1 — 1 1 5 9 1 6, 6 1 — 2 7 1 3 0 Nos. 8 and 6 1-2 7 2 2 16

To be manufactured by selecting appropriate conditions in accordance with the method proposed by the applicant in each specification etc. of Japanese Patent Application Nos. 61-9595 and 61-9596. Can be.

In such a cyclic olefin-based random copolymer, the cyclic olefin represented by the formula [I] or [π] has a structure represented by the following formula [πι] or [IV]. O is thought to form a repeating unit.

… [ΙΠ]

In the above formula [m], R ′ to R, R ·> to Rb, _m , n and q are the same as defined in the above formula [I].

· · · [IV]

In the above formula [IV], R ′ to R ¹⁹ , m, n, p and q are the same as defined in the above formula [π].

The content of fine particles having a particle size of 1 μm or more in the cyclic olefin-based random copolymer immediately after copolymerization, which is insoluble in hexane, is about 600 particles / lOOmg, which is extremely small. Does not affect the compact. Therefore, the cyclic olefin-based random copolymer immediately after the reaction does not substantially contain fine particles of a cyclohexane-insoluble cyclic olefin-based random copolymer having a particle diameter of 1 μm or more.

When the cyclic ortho-random copolymer copolymer pellet according to the present invention is melt-extruded from the extruder and pelletized to form the above-mentioned cyclic ortho-random copolymer copolymer pellet, Pellet toy with no force applied, and if necessary, a pellet-forming hexane-insoluble cyclic olefin system with a particle size of 1 μm or less. La It can be manufactured by filtering and removing fine particles of a random copolymer (hereinafter sometimes referred to as “cyclohexane-insoluble fine particles”) using a polymer filter installed at the outlet of the extruder. More specifically, for example, the copolymer powder or a concentrated solution of the copolymer is pre-heated to a temperature equal to or higher than the glass transition temperature (T g) of the copolymer and melted from an extruder. It can be manufactured by extruding, passing through a polymer filter made of a metal nonwoven fabric, and cutting with a pelletizer. At this time, as a method of reducing the number of insoluble fine particles in the extruder, for example, the copolymer powder or the concentrated solution of the copolymer to be sent to the extruder is preliminarily subjected to a glass transition temperature ( T g) Method to heat to near temperature, Method to keep the extruder vent temperature sufficiently high, Polymer filter to improve the filtration efficiency of polymer filter There is a method of filtering and extruding under conditions that do not make the pressure difference (differential pressure) before and after too large. o

That is, as described above, the cyclohexane-insoluble fine particles having a particle size of 1 yum or less contained in the cyclic olefin-based random copolymer pellets according to the present invention are obtained by the cyclic olefin-based particles obtained from the polymerization step. These insoluble fine particles are hardly contained in the random copolymer, and these insoluble fine particles are used when the cyclic olefin random copolymer powder produced in the polymerization step is melted and formed into pellets. It is considered that excessive shear stress is applied to the polymer, and fine powder generated when the cyclic olefin-based random copolymer pellet is dried or mixed is generated. Therefore, the cyclic olefin-based random copolymer obtained from the polymerization process No ,. Conditions were adopted so that excessive shear stress would not be applied to the cyclic copolymer based random copolymer when pelletizing the powder, and the generated insoluble fine particles were removed by a polymer filter or the like. In addition, by operating the copolymer pellets such that fine powder is not generated when the copolymer pellets are dried or mixed, cyclic cyclic random copolymer pellets can be obtained. Or the number of insoluble fine particles contained in a molded article produced from the pellet can be reduced.

Hereinafter, a method for producing the cyclic olefin-based random copolymer pellet according to the present invention as outlined above will be specifically described.

For example, from a reaction solution (copolymer solution) containing a cyclic olefin-based random copolymer obtained from the polymerization step as described above, as shown in FIG. Through the steps of precipitation filtration, extraction filtration, drying, blending of a stabilizer and the like, a cyclic copolymer random copolymer powder is prepared.

Demineralization is a process that removes the catalyst dissolved in the copolymer solution. That is, after performing the polymerization reaction as described above, the copolymer solution in which the cyclic olefin-based random copolymer is dissolved is withdrawn from the reactor and deashed.

In this step, hot water and a pH adjuster are added to the extracted copolymer solution. As the pH adjuster added here, for example, an aqueous solution of sodium hydroxide having a concentration of about 1 to 40% by weight is used. By adding the hot water and the pH adjuster in this way, the copolymerization reaction is stopped and the catalyst dissolved in the copolymer solution is pumped to the hot water side. Oil-water separation of the hot water and the copolymer solution to which the catalyst has been transferred By removing the phase, the catalyst is removed from the cyclic olefin-based copolymer.

The copolymer solution from which the catalyst has been removed through the deashing step is filtered again to remove any remaining impurities.

The cyclic olefin-based random copolymer is dissolved in the copolymer solution thus filtered. By adding a precipitation solvent to this copolymer solution, a dissolved cyclic olefin-based random copolymer can be precipitated. The precipitation solvent used here is a poor solvent for the cyclic olefin-based random copolymer, and usually, ketones such as acetate are used. The precipitation solvent is usually introduced into a precipitation drum provided with a stirrer and a baffle plate, and mixed with the copolymer solution under stirring in the precipitation drum.

The cyclic olefin-based random copolymer precipitated by adding the precipitation solvent is separated from the solvent as a wet cake.

The separated wet cake contains a small amount of impurities such as unreacted monomers, which are mainly cyclic olefin-based random copolymers. Therefore, the wet cake is removed again to remove these impurities. Disperse in a poor solvent (extraction solvent) for cyclic olefin-based random copolymers such as acetone to elute impurities contained in the wet cake into the extraction solvent.

After eluting impurities such as unreacted monomers, the extraction solvent is removed. For the removal of the extraction solvent, methods such as filtration and centrifugation can be used.

Even if the extraction solvent is removed as described above, the copolymer remains in a small amount of solvent. Therefore, the cyclic olefin-based random copolymer purified through the extraction step is still generally obtained as a diet cake.

Therefore, such a wet cake is usually subjected to a drying step to remove the solvent. In this drying step, the normal pressure drying step and the vacuum drying step can be combined. A general atmospheric drying step is performed using an atmospheric dryer in which the wet cake is heated to a temperature of 100 to 190 ° C. The drying time in the normal pressure drying step is usually 5 to 60 minutes.

In addition, the vacuum drying step is usually performed using a vacuum dryer in which the final pressure is reduced to 1 to 3 OTorr and heated to 100 to 190 ° C. The drying time in this vacuum drying step is usually 1 to 4 hours.

By passing through the drying step in this manner, a cyclic olefin-based random copolymer powder can be obtained.

For example, the softening temperature (TMA) of the cyclic olefin-based random copolymer generally obtained as a powder as described above is 70 ° C. or higher, preferably 70 to 70 ° C. It is in the range of 250 ° C, particularly preferably between 80 and 200 ° C, and more preferably between 90 and 180 ° C. In the present invention, the softening temperature (TMA) was measured based on the thermal deformation behavior of a sample molded into a sheet having a thickness of 1 m using a Thermo Mechanical Analyzer manufactured by DuPont. That is, a quartz needle is placed on the sheet, a load of 49 g is applied to the quartz needle, the temperature is raised at 5 ° C / min, and the temperature at which the needle enters 0.635 mmi $ is set to the softening temperature (TMA ).

In addition, this cyclic copolymer random copolymer The intrinsic viscosity [] measured in decalin at ° C is usually between 0.01 and 5 dl / g, preferably between 0.1 and 3 dl / g, particularly preferably between 0.2 and 3 dl / g. It is in the range of 2.5 dl / g. The glass transition temperature (T g) of the cyclic olefin-based random copolymer is usually 60 to 230 ° C., preferably

It ranges from 70 to 190.

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

Before supplying the cyclic olefin-based random copolymer powder thus obtained to the extruder, a stabilizer is usually blended.

In the cyclic olefin-based random copolymer powder obtained through the drying step as described above, since the reaction solvent, the precipitation solvent, the extraction solvent, and the like are almost completely removed in the drying step, the solvent is substantially removed. Does not contain. A first method for producing the cyclic olefin-based random copolymer pellet of the present invention is a cyclic olefin-based random copolymer powder substantially free of such a solvent. Before it is fed to the extruder, at a temperature of at least 50 ° C, preferably at least 80 ° C, and more preferably

Heat to a temperature of at least 80 ° C and below the thermal decomposition temperature of this copolymer. Therefore, in this first method, the cyclic olefin-based random copolymer is supplied to the extruder as a heated powder, or supplied to the extruder at least partially in a molten state. Sometimes.

The cyclic orphan-based random copolymer is equipped with a jacket or coil outside the container such as a hopper, silo or drum, and a device that heats by passing a heat medium through this jacket or coil. Use It can be heated to a predetermined temperature by a method, a method in which an induction heater or an electric heater is attached to a container, and a direct heating method is used. When a ring-shaped random copolymer is accommodated in a container and heated in this way, paddle blades and ribbon blades are placed in the container to increase the efficiency of heat conduction in the container. It is preferable to install a stirring blade such as a screw shaft, a rotating shaft to which a rod or a pin is attached, and heat while stirring. Further, by rotating or vibrating the container itself, the cyclic olefin-based random copolymer accommodated therein may be stirred.

Further, the copolymer can be heated by directly blowing a gas such as air or nitrogen gas or water vapor into the cyclic olefin-based random copolymer accommodated in the container. In addition, infrared rays, microwaves, and the like can be used for this heating.

Further, in the first method of the present invention, the cyclic olefin-based random copolymer is dissolved or suspended in, for example, a hydrocarbon-based solvent or a polar solvent such as an alcohol or a ketone. Turbidity, and flushing this solution or suspension while heating it in a heat exchanger such as a double tube heat exchanger, polycyclic heat exchanger, or plate heat exchanger. A method of heating while removing the solvent, a method of vaporizing and removing the solvent by using a thin film evaporator, and obtaining a preheated copolymer can be used. However, when these heat exchangers and thin film evaporators are used, it is necessary to impart sufficient heat so that the solvent is completely vaporized and the obtained copolymer is heated to a predetermined temperature. .

In the first method of the present invention, for example, the cyclic olefin-based random copolymer heated to a predetermined temperature as described above is supplied to an extruder. Manufacture pellets.

As the extruder used in this method, a known single-screw extruder, twin-screw co-directional extruder, twin-screw different-direction extruder, planetary screw extruder, or the like can be used.

FIG. 2 shows an example of an extruder used in the present invention.

As shown in FIG. 2, an extruder that can be used in the present invention includes a cylinder 1 having a resin discharge port 4 at a front end and a hopper 5 at a rear end, and a motor 3 in the cylinder 1. It has a screw 2 that rotates by power. A vent 6 is provided near the center of the cylinder 11, and the vent 6 allows the vaporized components in the cylinder 1 to be discharged. A spiral is formed in the screw 2, and the number of threads of this screw is usually one to three.

The cylinder 11 of the extruder is provided with temperature adjusting means 7 and 7a for controlling the temperature of the supplied copolymer powder by heating or cooling. The temperature adjusting means 7 and 7a include an adjusting means including an electric heater and a cold water pipe, an adjusting means for providing a drill hole and allowing a heating medium to flow therethrough to adjust the temperature, and an outer wall of the cylinder. An adjustment means for attaching a jacket to the jacket and flowing the heat medium through the jacket, an induction heater, and the like can be used.

In FIG. 2, the temperature adjusting means indicated by 7 is usually a heating means, and the temperature adjusting means indicated by 7a is a temperature adjusting means that can be used for both heating and cooling.

An extruder having the above structure is shown in FIG. 2, for example. As shown in the figure, the supply section where the copolymer is charged, the melting section where the supplied copolymer is heated and melted, the vent where the bent is formed, and the copolymer that has passed through the bent section in a molten state are compressed. It can be divided into a compression section that performs compression and a measurement section that extrudes resin to the discharge port. In addition, a resin outlet is formed in the tip direction of the measuring section, and the copolymer discharged in a molten state from the resin outlet is usually pelletized after passing through a polymer filter.

In the first method of the present invention, a cyclic olefin-based random copolymer heated to a predetermined temperature in advance is supplied from a hopper 5 into a cylinder 1 of an extruder. The cyclic olefin-based random copolymer supplied into the cylinder 1 reaches the vent portion by the heat from the heating means 7 while advancing as the screw 2 rotates. Most of them are in a molten state before they are melted. Therefore, in the compression section where the most shear stress is applied, the cyclic cyclic olefin-based random copolymer in the molten state moves in the direction of the resin outlet 4 with almost no shear stress, and hexane-insoluble fine particles are generated at the outlet. Difficult to read. That is, when a general resin is supplied to an extruder to produce a pellet, the resin supplied to the extruder is generated by heat from the heating means 7, screw 2 and resin. The resin is brought into a molten state by utilizing the shear heat generated by the shearing force applied to the resin by contact. In this way, when the cyclic olefin random copolymer is melted using shear insulation, the viscosity decreases and the fluidity becomes better when the copolymer transitions from the solid state to the molten state. In the meantime, a considerable shear stress is applied to this copolymer, and it is considered that cyclohexane-insoluble fine particles are formed and become weak. In the present invention, in consideration of the specialty of the cyclic olefin-based random copolymer, the cyclic olefin-based random copolymer is heated to a predetermined temperature and supplied to the extruder. Is melted, and the subsequent bent, compression, and metering sections are supplied with the cyclic-refined random copolymer in a state where the fluidity is high and shear stress is not easily applied. By doing so, the generation of fine particles insoluble in hexane is effectively suppressed.

The first production method is a method of heating a powdery cyclic olefin-based random copolymer obtained through a drying step to a predetermined temperature and supplying the same to an extruder. In the production method, a solution or dispersion containing a cyclic olefin-based random copolymer containing a solvent before passing through a drying step may be used instead of the above-mentioned copolymer powder.

In other words, in this method, as shown in Fig. 1, for example, the catalyst is removed in the decalcification step of the polymerization step, the decalcification step, the filtration step, the precipitation and filtration step, the extraction filtration step, the drying step, and the stabilizer compounding step. The copolymer solution after the filtration, the copolymer dispersion after the precipitation filtration step, the copolymer dispersion after the extraction filtration step, or removal of a part of the solvent from these dispersion liquids. You can use any of the cakes obtained by

Although the cyclic olefin-based random copolymer obtained through the above-mentioned steps contains a considerable amount of a solvent, in the present invention, the copolymer is heated to 50 ° without passing through a drying step. C or higher, preferably 80 ° C or higher, and more preferably from 80 ° C to a temperature lower than the thermal decomposition temperature of the copolymer. Heat and feed to extruder. It is preferable to supply the extruder with the amount of solvent remaining in the jet cake at the stage of being supplied to the extruder being 2% by weight or less.

For example, a case where a cyclic olefin random copolymer solution obtained through a demineralization process is used will be described as an example. At this stage, a cyclic olefin random copolymer is used. The coalescing is performed with aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, kerosene or the like, or their nitrogen derivatives; cyclohexane, methylcyclopentane And alicyclic hydrocarbons such as methylcyclohexane or halogen derivatives thereof; aromatic hydrocarbons such as benzene, toluene, xylene, and halogen derivatives such as black benzene. It is dissolved or dispersed in a hydrocarbon solvent or a mixed solvent of these.

In this method, it is preferable that a solvent or a dispersion medium is removed from the above-described copolymer solution or dispersion so as to be 20% by weight or less of the copolymer weight and supplied to an extruder.

To remove the solvent or the dispersion medium, the copolymer solution or dispersion is heated to flash, so that the content of the solution with respect to the cyclic olefin-based random copolymer is 20% by weight. % Or less, and by adding a poor solvent for the cyclic olefin random copolymer to the copolymer solution or dispersion, the cyclic olefin random copolymer can be obtained. A method can be adopted in which the solvent concentration is reduced to 20% by weight or less by precipitating the union and performing phase separation. At this time, in order to adjust the solvent concentration to 2 0 weight ^_0/0 or less, centrifugation may be performed an operation such as filtration. The thus obtained cyclic solvent containing a solvent in an amount of not more than 20% by weight The orphan-based random copolymer is a so-called wet cake, and the wet cake is preliminarily heated to a temperature of 5 (TC or more and supplied directly to an extruder. In the case of preheating in a solution state, a double-tube type or a multi-tube type can be used in addition to the above-mentioned method. It is also possible to use a heat exchanger with a set of static mixers or a plate-type heat exchanger, and the method of flashing to remove the solvent can be used for flashing. By setting the temperature to a high value, the temperature of the wet cake can be raised to 50 ° C or higher without any special heating step. Contains a small amount of cyclic olefin monomer There is also a call that is.

The pre-heated cyclic olefin-based random copolymer jet cake is supplied to an extruder and pelletized as in the case of the above-described powder.

However, when extruding using a wet cake containing a solvent as described above, it is necessary to remove the solvent in the extruder, so a vent is provided in the extruder. In this case, it is preferable that the vent installed has a high solvent removal efficiency, and a multistage vent or a vacuum vent is preferable.

The above is a method using a solution or a dispersion after the demineralization step, but the same operation can be performed in the case of using a dispersion obtained through a precipitation filtration step or an extraction filtration step.

In addition, it is preferable that a stabilizer is added to the cake at any stage before it is supplied to the extruder. In the second method of the present invention, the temperature of the cylinder at the melting portion starting point 8 where the heating of the copolymer supplied to the cylinder 1 from the hobber 5 which is the supply section of the extruder is started is supplied. This is a method in which pelletization is performed at a temperature 90 ° C or more higher than the glass transition temperature (Tg) of the copolymer obtained, and the temperature is raised from 110 ° C higher than Tg. It is preferable to set the temperature within a range of 10 ° C lower than the thermal decomposition temperature of the copolymer.

Furthermore, in this method, the temperature of the cylinder at the beginning of the melting section is higher than that of the other parts of the extruder, that is, the supply, vent, compression, and metering sections. It needs to be set high.

Here, the melting portion start end 8 is the vicinity of the portion where heat transfer from the heating means 7 to the copolymer supplied from the hopper 5 into the cylinder 1 starts, and usually, Means near the base end of the heating means 7 on the hopper 5 side.

By setting the temperature of the cylinder 1 as described above, the copolymer supplied into the extruder quickly becomes a molten state, so that even if the screw 12 is rotated, Excessive shear stress is not applied to the copolymer, and fine particles insoluble in hexane are unlikely to be formed in this extruder.

Further, in the present invention, the screw rotation speed of the extruder is within a range in which the supplied powder is completely melted at the bent portion, and is expressed as a specific energy of 0.05. It is preferable to set within the range of ~ 0.15 kwh / kg. That is, it is preferable to increase the throughput of the cyclic olefin-based random copolymer with respect to the screen rotation speed. The first method and the second method are performed using a general extruder. Force can and Hodokosuru This ^s, two of the disk Li Yu when using the twin screw extruder rather it may also be in mesh with each other, also engaged though rather than a Yore also, and these two The screw is rotated by the motor ⁵ ', and the two screws can be rotated in the same direction or in different directions.

However, when a twin-screw extruder is used, the generation of insoluble fine particles can be effectively suppressed by setting the rotation directions of the two screws to the same direction.

That is, in the third production method of the present invention, a twin-screw extruder having two screws rotating in the same direction is used.

FIG. 3 shows an example of a twin-screw extruder used in the third method of the present invention. As shown in FIG. 3, the twin-screw extruder used in the third method of the present invention has a resin outlet 14 at the front end and a hub 15 at the rear end. The cylinder 11 is provided with two screws 12a and 12b which rotate in the cylinder 11 by the power of a motor 13 and the like. In the twin-screw extruder, the two screws 12a and 12b are connected to the motor 13 so as to rotate in the same direction. When the screws 12a and 12b rotate in the same direction, the shear stress applied to the cyclic olefin-based random copolymer is reduced, and the cyclohexane is reduced. Generation of insoluble cyclic olefin-based random copolymer fine particles is suppressed.

The disk re-menu for this Yo I Do twin-force ^s the number of threads is that there is 1 to Article 3, a twin-screw extruder having a disk Li Interview one 1 Article or Article 2 in the present invention It is preferable to use it. Such a number of screens By using this, it is possible to reduce the shear stress applied to the cyclic olefin-based random copolymer.

Also, as shown in Fig. 4, these two screws are arranged so that the groove of one screw and the mountain of the other screw enter and join each other. This is preferred. By arranging the two screws in this way, it is possible to reduce the shear stress applied to the cyclic olefin-based random copolymer.

In the present invention, the specific power of the screw is preferably in the range of 0.05 to 0.15 kwh / kg. The groove depth is preferably a deep groove. When the depth of the groove is (h) and the diameter of the screw is (D), h / D is in the range of 0.16 to 0.19. By doing so, it is possible to more efficiently suppress the generation of cyclohexane-insoluble cyclic olefin-based random copolymer fine particles. Here, the value of h / D is calculated from the groove depth h and the screw diameter D expressed by using the same unit.

Et al. Is, in general to disk Li Yu twenty-one di Nguburo click and mouth first mixing segmenting door is also the often is provided with the power ^s of Turn-like, mixed and Gume Do you Yo of this in the present invention It is preferable to use a screw that does not have any hardware.

In the twin-screw extruder as described above, the cyclic olefin-based random copolymer is introduced from the hopper 15 to the supply part of the cylinder 11. The copolymer introduced into the supply section is transferred to the melting section with the rotation of the screws 12a and 12b rotating in the same direction. In particular, in the present invention, it is preferable to heat the cyclic ordinary random copolymer to a temperature of 50 ° C. or more and introduce it into a twin-screw extruder. In addition, the copolymer was heated to 80 ° C. It is preferable to heat as described above, and it is particularly preferable to heat the copolymer to a temperature from 80 ° C. to a temperature lower than the decomposition temperature of the copolymer.

A heating means 17 is provided in the cylinder 11 of the melting part of the twin-screw extruder used in the present invention. As the heating means, specifically, a heating means including an electric heater or a cold water pipe, a heating means for providing a drill hole and allowing a heating medium to flow through the inside thereof to adjust the temperature, and an outer wall of the cylinder It is possible to use a heating means for mounting a jacket on the top and allowing a heat medium to flow through the jacket, an induction heater, or the like. The copolymer transferred to the melting section is heated by the heating means to be in a molten state.

The copolymer in the molten state is discharged from the resin outlet through the bent portion, the compression portion, and the measurement portion.

As described above, the cyclic olefin-based random copolymer extruded in a molten state from an extruder such as a single-screw extruder or a twin-screw extruder is disposed at the tip of a nozzle of the extruder. Filtered through a polymer filter. The fourth production method of the present invention is characterized in that the difference in pressure applied to the molten cyclic copolymer before and after the polymer filter when the molten cyclic olefin-based random copolymer passes through the polymer filter (difference). The pressure should be below 90 kg / crf, preferably below 80 kg / erf, more preferably between 5 and 60 kg / erf.

As the polymer filter used here, a filter conventionally used for filtering a molten resin can be used. Specifically, a filter formed from a filter material such as a metal nonwoven fabric, a metal sintered body, a metal wire mesh, or a metal wire mesh is exemplified. I can do it. In addition, examples of the format of the polymer filter include a disk type, a tube type, and a pre-type. Et al is, in the material of the filter medium to form a poly Murph I filter one, SUS 3 04, SUS 3 1 6, SUS 3 1 6 L N Hastelloy, Inconel, nickel, Carpenter and titanium down like Can be mentioned.

The nominal diameter of the polymer filter is usually in the range of 1 to 200 m, preferably l to 150 u m, more preferably l to 70 m. Such a polymer filter is disposed at the tip of the nozzle of the extruder. In addition, one polymer filter can be disposed at the tip of the nozzle, or a plurality of filters can be disposed.

The temperature of the polymer filter when the molten cyclic olefin random copolymer passes through the polymer filter is usually the glass transition of the cyclic olefin random copolymer. Temperature (Tg) + 100 ° C to Tg + 250 ° C, preferably Tg + 110 ° C to Tg + 200t: and more preferably T g + 130: Set to a temperature within the range of Tg + 160 ° C.

The cylinder temperature of the extruder at this time is usually Tg + 50: to Tg + 250 ° (:, preferably, Tg + 70t: to Tg + 20). 0 ° C, more preferably within the range of Tg + 80t: ~ Tg + 160 ° C. Both the cyclic olefin-based random melted as described above are used. By allowing the polymer to pass through the polymer filter at a predetermined differential pressure, insoluble fine particles can be efficiently removed, and when the copolymer passes through the polymer filter. Do not apply excessive shear stress to the copolymer Thus, no new insoluble fine particles are formed in the copolymer when passing through the polymer filter.

The cyclic olefin-based random copolymer filtered by the polymer filter as described above is then shaped into a predetermined shape to produce pellets.

There is no particular limitation on the shape and size of the thus obtained copolymer pellets, and the pellets can be formed into various shapes and sizes.

In general, the copolymer pellet thus obtained is put into water and cooled, and therefore, moisture is attached to this pellet. Therefore, in order to remove the water, the obtained copolymer pellet is generally dried, and sometimes the pellet is mixed.

In the fifth production method of the present invention, the cyclic ortho-random copolymer is pelletized, and then the obtained pellet is dried and / or mixed to obtain the cyclic ortho-random copolymer. During the production of pellets, when drying and / or mixing, fine powders generated from cyclic olefin-based random copolymer pellets (such as abrasion powder of pellets or fragments of crushed pellets). ) Is dried and / or mixed under mild conditions so that the amount is less than 100 ppm. In particular, in the fifth method, it is preferable to dry and / or mix the pellet so that the fine powder is 60 ppm or less, and further preferably to 20 ppm or less. It is particularly preferred to dry and / or mix the pellets first.

Cyclic olefin random copolymer pellets produced by the present invention The weight of each pellet is usually about 0.01 to 0.03 g, and in the present invention, the fine particles generated during drying and / or mixing are 1% of the weight of this pellet. It means particles with a weight of less than / 5, preferably less than 1/10, and more preferably less than 1/20.

In the fifth method of the present invention, examples of the apparatus used for drying and / or mixing the pellets include a known powder drying apparatus and a known powder apparatus. Specifically, the rotation axis is horizontally arranged with respect to a horizontal cylindrical container, an inclined cylindrical container, a V-shaped container, a double cone container, a cubic container, an S-shaped container, or a continuous V-shaped container. A container rotating type device for placing and rotating a container can be cited. In this container rotating type device, the rotating shaft may be provided with stirring blades or the like. Further, in the fifth method of the present invention, a stirrer such as a ribbon, a screw or a conical screw, a rotating shaft equipped with a rod or a pin, a screw, a needle, a disk, or the like is provided in a container. Vertically or horizontally mounted, mechanical stirring type device that rotates this stirrer, device that flows and stirs by passing air through the container, pneumatic transport device, etc., pulls out the pellet from the container, returns it to the container again, circulates it and mixes it. It is also possible to use a device that performs such operations. Further, in the fifth method of the present invention, a static mixer device used for free-falling the pellet from the upper portion of the container by gravity, or a device for simultaneously dropping the pellet from various parts of the container and stirring and mixing. Etc. can also be used.

These devices may include a vacuum device for drying the pellet, a device for blowing gas such as air or nitrogen into the container, and a heating device using a jacket or a coil or a heating medium. . In the fifth method of the present invention, when the pellets are dried and / or mixed by using the above-described pellet drying and / or mixing apparatus, the cyclic-olefin random copolymer is used. In order to reduce the amount of fine particles generated from the coalesced pellets to 100 ppm or less, for example, when rotating the container, reduce the rotation speed of the container as much as possible, and the pellet in the container The force must be such that it does not collide with the inner wall, or the pellets do not collide with each other. When stirring with a stirrer, the stirring speed should be as low as possible to prevent excessive shear stress from being applied to the pellet when the stirrer comes into contact with the pellet. The gap between the inner wall and the inner wall is made as wide as possible, so that the pellet is not caught in the gap and the shearing stress is not applied to this pellet by the rotation of the stirring blade. In addition, the surface area of the stirring blade should be made as small as possible so that the pellet does not rub against the surface of the stirring blade or the inner wall surface of the vessel with strong force, or the shape of the stirring blade should be rounded. If the pellet is in contact with the agitating blade, it can be quickly escaping from the blade surface if it is attached or given an appropriate angle.

Among these methods, for example, when using a vessel equipped with a vertical ribbon-type stirrer, the helical angle of the ribbon is set so that the pellet is lowered toward the bottom of the vessel by stirring. It is preferable to set this angle so that it is scraped up toward the top of the container, rather than upright. When the angle is such that the pellet is pushed down, a large pressure is generated to push the pellet into the bottom of the container, and excessive shear stress is applied to the pellet.

In addition, the pellets may be agitated by airflow, or the pellets may be If the pellets are circulated and agitated by feeding, etc., or dropped freely by gravity, reduce the air flow speed or pellet transport speed as much as possible so that the pellets Avoid high-speed contact with the steel and reduce the shear stress on the pellet as much as possible.

Furthermore, the amount of pellets charged into the container should be as small as possible so that the pressure generated by the weight of the pellet does not apply excessive shearing stress to the pellet at the bottom of the container. It is preferable to do so.

It is also preferable to increase the smoothness of the inner wall surface of the vessel and the surface of the stirring blade as much as possible. Specifically, the inner wall surface of the vessel and the surface of the stirring blade are preferably polished with a puff of 200 or more, more preferably with a puff of 300 or more, and particularly preferably electrolytic polishing. It is preferable to make the inner wall surface of the vessel and the surface of the stirring blade smoother, reduce the coefficient of friction between the wall surface and the blade surface when the pellet comes into contact, and reduce the shear stress applied to the pellet. Sile,.

The cyclic olefin-based random copolymer pellets of the present invention can be produced by employing the above-described first to fifth methods alone, and these methods can be arbitrarily combined. Pellets can also be manufactured.

The sixth manufacturing method of the present invention is the most preferable manufacturing method among the combinations of the first to fifth manufacturing methods.

That is, the sixth manufacturing method of the present invention, as described above,

(a) ethylene,

(b) The softening temperature (TMA) obtained by copolymerization with at least one kind of cyclic olefin represented by the above formula [I] or [Π] is 7 (TC or higher). The cyclic olefin-based random copolymer is supplied to the extruder and melted. When the cyclic olefin-based random copolymer is extruded to produce a copolymer pellet,

Similarly to the first method, a cyclic olefin-based random copolymer heated to a temperature of 50 ° C. or more in advance is supplied to a twin-screw extruder.

The twin-screw extruder used here is the extruder used in the second method, and the screw rotates in the same direction.

In addition, as described in the third method, the twin-screw extruder adjusts the cylinder temperature at the beginning of the molten zone from the glass transition temperature (Tg) of the copolymer supplied to the extruder. The temperature of the extruder is higher than that of the extruder by 90 ° C or more.

As described in the fourth method, the cyclic olefin-based random copolymer extruded in a molten state from the extruder was set to a polymer file having a pressure difference of 90 Kg / Adjust to less than cnf and pass through the polymer filter.

And, as specified in the fifth method, the amount of fine powder generated from the cyclic olefin-based random copolymer pellets shaped as described above is 10 O ppm or less. Dry and / or mix.

In the sixth method, the technical items described in the first to fifth methods can be appropriately adopted to limit the range of numerical values and the like.

As described above, by producing the cyclic-olefin-based random copolymer pellets by the first to sixth production methods, the cyclic-olefin-based random copolymer pellets are produced. The number of cyclohexane-insoluble cyclic olefin-based random copolymer fine particles having a particle size of 1 μm or more contained in 3 O mg is 60,000 or less, preferably 50,000 or less, and Preferably it can be less than 30,000.

The cyclic olefin-based random copolymer belt according to the present invention can be used, for example, in the field of optical materials such as optical disk substrates and optical fibers, transparent films, transparent containers and the like. Used in the field of transparent containers and packaging materials. Since Perret tree bets invention Koto has a characteristic called contain only very small amounts of hexane-insoluble cyclic O reflex fin system random copolymer particles into the grain径力⁵ '1 m or more Sik Russia, It is particularly suitable as a forming raw material for forming optical disk substrates and films with high transparency due to less read errors due to uneven substrate.

The pellet of the present invention may be a ring-opened ring obtained by ring-opening the same or different ring-opened monomer in addition to the above-mentioned ring-opened random copolymer. It can also be formed using a polymer, a ring-opening copolymer or a hydrogenated product thereof. Such a cyclic olefin ring-opening polymer, a ring-opening copolymer and a hydrogenated product thereof will be described by taking the cyclic olefin represented by the above formula [I] as an example. The ring-opening (co) polymer can be obtained by ring-opening (co) polymerizing the cyclic olefin represented by the formula [I] in the presence of a ring-opening polymerization catalyst. In this ring-opening (co) polymer, the cyclic olefin represented by the formula [I] is considered to have a structure represented by the following formula [V].

... [V] In the above formula [V], m, n, q and R 'to R's and R » ^Rb are the same as defined in the above formula [I].

The hydrogenated product can be obtained by reducing this ring-opened (co) polymer in the presence of a reduction catalyst.

In this hydrogenated product, the cyclic olefin represented by the formula [I] is considered to have a structure represented by the following formula [VI].

[VI] In the above formula [VI], m, n, q and R ′ to R ′ 8 and R _a ,

R ^b is the same as defined in the above formula [I].

Examples of such polymers include ring-opening copolymers of tetracyclododecene with norbornene and their derivatives, and hydrogenated products thereof.

In addition, the above ring-opening polymers, ring-opening copolymers, hydrogenated products thereof, and cyclic olefin-based random copolymers (hereinafter collectively referred to as cyclic olefins) (Sometimes referred to as a resin)) may be partially modified with unsaturated rubonic acid or the like such as maleic anhydride. Such a modified product is obtained by combining 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. It can be produced by reacting. In this case, the content of the structural unit derived from the modifying agent in the modified product of the cyclic olefin resin is usually 50 mol% or less, preferably 10 mol% or less. Such a modified cyclic olefin-based resin can also be produced by blending a modifier with the cyclic olefin-based resin so as to obtain a desired modification rate and performing a graft polymerization. Alternatively, a modified product having a high modification rate may be prepared in advance, and then the modified product may be mixed with an unmodified cyclic olefin-based resin.

In the present invention, the above-mentioned cyclic olefin-based random copolymer, ring-opened polymer, ring-opened copolymer, hydrogenated product thereof, and modified product thereof are used alone. Or they can be used in combination.

In addition to the above-mentioned cyclic olefin-based resin, if desired, Another cyclic olefin-based resin having a softening temperature (TMA) of less than 70 ° C. may be blended and used.

Further, when producing the cyclic olefin-based random copolymer pellet of the present invention, a rubber component for improving impact strength may be blended in addition to the cyclic olefin-based resin. , Heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, anti-violence agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. The mixing ratio is an appropriate amount.

For example, as a stabilizer to be blended as an optional component, specifically, tetrakis [methylen-3 (3,5-di-t-butyl-4-hydroxyphenyl)] pionone Methane,-(3,5-di-t_butyl-4-hydroxyhydroxy) propionic acid alkyl ester, 2,2'-oxamidobis [ethyl-3 (3,5— Phenolic antioxidants such as propionate: zinc stearate, calcium stearate, and 12-hydroxystearic acid Fatty acid metal salts such as calcium; glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaeryth Retort stealth, pentaerythritol Examples include fatty acid esters of polyhydric alcohols such as restearates, and phosphorus-based stability such as tris (2,4-di-t-butylphenyl) phosphite. Wear. These may be used alone or in combination. For example, tetrakis [methylen-3 (3,5-di-t-butyl-4-hydroxy xyphenyl) ) Propionate] methane and tris (2,4-di-t-butylphenyl) phosphite, zinc zinc theate and glycerine monostearate A combination with a rate can be exemplified.

In the present invention, it is particularly preferable to use in combination with a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol, and the fatty acid ester of the polyhydric alcohol is an alcoholic compound of a trihydric or higher polyhydric alcohol. It is preferable that the polyhydric alcohol fatty acid ester in which a part of the hydroxyl groups is esterified. Examples of such fatty acid esters of polyhydric alcohols include glycerin monostearate, glycerin monolaurate, glycerin monomyristate, and glycerin monopalmitate. Glycerin fatty acid esters such as glycerin distearate, glycerin dilaurate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol monolaurate, Fatty acid esters of pentaerythritol such as pentaerythritol distearate and pentaerythritol tristearate are used. Such a phenolic antioxidant is usually 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. It is more preferably used in an amount of 0 to 2 parts by weight, and the fatty acid ester of the polyhydric alcohol is usually 0 to 10 parts by weight based on 100 parts by weight of the cyclic olefin resin. Parts, preferably from 0 to 5 parts by weight.

Also, as long as the properties of the pellets are not impaired, the cyclic olefin-based random copolymer pellets ί, silica, K-algae earth, alumina, titanium oxide, magnesium oxide, pumice stone Powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, calcium titanate, barium sulfate, sulfite power Lucium, talc, creed, my strength, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide A filler such as ribden, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, or polyamide fiber may be contained.

[Industrial applicability]

As described above, the cyclic olefin-based random copolymer pellet of the present invention substantially contains fine particles of a cyclohexain-insoluble cyclic olefin-based random copolymer having a particle size of 1 μm or less as described above. Not. Therefore, in the optical disc formed from the pellet, a reading error caused by the substrate is not likely to occur, and the film formed from the pellet is excellent in transparency. Furthermore, these discs and films not only have excellent optical properties as described above, but also have heat resistance, aging resistance, chemical resistance, solvent resistance, dielectric properties and dielectric properties. Excellent mechanical properties.

The cyclic olefin-based random copolymer pellet according to the present invention having such properties is prepared by preliminarily preparing the cyclic olefin-based random copolymer obtained from the polymerization step at 50 ° C or more. Heating to the temperature of the extruder and feeding it to the extruder, setting the starting temperature of the melting point of the cylinder in the extruder to a specific temperature, and using a twin-screw extruder, the screw rotates in the same direction And extruding the melted copolymer using a polymer filter before and after the polymer filter. Pressure difference is not higher than the specified value, and pellets are broken when the cyclic olefin random copolymer pellets are dried or mixed. The method can be easily carried out by setting the drying conditions or the mixing conditions so that the amount of the fine particles is kept at 10 Oppm or less, and by combining these methods.

[Example]

Hereinafter force ⁵ to be described I by the present invention embodiment ', the present invention is not be to be limited to these examples.

The methods for measuring and evaluating various physical properties in the present invention are described below.

(1) Method for measuring the number of fine particles of cyclic olefin-based random copolymer insoluble in hexagonal hexane having a particle size of 1 μm or more

The cyclic olefin-based random copolymer pellets were measured using a KS-60 type sensor with a fine particle force center (Lion Corporation: KL-011 type). Dissolve 3 g / liter in cyclohexane containing 2〇0 or less microparticles with a particle size of 1 μm or more contained in O ml at a rate of 3 g / liter. The number was determined by measuring the number of fine particles having a particle diameter of 1 μm or more contained in 10 ml measured by a fine particle counter.

(2) Evaluation method for reading errors on optical disk substrates

From the cyclic olefin-based random copolymer pellets obtained in Examples and Comparative Examples, spiral 13 group diameter 13 O ram disk substrates were prepared, and spatters were formed on the substrates. use data _{device, S i N x / T b} F e C o / S i N x / a l laminated film [film thickness of each layer (e Ngusuromu); iota -12-

The composition of 100/250/300 / 400A Tb / Fe / Co: 71/23/6 atm%] was formed, and the disk bit error rate (BER) was measured by the following method. .

Evaluation conditions

Write frequency 1 MHz

Write pulse width 5 0 0 ns

Erasing power 10 mW

Write power 8 mW

Playback power: 1.5 mW

Bias magnetic field 300 Elsted

B E R measurement area Radius 40 to 4 5

Example 1

Manufacture of cyclic olefin-based random copolymer

[Catalyst preparation]

V 0 (〇 C ₂ H ₅₎ the C 1 ₂ was diluted with hexane Sik Russia, vanadium concentration 1 8.6 millimeter mol / l - was prepared Banajiu beam catalyst is hexane consequent filtration. On the other hand, ethyl aluminum sesquichloride (A

_{_{.. 1 (C 2 H 5}} ), 5 C 1, 5) was diluted with hexane and the consequent Russia, the Aluminum Niu beam concentration 1 6 4 millimeter mol / l - organic Al is hexane consequent b A mini catalyst was prepared.

[Compound]

A polymerization vessel equipped with baffles and stirrers with an inner diameter of 700 thighs, a total volume of 570 liters, and a reaction volume of 300 liters, and a heat transfer area of 19.4 And a vertical multi-tube cooler, Equipped with a circulation line that draws out the polymerization solution from the bottom, circulates the drawn out polymerization solution through a multi-tube cooler, and returns it to the polymerization reactor, and a circulation pump that is installed in the circulation line. polymerization apparatus using the system, and ethylene-les down, Te preparative Rashiku port represented by the following formula [4, 4, 0, I 2 '5, I 7 · 1 0] - 3- dodec emissions (cyclic O Lev I down, hereinafter referred to simply as there is and this referred to as "Te door Rashiku Russia dodec down".) and Bok butene down the about 1.2 mol ^_0/0 continuously KoTsuta the co-polymerization reaction to cormorants by including.

In carrying out this reaction, the vanadium catalyst (V catalyst) prepared by the above method is used in an amount such that the concentration of V catalyst in the polymerization reactor becomes 0.35 mmol / liter. It was fed into the polymerization vessel. In addition, cyclohexane, a polymerization solvent, was used so that the concentration of the V catalyst immediately before being supplied to the polymerization reactor was 1.8 times the dilution factor of the catalyst in the polymerization reactor. This V catalyst was diluted and supplied in advance.

On the other hand, ethyl aluminum methoxychloride as an organic aluminum compound was supplied into the polymerization reactor in such an amount that Al / V = 8.0 ₍ and was supplied to the polymerization reactor). The V catalyst and the organic catalyst were diluted beforehand with a cyclohexane polymerization solvent so that the concentration immediately before the concentration in the polymerization vessel became 11 times as high as the dilution ratio. The point where the aluminum catalyst is supplied is near the tip of the upper blade of a stirrer with two vertical disc bins with a diameter of 0.25 m in two stages. Is also a strong part, so that dispersion mixing can be performed promptly.

Cyclohexane used as a polymerization solvent was supplied into the polymerizer at a rate of 233.3 kg / h. Ethylene was supplied at a rate of 2.69 kg / h, and hydrogen gas as a molecular weight regulator was supplied at a rate of 2.2 N liter / h to the gas phase in the polymerization reactor. The polymerization liquid was vigorously stirred with a power of 4.3 kw / kL by a stirrer.

The jacket attached to the polymerization vessel external and multitubular cooler shell side, 2 5 weight ^_0/0 meth Nord water Ri by the and this circulating in the refrigerant, the polymerization temperature is 1 0 ° C The temperature was controlled so that Nitrogen gas was introduced into the polymerization vessel to control the pressure so that the polymerization pressure was 1.0 kg / cm ² -G.

The following method was used to clean the inner wall of the polymerization vessel. In other words, a pan (spray disk) with a hole was attached to the gas phase of the shaft connecting the stirrer and the stirring blade. Cyclohexane solvent in an amount of 30 kg / h and tetracyclododecene in an amount of 14.2 kg / h were added to the spray disk. -While supplying butene at a rate of 0.41 kg / h, the shaft is rotated, and cyclohexane and tetracyclododecene and 1-butene are supplied by rotating the shaft. Due to the generated centrifugal force, it was scattered from the hole of the spray disk and sprayed on the inner wall of the polymerization vessel. The sprayed tetracyclododecene, cyclohexane and 1-butene were mixed into the liquid phase along the inner wall.

The copolymerization reaction between ethylene and dodecene and 1-butene was carried out continuously under the above conditions. A cyclohexane solution having a concentration of 34 g / liter of dodecene / 1-butene copolymer was obtained.

[Deashing]

To a copolymer solution of ethylene and tetracyclododecene extracted from the polymerization vessel was added 8 CTC hot water and a 4% by weight NaOH solution as a PH regulator. When the copolymerization reaction is stopped, the catalyst residue remaining in the copolymer solution is removed from the copolymer solution (demineralization), and the copolymer solution after demineralization is once subjected to an inner diameter of 900 mm. , and the effective volume is 1. 0 m ³ and is stored in a container equipped with a stirrer, copolymerization solution this decalcified in jacket attached to the outside of the container by flowing cold water to about 3 0 to 4 0 ° Cooled to C.

[Filtering]

The copolymer solution thus obtained was good earthenware pots, 2 in an amount of 6 1 kg / h, the external径力^s 6 3. 5 mm, an inner diameter of force 2 8 mm, a nominal diameter 1 m is 1 m long The filter was supplied to a filter containing 34 cotton wound filters (vertical type wind filters manufactured by Nippon Roki Co., Ltd.) to continuously filter.

Next, a nonwoven nonwoven nonwoven fabric with a nominal diameter of 2 m, having an outer diameter force of ^s 64 mm, an inner diameter of 51 mm, and a length of 476 strokes, is a nonwoven fabric type filter (manufactured by Bolston). BX filter) was supplied at a rate of 261 kg / h to a filter containing three filters and continuously filtered. At this time, the pressure difference between the filter and the front and rear (differential pressure) was less than 1.5 kg / cm ² .

Next, a depth-type nonwoven fabric made of Hookey Grass-Mikloff Ibar with a nominal diameter of 0.9 で m, which has an outer diameter of 5.9 mm, an inner diameter of 51 mm, and a length of 476 mm. A filter containing three filters (AQ filters manufactured by Bolston) was supplied at a flow rate of 261 kg / h to continuously filter. At this time, the pressure difference was 1.5 kg / cm ² or less.

In addition, a depth-type filter made of nonwoven fabric made of Houkey Glasmacro Fiber with a nominal diameter of 0.3 m, which has an outer diameter of 59 mm, an inner diameter of 51 thighs, and a length of 476 mm ( A filter containing three AAQ filters (Bolston Co., Ltd.) was supplied at a flow rate of 261 kg / h to continuously filter. At this time, the differential pressure was 1.5 kg / cm ^ or less.

Finally, a pleated filter made of SUS304 metal non-woven fabric with a nominal diameter of 0.3 mm, which has an outer diameter of 61 mm and a length of 5100 mm (PSP 0 manufactured by Brownswick) The filter was supplied continuously at a rate of 26 1 kg / h to a filter containing one filter and the filter was continuously filtered.

[Deposition]

The polymer solution 26 1 Kg / h after the deashing step and the filtration step and 1200 kg / h of acetone were supplied to a precipitation drum with a stirrer (first precipitation drum) and mixed. The copolymer was deposited in the first deposition drum by adjusting the temperature of the liquid to 30 ° C and stirring.

Next, the acetate dispersion of the copolymer precipitated in the first deposition drum was supplied to a deposition drum (second deposition drum) equipped with a baffle plate and a stirrer to precipitate the polymer again. .

[Filter separation]

The dispersion obtained by the second deposition drum was filtered, and the filtrate and the polymer produced by the polymerization reaction were separated as a wet cake. In the filtrate, unreacted monomer and cyclohexane as a polymerization solvent were precipitated. It includes the acetate used in the process.

The separated filtrate was separated into each component and reused.

[Extraction]

Next, a dispersion was prepared by dispersing the copolymer wet cake in acetonitrile so as to have a concentration of about 2 Og / liter, and this dispersion was subjected to pressurization in an extraction tank under pressure. Heated to 0 ° C. In this way, the dispersion of the copolymer / jet cake was heated to elute unreacted monomers remaining in the copolymer / jet cake into the acetate.

[Centrifugation]

The copolymer dispersion cake that had undergone the above-described extraction step was subjected to solid-liquid separation using a centrifugal separator, thereby obtaining a copolymer-jet cake.

[Dry]

First, the copolymer wet cake obtained through the above-mentioned centrifugation step was dried at normal temperature by heating at 90 ° C. for 20 minutes using a normal pressure dryer.

The copolymer wet cake was passed through a normal-pressure dryer heated with steam at a pressure of 1 Kg / cm ² G, and dried by heating for 20 minutes.

The copolymer jet cake dried under normal pressure as described above was then vacuum dried using a vacuum dryer. The vacuum dryer was heated with steam at a pressure of 2 Kg / cm2 G, and the final pressure during vacuum drying was adjusted to 1 O Torr.

A copolymer powder having undergone the above-mentioned atmospheric drying step was introduced into the vacuum dryer and dried for 3 hours to obtain a copolymer powder. Based on 100 parts by weight of the obtained copolymer powder, tetrakis [methylen-3- (3,5-di-t-butyl-4-hydroxy) was used as a stabilizer. (Kisifenyl) propionate] metane (manufactured by Nippon Ciba-GaiGi Co., Ltd., Irganox 1010) 0.6 parts by weight, tris (2,4-di-1-butylphenyl) (Enyl) phosphite (Nippon Ciba-Gaiichi Co., Ltd., phosphite 168) 0.25 weight 咅 [5, monoglyceride stearate 0.6 weight Parts and 0.02 parts by weight of zinc stearate were added.

Manufacture of copolymer pellets

[Peletize]

4 4 strokes of this copolymer powder? 5 Different direction twin screw extruder (TX E-44 SS, Nippon Steel Works Co., Ltd., L / D = 30) is supplied at room temperature, melt-extruded, and pelletized about 3 mm in diameter. Manufactured.

This extruder is made of nitriding iron-based special steel. The barrel temperature of the melting part was 260 ° C, and the temperatures of the bent part, compression part, and light part after that were 250 ° C. The screw rotation of the extruder was set so that the specific energy force was 0.15 kwh / kg.

At the end of this extruder, a leaf-type polymer filter (manufactured by Nippon Seisen Co., Ltd.) made of SUS metal non-woven fabric with a nominal diameter of 5 m was attached, and the melt-extruded copolymer was filtered. . At this time, the difference in pressure (differential pressure) around the filter was set to 40 kg / _cm '.

[Pellet drying / classification]

Moisture adhering to the obtained copolymer pellets is dried, and before filling the product container, fine particles weighing 1/10 or less of the pellets by wind-drying, specifically, Is abrasion powder generated during pellet drying. Particle pellets, crushed pellet debris, and fine foreign matter adhering to the pellets were removed.

The number of cyclohexane-insoluble fine particles in the cyclic olefin-based random copolymer pellets obtained in this manner was measured by the above method. It was 0/30 mg. After using this pellet to create a substrate, an optical disk was manufactured, and the bit error rate (BER) was measured by the above method. Met. Comparative Example 1

A pellet was produced in the same manner as in Example 1 except that the filtration was not performed with a metal nonwoven fabric made of SUS in the pelletizing step.

The number of cyclohexane-insoluble fine particles in the cyclic olefin-based random copolymer pellets thus obtained was measured by the method described above, and was found to be 6200/30 mg. Was. After creating a substrate using this pellet, a light disc prepared, the roller was measured bit Toera one rate a (BER) in the manner described above, 1 0. Ί X 1 0 - was ⁶ .

Example 2

In Example 1, the cyclic olefin-based random copolymer padder obtained in the drying step was preheated as follows.

[Preheating]

The copolymer Bauda obtained in the drying step, was placed in a jacket with a lateral cylindrical container having a capacity of 2 m ³ equipped with a paddle stirring blade. The cyclic olefin-based random copolymer padder was heated to about 90 to 100 while stirring the steam through the jacket with a paddle stirring blade. [Pelletize]

Copolymer powder preheated as described above-1 Okg, a 4-way 5 twin-screw extruder equipped with one air vent (TEX-, manufactured by Japan Steel Works, Ltd.) 4 SS, L / D = 30) immediately, and melt-extrusion was performed. In this twin-screw extruder, the surface of the portion that comes into contact with the molten resin is formed of a nitriding-treated iron-based special steel.

The temperature of the melt section cylinder of the extruder was set at 210 ° C. The cylinder temperature in the vent section was 250 ° C, the cylinder temperature in the compression section was 250 ° C, and the cylinder temperature in the metering section was 250 ° C.

The screw speed of the extruder was set to 125 rpm in the cylinder whose temperature was set as described above, and the copolymer was melt-extruded.

The copolymer melt-extruded with a leaf-type polymer filter (made by Nippon Seisen Co., Ltd.) of SUS metal non-woven fabric with a nominal diameter of 5 m at the end of the extruder is filtered, and a pellet with a diameter of about 3 mm is filtered. Obtained.

At this time, the pressure difference of the polymer filter was about 40 kg / cm ² .

[Pellet drying, classification]

After removing the water adhering to the pellets of the obtained copolymer in the drying process, before filling the product container, use an air classifier to make it less than 1/10 of pellets Abrasive powder, pellets with small particle size, pellets of crushed pellets, fine foreign matter attached to pellets, etc. were removed.

The number of fine hexane-insoluble particles in the cyclic olefin-based random copolymer pellets thus obtained was measured by the above-mentioned method, and was found to be 2900/30 mg. . Example 3

In the same manner as in Example 2, except that the operation in the preheating step was changed as follows, and the cyclic olefin-based random copolymer was in a molten state and immediately supplied to the extruder in this state. Thus, a cyclic copolymer random copolymer belt was produced.

[Preheating]

A cyclic olefin-based random copolymer powder containing a stabilizer was supplied to a hopper with a 1-ms content jacket. 20 kg / cm ² G steam was introduced into the jacket, and the copolymer powder was heated to 200 ° C. and melted.

The number of fine hexane-insoluble particles in the cyclic olefin-based random copolymer pellet obtained in this manner was measured by the above-mentioned method. / 30 mg. After creating a substrate using this pellet, to produce a light di scan click, bit error rate with (BER) and was measured by the method described above rollers, 2 7 X 1 0 - it was ^6..

Comparative Example 2

A pellet was produced in the same manner as in Example 2, except that the copolymer powder was supplied to the extruder at 3 TC without preheating.

The cyclic olefin-based random copolymer pellets thus obtained were subjected to the above method to measure the number of fine particles insoluble in the mouth of the cycloolefin. there were. After a substrate was formed using this pellet, an optical disc was manufactured, and the bit error rate (BER) was measured to be 15.0 X 10 by the above method.

In addition, without classifying the pellets obtained as described above, The pellets were dried in a drying container used in Example 7 described below, which was intermittently rotated at a speed of 17 rpm with a stirrer provided with a ribbon-type stirrer, for 24 hours. The total stirring time at this time was set to 180 minutes.

The number of cyclohexane-insoluble fine particles in the copolymer pellets dried as described above was measured by the above method and found to be 6600/30 mg. After a substrate was made using this pellet, an optical disk was manufactured, and the bit error rate (BER) was measured by the method described above. The result was 15.5 X 10_e. .

Example 4

The glass transition temperature (T g) of the copolymer powder obtained in the “Production of cyclic copolymer random copolymer” step of Example 1 was measured, and it was found to be 129 ° C.

[Pelletize]

The copolymer powder having a glass transition temperature of 129 ° C obtained in the step of “Production of a cycloolefin random copolymer” of Example 1 was supplied at a supply amount of 10 Kg / h to obtain a copolymer having a glass transition temperature of 445 ° C. It was fed to a directional twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX-44 SSL / D = 30) at room temperature and melt-extruded. This extruder has one atmospheric vent.

The temperature of the melted cylinder of the extruder was set at 26 CTC at the part closest to the hopper. This temperature is 131 ° C higher than the glass transition temperature of the supplied copolymer powder. The temperature of the melted part cylinder was the highest in this part. The cylinder temperature in the vent section was 250 ° C, and the cylinder temperature in the compression section was 250 ° C. The binder temperature was 250 ° C.

The copolymer was melt-extruded in the cylinder whose temperature was set as described above, with the screw speed of the extruder being set such that the relative energy was 15 kwh / kg.

The copolymer melt-extruded with a leaf-type polymer filter (made by Nippon Seisen Co., Ltd.) of SUS metal nonwoven fabric with a nominal diameter of 5 m at the end of the extruder is filtered to obtain a pellet with a diameter of about 3 mm. Was.

[Pellet drying, classification]

After removing the water adhering to the pellets of the obtained copolymer in the drying process, before filling the product container, the air classifier was used to remove less than 1/10 of the pellet. The aperylene random copolymer thus obtained is obtained by removing heavy abrasion powder of pellets, small-diameter pellets, crushed pellet fragments, and fine foreign matters adhering to the pellets. The number of fine hexane-insoluble particles in the pellet was measured by the above-mentioned method, and as a result, it was 2.7000 particles / 30 mg.

Comparative Example 3

Example 4 was the same as Example 1 except that the cylinder temperature at the beginning of the melted portion of the extruder was set to 21 CTC, which is 81 ° C higher than the glass transition temperature (Tg) of the copolymer used. Pellets were manufactured in the same manner.

The number of cyclohexane-insoluble fine particles of the cyclic olefin-based random copolymer pellet obtained in this manner was measured by the above method, and it was found that the number was 6500/30 mg. It was. Example 5

[Pelletizing]

The copolymer powder having a glass transition temperature of 129 ° C. obtained in the “Production of Cyclic olefin-based random copolymer” step of Example 1 was supplied at a feed rate of 10 kg / h to 44 kg. A twin-screw extruder (TEX-44SS, L / D = 30, manufactured by Nippon Steel Works, Ltd.) equipped with two screws rotating in the same direction at room temperature to perform melt extrusion. Was. The two screws provided in this extruder are joined to a motor so that they rotate in the same direction. The depth of the groove (h) of the screw provided in this twin-screw extruder is 4 gangs, and the number of the screw is two. In addition, no mixing elements are provided. This extruder has one atmospheric vent.

In addition, the temperature of the cylinder in the melting section of this twin-screw extruder was set to 210 ° C, and the temperature of the cylinder in the other cylinders (vent, compression, and metering) was set to 2 The temperature was set at 50 ° C.

In the cylinder whose temperature was set as described above, the relative energy was 0.15 kwh / kg, and the screw of the extruder was rotated in the same direction at a rotation speed of 125 rpm. The copolymer was melt-extruded at a setting.

The copolymer melt-extruded with a leaf-type polymer filter made of SUS metal non-woven fabric with a nominal diameter of 5 m at the end of the extruder (manufactured by Nippon Seisen Co., Ltd.) is filtered and a pellet with a diameter of about 3 mm I got it.

[Pellet drying, classification]

Moisture adhering to pellets of the obtained copolymer is removed in the drying step. After removal and before filling into the product container, the air classifier uses 風力 1/10 or less of the pellets for abrasion powder, small particle pellets and crushed pellets. 6. Removes debris and small foreign matter adhering to the pellet.

The number of cyclohexane-insoluble fine particles in the thus obtained cyclic olefin-based random copolymer pellet was measured by the above method, and found to be 2800/30 mg. After creating a substrate using this pellet, a light disc produced was measured bit Toerare preparative (BER) in the manner described above, 4. 8 X 1 0 - was ^6.

Comparative Example 4

In Example 5, a cyclic olefin-based random copolymer pellet was produced in the same manner as in Example 5, except that a different-direction twin-screw extruder having a different screw rotation direction from the twin-screw extruder was used. .

The number of fine particles of the cyclic olefin-based random copolymer of 1 μm or more contained in the cyclic olefin-based random copolymer obtained in the above manner was measured. As a result, it was 6500/30 mg.

Example 6

[Pelletize]

The copolymer powder having a glass transition temperature of 129 ° C. obtained in the “Production of cyclic copolymer based random copolymer” process of Example 1 was supplied at a supply rate of 10 kg / h. Was supplied at room temperature to a different direction twin-screw extruder (manufactured by Nippon Steel Works Co., Ltd., TEX-44 SSL / D = 30) to perform melt extrusion. This extruder has one atmospheric vent. The copolymer melt-extruded with a leaf-type polymer filter (made by Nippon Seisen Co., Ltd.) of SUS metal non-woven fabric with a nominal diameter of 5 m at the tip of the extruder is filtered to obtain a 3 mm diameter. I got a pellet. The temperature of the polymer filter was set at 280 ° C., which is higher than the glass transition temperature (T g) of the cyclic olefin-based random copolymer used by 151 ° C.

The temperature of the molten part cylinder of this extruder was 260 ° C. In addition, the cylinder temperature of other parts (vent part, compression part, lightweight part) is 25

The temperature was set to 0 ° C.

[Pellet drying, classification]

Fine particles weighing 1/10 or less of the pellet were removed from the obtained cyclic copolymer-based random copolymer pellet by an air classifier. Specifically, pellets generated during pellet drying, pellets with small grain size, pellets of crushed pellets, and fine foreign matter adhering to the pellets were removed.

Next, the moisture adhering to the cyclic-olefin-based random copolymer pellet was dried and removed, and the pellet was filled in a product container.

The number of cyclohexane-insoluble fine particles contained in the thus obtained cyclic olefin-based random copolymer pellet was determined by the above method to be 2.7000. Individual / 30 mg.

Comparative Example 5

In Example 6, the difference in pressure before and after the polymer filter when the cyclic off-based random copolymer passed through the polymer-filter was used. A cyclic olefin-based random copolymer pellet was produced in the same manner except that (differential pressure) was set to about 100 kg / Crrf.

The number of cyclohexane-insoluble fine particles of 1 "m or more contained in the cyclic olefin-based random copolymer pellets obtained as described above was measured, and After preparing a substrate using this pellet, an optical disk was manufactured, and the bit error rate (BER) was measured by the method described above. It was 0-e.

Example 7

[Peletize]

The copolymer powder obtained in the “Production of cyclic copolymer-based random copolymer” process of Example 1 has a single air vent. It was supplied to TEX-44 SS (L / D = 30) manufactured by Steel Works, Ltd. at room temperature and melt-extruded.

At the end of the extruder, a leaf-type polymer filter made of SUS metal non-woven fabric with a nominal diameter of 5 m (manufactured by Nippon Seisen Co., Ltd.) was attached, and the melt-extruded co-polymer was filtered. A pellet with a diameter was obtained.

[Pellet drying]

The obtained pellets (560 kg) were charged into a jacketed container having an inner diameter of 110, an inner volume of 1.75 D and a vertically equipped bonnet type stirrer. The container and stirrer are made of SS304, the surface of which is polished with puff polishing 250 and then mirror-finished or electrolytically polished o

Inside this container are two 1101 banded ribbon wings and 2 50 banded ribbon wings. Each ribbon wing is arranged, and the helical angle of each of the ribbon wings is 900 in band. These two wings are also arranged so as to raise the bevel by rotation.

The ribbon type stirrer is designed such that a gap of 25 to 30 is formed between the tip of the ribbon blade and the upper inner wall of the vessel, and a gap of 40 to 5 On ™ is formed at the lower part of the vessel inner wall. Are located.

A jacket was arranged on the outer periphery of the container. The temperature of the jacket was adjusted to 60 ° C, and the inside of the container was evacuated to dry the pellets.

The pellets were dried for 24 hours by intermittently rotating the stirrer equipped with the above-described ribbon-type stirrer at a speed of 4 rpin. The total stirring time at this time was 48 minutes.

The pellets dried as described above were directly charged into a product container without removing fine powder by classification.

The number of cyclohexane-insoluble fine particles contained in the cyclic olefin-based random copolymer pellet obtained in this manner was measured by the above method. Individual / 30 mg.

Comparative Example 6

In Example 7, the gap between the ribbon blade and the inner wall surface of the lower part of the vessel was 25 to

It was narrowed to 30 mm, and the 50 mm wide blade of the two ribbon blades was arranged so that the pellet was swept down toward the bottom of the container by rotation. Further, the rotation speed of the stirrer was increased to 17 rpm, and the total stirring time was set to 180 minutes. Except for the above, a cyclic olefin-based random copolymer pellet was produced in the same manner as in Example 7. As a result of measuring the number of fine particles insoluble in hexahedral hexane having a particle size of 1 μm or more contained in the cyclic olefin-based random copolymer pellets obtained as described above, 65 It was 0.000 pieces / 30 _mg . After a substrate was created using this pellet, an optical disc was manufactured and the bit error rate (BER) was measured by the method described above. 7

Example 8

[Peletize]

In the same manner as in Example 3, the copolymer powder having a glass transition temperature of 12 ° C. obtained in the “Production of cyclic olefin-based random copolymer” step of m ³ of the jacket with Ho Tsu path - was supplied to. 20 kg / cm ² G steam was introduced into the jacket, and the copolymer powder was heated to 200 ° C. and melted. A twin-screw extruder equipped with two screws that rotate in the same direction of 44 mm ^ at a feed rate of 1 OKg / h (TEX, manufactured by Nippon Steel Works, Ltd. — 44 SS, L / D = 30) and melt-extruded. The two screws provided in this extruder are joined to the motor so that they rotate in the same direction. This extruder has one atmospheric vent.

The depth of the groove (h) of the screw provided in this twin-screw extruder is 4 mm, and the number of the screw is two. In addition, no mixing elements are provided.

In addition, the temperature of the cylinder in the melting section of this twin-screw extruder was set to 26 (TC), and the temperature of the cylinder in the other cylinders (vent, compression, and metering) was set to 2 (TC). The temperature was set to 50 ° C. The specific energy becomes 0.15 kwh / kg within the cylinder set at the temperature as described above, and the screw of the extruder rotates at 125 rpm in the same rotation direction. And the copolymer was melt extruded.

The copolymer melt-extruded through a leaf-type polymer filter (made by Nippon Seisen Co., Ltd.) of SUS metal non-woven fabric with a nominal diameter of 5 m at the end of the extruder is filtered to obtain a pellet with a diameter of about 3 band. Was. The temperature of the polymer filter was set to 280 ° C., which is higher than the glass transition temperature (T g) of the cyclic olefin-based random copolymer used by 151 ° C.

[Pellet drying, classification]

Fine particles weighing 1/10 or less of the pellet were removed from the obtained cyclic copolymer-based random copolymer pellet by an air classifier. More specifically, pellet abrasion powder generated during pellet drying, small-diameter pellets, crushed pellet debris, and fine foreign matter attached to the pellets were removed.

Next, the water adhering to the cyclic-olefin-based random copolymer pellet was dried and removed, and the pellet was filled in a product container.

The number of fine hexane-insoluble particles contained in the cyclic olefin-based random copolymer pellet thus obtained was determined to be 500,000 by the above method. / 30 mg, and the amount of cyclohexane-insoluble fine particles contained in this cyclic olefin-based random copolymer pellet was extremely small. A substrate is also formed using this copolymer pellet. After the fabrication, an optical disc was manufactured, and the bit error rate (BER) was measured by the above-mentioned method, and it was 1.2 X 10-6.

Comparative Example 7

[Peletize]

In Example 8, a twin-screw extruder in which the rotation direction of the screw of the twin-screw extruder was changed to a different direction was used without adding a preheating to a cyclic r-type random copolymer bow of 30 r. Supply melter and extrude, filter

A cyclic olefin-based random copolymer pellet was produced in the same manner except that the filtration was performed at 100 kg / cm ² .

[Pellet drying]

The obtained pellets were charged into the drying container used in Example 7, and a stirrer equipped with a ribbon-type stirrer was intermittently rotated at a speed of 17 rpm to dry the pellets for 24 hours. Was. The total stirring time at this time was 180 minutes.

When the number of fine particles insoluble in hexahedral hexane contained in the cyclic olefin-based random copolymer pellet thus obtained was measured by the above method, it was found that 100,000 was obtained. The number was more than 0.000 / 30 mg, and accurate number could not be measured.

After a substrate was formed using this pellet, an optical disk was manufactured, and the bit error rate (BER) was measured by the above method, and it was 35.2 X 10-e.

Claims

The scope of the claims

1. (a) Ethylene and

(b) Cyclic olefin-based random copolymers having a softening temperature (TMA) of 70 ° C or more obtained by copolymerization with a cyclic olefin represented by the following formula [I] or [Π] 6 microparticles of a cyclohexane-insoluble cyclic olefin-based random copolymer fine particle having a particle diameter of 1 μm or more, which is a polymer pellet and contained in 3 O mg of the pellet, A cyclic olefin-based random copolymer pellet characterized in that the number is 10,000 or less;

· · · [I]

[In the above formula [I], n is 0 or 1, m is 0 or a positive integer, Q is 0 or 1, R ¹ to R 18 and R. And R b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group;

R and ⁵ to R may be bonded to each other to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R! ⁶ or R ¹⁷ and R ^{1 e} may form an alkylidene group];

··· C π]

[In the above formula [Π], ρ and q are 0 or a positive integer, m and n are 0, 1 or 2, and

R ′ to R i «are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group,

The carbon atom to which R ⁹ or R ¹ ° is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or alkylene having 1 to 3 carbon atoms. May be linked through a group,

Further, it may be n = m = 0 Noto-out R i 5 and R i2 or R _{I 5} and the R _IE connected to form a monocyclic or polycyclic aromatic ring;];

2. (a) Ethylene and

(b) a softening temperature (TMA) obtained by copolymerization with at least one kind of cyclic olefin represented by the following formula [I] or [D] is 70 ° C or more; In producing the copolymer belt by feeding the cyclic orphan-based random copolymer to an extruder and extruding the copolymer in a molten state from the extruder,

The cyclic olefin copolymer is characterized in that the cyclic olefin random copolymer is preliminarily heated to a temperature of 50 ° C or more, supplied to an extruder, and formed into a pellet. A method for producing a random copolymer pellet;

… [I]

[In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and 1 ^ ′ to 1 ^ 8 ぉ. And R _{b each} independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group;

R to R may be bonded to each other to form a monocyclic or polycyclic ring Rather good, and rather it may also be monocyclic or polycyclic have a double bond, also in the R 1 ⁵ and R ^16, or form a alkylene re den group and R ¹⁷ and R ¹⁶ May be used];

· · · [Π]

[In the above formula [n], p and q are 0 or a positive integer, m and n are 0, 1 or 2,

R ′ to R ⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group;

R 9 or R 1. And the carbon atom to which R is bonded or the carbon atom to which R ′ ′ is bonded, directly or via an alkylene group having 1 to 3 carbon atoms. Well,

Further, n = m = 0 and Noto-out R i 5 and R _{I 2} or R _{I 5} and R 'e may form a monocyclic aromatic ring or polycyclic bonded互Re, the ].

3. The cyclic olefin-based random copolymer supplied to the extruder is a cyclic olefin-based random copolymer powder that does not substantially contain a solvent. 3. A method for producing the cyclic olefin-based random copolymer pellet according to claim 2.

4. The cyclic olefin-based copolymer according to claim 2, wherein the cyclic olefin-based random copolymer supplied to the extruder contains a solvent in an amount of 20% by weight or less. Method for producing random copolymer pellets.

5. Cyclic olefin random copolymer obtained in 30 mg of cycloolefin hexane-insoluble cycloolefin random copolymer with a particle size of 1 ^ m or more contained in 30 mg of the obtained cyclic olefin random copolymer. The method for producing a cyclic olefin-based random copolymer pellet according to any one of claims 2 to 4, wherein the number of fine particles is 60,000 or less. .

6. (a) Ethylene and

(b) A cyclic polymer having a softening temperature (TMA) of 70 ° C or more obtained by copolymerization with at least one cyclic olefin represented by the following formula [I] or [π] In producing the copolymer pellet by feeding an orphanic random copolymer to an extruder and extruding it from the extruder in a molten state,

Cylinder-temperature force at the beginning of the melted part of the extruder is 90 ° C. or more higher than the glass transition temperature (Tg) of the copolymer supplied to the extruder, and Cyclic cyclic olefin copolymer characterized in that a cyclic cyclic olefin copolymer is supplied to an extruder set higher than the other parts of the extruder and formed into a pellet. Method of manufacturing the let;

… [I]

[In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ′ to R ′ 8 and R. And R b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group;

R> ⁵ to R, s may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond; 'in the ⁵ and R 1 ^6, or R' ⁷ and R 18 and in may form a alkylene Li Den group];

· · · [Π]

[In the above formula [Π], p and q are 0 or a positive integer, m and n are 0, 1 or 2,

R ′ to Ri »each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group;

The carbon atom to which R 9 or R 1 0 is attached, R 1 ³ are bonded to the in which carbon atom or a carbon atom to which R ^{1 1} is bonded directly or TansoHara element having 1-3 alkyl It may be linked via a len group,

Further, n = m = 0 Noto-out and R i 5 and R i ₂ and R i 5, R ₁₉ may form a monocyclic or polycyclic aromatic ring bonded to each other.

7. Cyclohexane-insoluble cycloolefin-based random copolymer fine particles having a particle size of 1 or more contained in 30 mg of the obtained cyclic olefin-based random copolymer are obtained. 6 0, 0 0 0 or less 7. The method for producing a cyclic olefin-based random copolymer bellet according to claim 6, wherein

8. (a) Ethylene,

(b) a ring having a softening temperature (TMA) of at least 70 t obtained by copolymerization with at least one cyclic olefin represented by the following formula [I] or [π] When the copolymer-based random copolymer is supplied to a twin-screw extruder and extruded from the twin-screw extruder in a molten state, the copolymer bellet is produced.

A cyclic orphan random copolymer characterized in that a cyclic orphan random copolymer is supplied to a twin-screw extruder in which a screw rotates in the same direction and formed into a pellet. A method for producing a copolymer bellet;

· · · [1]

[In the above formula [I], n is 0 or 1, m is 0 or a positive integer, Q is 0 or 1, and! ^ ~ And R b each independently consist of a hydrogen atom, a halogen atom and a hydrocarbon group Represents an atom or group selected from the group;

RI ⁵ ~ RI ⁸ is rather good even if rather good also form a monocyclic or polycyclic bonded to each other, and the monocyclic or polycyclic ring having a double bond and, R ^'5 And R ¹⁶ or R ¹⁷ and R ^{1 て}も may form an alkylidene group];

… [Π]

R ′ to Ris are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group;

The carbon atom to which Rs or R10 is bonded and the carbon atom to which R is bonded or the carbon atom to which RH is bonded are directly or an alkylene group having 1 to 3 carbon atoms. May be connected via When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

9. The production of a cyclic olefin-based random copolymer pellet according to claim 8, wherein the screw number of the twin-screw extruder is one or two. Method.

10. The production of a cyclic copolymer-based random copolymer pellet according to claim 8, wherein two screws of a twin-screw extruder are combined with each other. Method

1 1. Cyclohexane-insoluble cycloolefin-based random copolymer fine particles with a particle size of 1 μm or more contained in 3 mg of cyclic olefin-based random copolymer pellets. 60. The cyclic olefin-based random copolymer pellet according to any one of claims 8 to 10, wherein the number is not more than 60,000. Manufacturing method.

1 2. (a) Ethylene and

(b) a cyclic olefin having a softening temperature (TMA) of 70 ° C or more, obtained by copolymerizing a cyclic olefin represented by the following formula [I] or [π]; When the copolymer is supplied to an extruder and extruded from the extruder in a molten state to produce the copolymer pellet, the copolymer is melt-extruded from the extruder and then melted. An annular system characterized by adjusting the differential pressure across the polymer-based random copolymer to 90 kg / crf or less before and after passing the polymer filter through the polymer filter. A method for producing a olefin-based random copolymer pellet;

· · · [I]

[In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ′ to R18 and R. And R _{b each} independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group;

R 1 ⁵ ~ R is rather good may have a bond to each other to form a monocyclic or polycyclic rather it may also, and the monocyclic or polycyclic double bond to each other and, R ^'5 and R 'in the ⁶ or R' ⁷ and R 1 s and in may form a alkylene Li Den group];

[π]

R ′ to R is each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group;

The carbon atom to which R 9 or RI ° is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. May be connected via

Further, n = m = 0 and Noto-out R ¹⁵ Metropolitan or R '5 and R IS may form a monocyclic or polycyclic aromatic ring bonded to each other.

13. The cyclic orphan according to claim 12, wherein the cyclic orphan-based random copolymer is heated to 50 tons or more in advance and supplied to an extruder. A method for producing a random copolymer copolymer pellet.

14 4. Cyclohexane-insoluble cycloolefin-based random copolymer fine particles having a particle size of 1 m or more contained in 30 mg of the obtained cyclic olefin-based random copolymer pellet are obtained. The method for producing a cyclic olefin-based random copolymer pellet according to claim 12 or 13, wherein the number is not more than 60,000.

15. (A) Ethylene and

(b) A cyclic polymer having a softening temperature (TMA) of 70 ° C or more obtained by copolymerization with at least one cyclic olefin represented by the following formula [I] or [D] When a copolymer random pellet is supplied to an extruder and extruded from the extruder in a molten state, the copolymer pellet is produced.

The pellets extruded from the extruder are dried and / or mixed so that the amount of fine powder generated from the cyclic olefin-based random copolymer pellet is 100 ppm or less when the pellet is extruded. Drying and / or blending the pellets to produce a cyclic olefin-based random copolymer pellet;

· · · [I]

[In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and '~ 1 ^' 8 ぉ 11. And R b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group;

R ~ R ^'8 is rather good may have a bond to each other to form a monocyclic or polycyclic rather it may also, and the monocyclic or polycyclic double bond to each other and, R' 5 and R 'in the ⁶ or R' ⁷ and R 1 e and in may form a alkylene Li Den group];

R 18 _R 19

· · · [N]

R ′ to R are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group,

Or the carbon atom to which R 10 is bonded and the carbon atom to which R> ³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or alkylene having 1 to 3 carbon atoms. May be linked through a group,

When n = m = 0, R ¹⁵ and R ¹² or R i 5 and R _{I 9} may combine with each other to form a monocyclic or polycyclic aromatic ring.

1 6. The cyclic cyclic random copolymer pellets obtained are contained in 30 mg and have a particle size of 1 / "m or more. It is characterized in that the number of polymer particles is less than 600,000 16. The method for producing a cyclic olefin-based random copolymer pellet according to claim 15, wherein:

1 7. (a) Ethylene and

(b) a softening temperature (TMA) obtained by copolymerization with at least one kind of cyclic olefin represented by the following formula [I] or [Π] is 70 ° C or more; When the cyclic orphanic random copolymer is supplied to an extruder and extruded from the extruder in a molten state, the copolymer pellet is produced.

The cyclic olefin-based random copolymer heated in advance to a temperature of 50 ° C or higher was heated at the beginning of the melted section at the glass transition temperature (Tg) of the copolymer fed to the extruder. ), The temperature at the beginning of the melting part is set higher than the other parts of the extruder, and the rotation directions of the two screws are in the same direction. The copolymer is fed to a certain twin-screw extruder and extruded from the extruder in a molten state, and then the copolymer is subjected to a differential pressure of 90 Kg / C rrf or less before and after the polymer filter. After passing through a polymer filter after adjusting the particle size, the mixture is shaped into a pellet, and the amount of fine powder generated from the shaped cyclic olefin-based random copolymer pellet is formed. Drying and / or mixing the pellet so that the content is less than 100 ppm. The method of manufacturing Jo O Les Fi emission system run-dam copolymer Bae LESSON DOO;

· · · [I]

[In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, 1 ^ 'to 1 ^ 8 and 1 ^, R _b represents an atom or a group independently selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group;

RI ⁵ ~ R is rather good even if rather good also form a monocyclic or polycyclic bonded to each other, and the monocyclic or polycyclic ring having a double bond and, R ^'5 and R 'in the ⁶ or R' ⁷ and R 'e and in may form a alkylene Li Den group];

[π]

[In the above formula [u], p and q are 0 or positive integers, m and n are 0, 1 or 2,

The carbon atom to which R 9 or RI 0 is bonded and the carbon atom to which R is bonded or the carbon atom to which R ¹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. May be connected via

Further, when n = m = 0, R ¹⁵ and R ¹² or R> 5 and Rie may combine with each other to form a monocyclic or polycyclic aromatic ring.]

1 8. Cyclic olefin-based random copolymer fine particles with a particle size of 1 m or more contained in 30 mg of the obtained cyclic olefin-based random copolymer pellet 20. The cyclic olefin-based random copolymer according to claim 17, wherein the number is 60,000 or less. The method of manufacturing the let.