JP2002105131A - Cyclic olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclic olefinic polymer which has low birefringence, excellent mechanical characteristics, precision moldability, moisture resistance (low water absorption), and the like, is especially free from even a slight color, and has extremely high transparency. SOLUTION: This cyclic olefinic polymer characterized by comprising the copolymer of a 2 to 20C α-olefin with a cyclic olefin having a specific structure and having a light transmittance of >=85% at 400 nm, when a 3 mm-thick molded product of the polymer is measured. The preferable cyclic olefinic polymer is obtained by hydrogenating a polymer selected from an α-olefin cyclic olefin random copolymer obtained by copolymerizing the 2 to 20C α-olefin with the cyclic olefin, and its graft-modified products.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclic olefin polymer having low water absorption and excellent transparency.

[0002]

BACKGROUND OF THE INVENTION Generally, a transparent resin utilizes the property that light is easily transmitted therethrough so that the contents can be easily confirmed when made into a container or a packaging material, and that it is easy to carry and process. It has been used not only for industrial materials and general consumer materials, but also for pharmaceuticals, foods, laboratory equipment, optical applications, and the like. Specifically, it is suitably used as a transparent container for foods and pharmaceuticals, as well as lenses for optical devices such as spectacle lenses and pickup lenses, fθ lenses, and MO,
It is also used for optical recording media such as DVD and CD.

In recent years, in optical products, higher densification and higher precision have progressed, and the required performance may not be able to be satisfied by using conventionally used polymethyl methacrylate and polycarbonate. Therefore, Japanese Patent Application Laid-Open No. 11-142
The use of cyclic olefin-based polymers having low birefringence, high heat resistance and high moisture resistance as disclosed in Japanese Patent No. 645 is increasing.

Further, regarding food packaging materials, medical packaging materials, films and sheets, transparency, high moisture resistance, heat resistance,
From the viewpoints of easy disposal, light weight, and the like, conversion from a material using glass, a halogen-containing resin, a polyolefin resin, or the like to a material using a cyclic olefin polymer has begun.

On the other hand, a cyclic olefin polymer is considered to be a structurally colorless and transparent resin. However, a molded article made of a conventional cyclic olefin polymer may appear slightly colored, Was required.

[0006]

DISCLOSURE OF THE INVENTION The present invention is excellent in low birefringence, heat resistance, mechanical properties, precision moldability, moisture resistance (low water absorption) and the like, and is particularly high without any coloring. An object is to provide a cyclic olefin polymer having transparency.

[0007]

Means for Solving the Problems The present inventors have found that the above-mentioned coloring is slight light absorption seen near 400 nm in the visible light range, and hydrogenate the cyclic olefin polymer. As a result, it was found that the hue was improved, and the present invention was completed.

The cyclic olefin polymer according to the present invention comprises:
400 n, which is composed of a copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula (I) or (II) and having a thickness of 3 mm,
The light transmittance at m is 85% or more.

[0009]

Embedded image (In the above formula (I), n is 0 or 1, m is 0 or an integer of 1 or more, q is 0 or 1, and R ¹ to
R ^18, R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ^{1 5} to R ¹⁸
In may form a monocyclic or polycyclic bonded to each other, and may be monocyclic or polycyclic have a double bond, also an R ^{1 5} and R ^{1 6} or R, ^{1 7} and with a R ^{1 8} may form an alkylidene group. ),

[0010]

Embedded image (In the above formula (II), p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹
Each independently hydrogen atom ^9, a halogen atom, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ and R ^{1 0} are attached, R ^{1 3} or with the carbon atom to which R ^{1 1} is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when the n = m = 0, and R ^{1 5} R
^{1 2} or R ^{1 5} and R ^{1 9} and may form a monocyclic or polycyclic aromatic ring bonded to each other. ).

In the present invention, the number of carbon atoms is 2 to 20.
And a cyclic olefin random copolymer obtained by copolymerizing an α-olefin of the formula (I) or the cyclic olefin represented by the formula (I) or (II), and a pretreatment weight selected from a graft-modified product thereof. The coalesced polymer is preferably a cyclic olefin polymer obtained by hydrogenation treatment.

Further, it is preferable that the hydrogenation treatment is performed in a solvent containing a cyclic saturated hydrocarbon as a main component.
Further, it is preferable that the hydrogenation treatment is performed in a solvent containing 50% by weight or more of cyclohexane.

According to the present invention, plastic lenses, containers, transparent sheets or transparent boards, and optical recording media comprising the cyclic olefin polymer are provided as preferred uses of the cyclic olefin polymer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic olefin polymer according to the present invention is a copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula (I) or (II). AS made of 3mm thick molded body
A polymer having a light transmittance at 400 nm of 85% or more according to TM D1003.

The cyclic olefin polymer of the present invention is preferably obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms with a cyclic olefin represented by the following formula (I) or (II). It is obtained by hydrogenating at least one pre-treatment polymer selected from the group consisting of the obtained α-olefin / cyclic olefin random copolymer and its graft-modified product.

Here, the cyclic olefin represented by the formula (I) or (II) constituting the cyclic olefin polymer will be described. The cyclic olefin used in the present invention is
It is represented by the following formula (I) or (II).

[0017]

Embedded image

In the above formula (I), n is 0 or 1,
m is 0 or an integer of 1 or more, and q is 0 or 1. When q is 1, R ^a and R ^b are each independently an atom or a hydrocarbon group shown below, and q
Is 0, the bond between R ^a and R ^b is lost, and the carbon atoms on both sides are bonded to form a 5-membered ring.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom,
It is a bromine atom or an iodine atom.

The hydrocarbon groups each independently 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. And the aromatic hydrocarbon group includes a phenyl group and a naphthyl group. These hydrocarbon groups may have their hydrogen atoms replaced by halogen atoms.

In yet above formula ^{(I), R 1 5 ~R} 18
May be bonded to each other (together with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed may have a double bond. Here, specific examples of the formed monocyclic or polycyclic ring are shown below.

Embedded image

In the above examples, the carbon atoms numbered 1 or 2 are each represented by R ¹⁵ (R
¹⁶ ) or a carbon atom to which R ¹⁷ (R ¹⁸ ) is bonded. Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

[0023]

Embedded image

In the above formula (II), p and q are 0 or 1.
Where m and n are 0, 1 or 2. The R ¹ to R ^{1 9} are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group. The halogen atom has the same meaning as the halogen atom in the formula (I).

The hydrocarbon groups are each independently an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group. Is mentioned. 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. A cyclohexyl group is mentioned, and as the aromatic hydrocarbon group, an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group are exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. These hydrocarbon groups and alkoxy groups are
It may be substituted by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0027] Here, the carbon atom to which R ⁹ and R ^{1 0} is attached, the carbon atom to which R ^{1 3} carbon atoms or R ^{1 1} are bonded is bonded, directly or number of carbon atoms 1 to
And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are linked via an alkylene group, a group represented by R ⁹ and R ^{1 3} is, or a group represented by R ^{1 0} and R ^{1 1,} together jointly, a methylene group (-CH ₂ -), ethylene group (-CH ₂ CH ₂ -) or propylene group _{(-CH 2 CH 2 CH 2 -} ) to form one alkylene group of the.

Furthermore, when ^{n = m = 0, R 1} 5 and R ^{1 2} or R ^{1 5} and R ^{1 9} and may form an aromatic ring bonded to a monocyclic or polycyclic one another . As monocyclic or polycyclic aromatic ring in this case, for example, R ¹ as described below ⁵ and R ^{1 2}
Is a group further forming an aromatic ring.

Embedded image Here, q has the same meaning as q in the formula (II).

Specific examples of the cyclic olefin represented by the above formula (I) or (II) are shown below.
As an example,

Embedded image (Also referred to as norbornene. In the above formula, the numbers 1 to 7 represent the position numbers of carbon atoms) and derivatives obtained by substituting the compound with a hydrocarbon group. .

As the substituted hydrocarbon group, 5-methyl, 5,
6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5-phenyl, 5-benzyl, 5-tolyl, 5- (ethyl Phenyl), 5-
(Isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl), and 5,6-diphenyl.

As other derivatives, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a -
Bicyclo [2.2.1] -2-heptene derivatives such as hexahydroanthracene can be exemplified.

In addition, tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene and other tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives, tricyclo [4.4.0.1
^2,5 ] -3-undecene, 10-methyltricyclo [4.4.0.1 ^2,5 ]
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives such as -3-undecene,

Embedded image In shown as tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (in subsequent simply in. The formula of tetracyclododecene, 1 to 12 numbers indicate the position numbers of carbon.),
And derivatives thereof substituted with a hydrocarbon group.

As the hydrocarbon group of the substituent, 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl,
8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-
Dimethyl, 2,10-dimethyl, 8,9-dimethyl, 8-ethyl-9-
Methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl, 9,11,12-
Trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-
11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9-methyl, 8-ethylidene-9-ethyl,
8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8
-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9- Ethyl, 8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl
-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8-
(Biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8-
(Anthracenyl) and 5,6-diphenyl.

Still other derivatives include adducts of (cyclopentadiene-acenaphthylene adduct) with cyclopentadiene.

Further, tetracyclo [4.4.0.1^2,5.1^7,10] -3
-Dodecene derivative, pentacyclo [6.5.1.1^3,6.0^2,7.0
^9,13] -4-pentadecene and its derivatives, pentacyclo
[7.4.0.1^2,5.1^9,12.0^8,13] -3-pentadecene and its
Derivative, pentacyclo [6.5.1.1^{Three , 6}.0^{Two , 7}.0^{9 ,13}] -4,10-
Pentadecadiene compound, pentacyclo [8.4.0.1^2,5.1
^9,12.0^8,13] -3-Hexadecene and its derivatives, penta
Cyclo [6.6.1.1^3,6.0^2,7.0^{9, 14}] -4-hexadecene and
Its derivative, hexacyclo [6.6.1.1^3,6.1^10,13.0^2,7.0
^9,14] -4-Heptadecene and its derivatives, heptacyclo
[8.7.0.1^2,9.1^4,7.1^{11, 17}.0^3,8.0^12,16] -5-Eikosen
And its derivatives, heptacyclo [8.7.0.1^3,6.1^{1 0,17}.1
^12,15.0^2,7.0^11,16] -4-eicosene and its derivatives,
Heptacyclo [8.8.0.1^2,9.1^4,7.1^11,18.0^3,8.0^12,17]-Five
-Heneicosene and its derivatives, octacyclo [8.8.
0.1^2,9.1^4,7.1^11,18.1^13,16.0^3,8.0^12,17] -5-Docosene
And its derivatives, nonacyclo [10.9.1.1^4,7.1^13,20.1
^15,18.0^2,10.0^3,8.0^12,21.0^14,19] -5-pentacocene and
And its derivatives, nonacyclo [10.10.1.1^{Five , 8}.1^{1 Four , 2 1}.1^{1 6 , 1
9}.0^{2,1 1}.0^{Four , 9}.0^{1 Three , 2 Two}.0^{1 Five , 20}] -6-Hexacocene and its
And the like.

Specific examples of the cyclic olefin represented by the above formula (I) or (II) which can be used in the present invention are as described above. More specific structures of these compounds are as follows. These are shown in paragraphs [0032] to [0054] of JP-A-7-1445213. In the present invention, those exemplified in the specification can be used as cyclic olefins.

As a method for producing the cyclic olefin represented by the above formula (I) or (II), for example, a Diels-Alder reaction between cyclopentadiene and an olefin having a corresponding structure may be mentioned. I can do it.

These cyclic olefins can be used alone or in combination of two or more.

The pre-treatment polymer comprising a cyclic olefin used in the present invention is prepared by the above-mentioned formula (I) or (I)
Using the cyclic olefin represented by I), for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, and
115916, 61-271308, 61-272216, 62-25240
It can be produced by appropriately selecting conditions in accordance with the methods proposed in JP-A Nos. 6 and 62-252407.

The α-olefin / cyclic olefin random copolymer having 2 to 20 carbon atoms contains a structural unit derived from the α-olefin in an amount of usually 5 to 95 mol%, preferably 20 to 80 mol%. % Of structural units derived from cyclic olefins, usually in an amount of 5 to 95 mol%, preferably 20 to 80 mol%.
The composition ratio of α-olefin and cyclic olefin is
It is measured by ¹³ C-NMR.

Here, an α-olefin / cyclic olefin random copolymer having 2 to 20 carbon atoms, α
-The olefin will be described. The α-olefin may be linear or branched, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene,
Linear α-olefin having 2 to 20 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; 3-methyl-1-butene;
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, etc. having 4 to 2 carbon atoms
And 0 branched α-olefins. Among these, linear α-olefins having 2 to 4 carbon atoms are preferred, and ethylene is particularly preferred. Such linear or branched α-olefins can be used alone or in combination of two or more.

The α-olefin / cyclic olefin random copolymer has 2 to 20 carbon atoms as described above.
The structural units derived from α-olefins and the structural units derived from cyclic olefins are randomly arranged and bonded to have a substantially linear structure. The fact that this copolymer is substantially linear and does not have a substantially gel-like cross-linked structure means that when this copolymer is dissolved in an organic solvent, the solution contains an insoluble component. You can confirm by not having. For example, when the intrinsic viscosity [η] is measured, it can be confirmed by completely dissolving this copolymer in decalin at 135 ° C.

In the α-olefin / cyclic olefin random copolymer used in the present invention, at least a part of the cyclic olefin represented by the above formula (I) or (II) has the following formula (III) or (IV) Are considered to constitute the repeating unit represented by.

[0044]

Embedded image In the above formula (III), n, m, q, R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meanings as in formula (I).

[0045]

Embedded image In the above formula (IV), n, m, p, q and R ^{1 to} R ^1
9 has the same meaning as in formula (II).

The α-olefin used in the present invention
If necessary, the cyclic olefin random copolymer may have a structural unit derived from another copolymerizable monomer within a range that does not impair the object of the present invention.

Examples of such other monomers include olefins other than the above-mentioned α-olefins having 2 to 20 carbon atoms or cyclic olefins. Specifically, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene and cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-
Cycloolefins such as 1H-indene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2- Non-conjugated dienes such as norbornene can be mentioned. These other monomers can be used alone or in combination.

When the α-olefin / cyclic olefin random copolymer contains structural units derived from other monomers as described above, it is usually 20 mol%.
Hereinafter, it is more preferable that the amount be 10 mol% or less.

The α-olefin / cyclic olefin random copolymer used in the present invention has 2 to 20 carbon atoms.
And the cyclic olefin represented by the formula (I) or (II) can be produced by the production method disclosed in the above publication. Among these, a production method in which the copolymerization reaction is carried out in a hydrocarbon solvent and a catalyst formed from a vanadium compound and an organic aluminum compound soluble in the hydrocarbon solvent is preferable.

In this copolymerization reaction, a solid metallocene catalyst of Group IV of the periodic table may be used. Here, the solid group IV metallocene catalyst of the periodic table is a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organic aluminum oxy compound, and an organic aluminum compound optionally blended. Catalyst. Here, examples of the transition metal of Group IV of the periodic table include zirconium, titanium and hafnium, and these transition metals are catalysts having a ligand containing at least one cyclopentadienyl skeleton. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group or an indenyl group, a tetrahydroindenyl group, and a fluorenyl group which may be substituted with an alkyl group. These groups may be bonded via another group such as an alkylene group. Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

As the organoaluminum oxy compound and the organoaluminum compound, those usually used for producing polyolefins can be used. Examples of such a solid group IV metallocene catalyst of the periodic table include those described in, for example, JP-A-61-221206, JP-A-64-106, and JP-A-2-173112. Can be used.

In the present invention, the graft-modified product used as the polymer before the hydrogenation treatment is a graft-modified product of the above-mentioned ethylene / cyclic olefin random copolymer.

Examples of the modifier used herein include unsaturated carboxylic acids, and specific examples thereof include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid and crotonic acid. , Isocrotonic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,
Unsaturated carboxylic acids such as 3-dicarboxylic acid (nadic ^TM), further derivatives such as unsaturated carboxylic acid anhydrides of these unsaturated carboxylic acids, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, Examples thereof include unsaturated carboxylic acid ester compounds.

More specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, citraconic anhydride, maleyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

Of these, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic anhydrides such as maleic acid, Nadic acid ^TM and anhydrides of these acids are preferably used. These modifiers can be used in combination of two or more.

Such a graft-modified ethylene / cyclic olefin random copolymer can be produced by blending a modifier with the copolymer so as to obtain a desired modification ratio and graft-polymerizing the copolymer. A modified product having a high modification rate may be prepared in advance, and then the modified product and an unmodified ethylene / cyclic olefin random copolymer may be mixed so as to have a desired modification rate.

In order to obtain a graft-modified product from the ethylene / cyclic olefin random copolymer and a modifying agent, conventionally known polymer modification methods can be widely applied. For example, a method in which a modifier is added to an ethylene / cyclic olefin random copolymer in a molten state to cause graft polymerization (reaction), or a method in which a modifier is added to a solvent solution of the ethylene / cyclic olefin random copolymer to cause a graft reaction. A graft-modified product can be obtained by a method or the like.

Such a graft reaction is usually carried out at 60 to 3
It is performed at a temperature of 50 ° C. The graft reaction can be performed in the presence of a radical initiator such as an organic peroxide and an azo compound.

In the present invention, any one of the above-mentioned ethylene / cyclic olefin random copolymers and graft-modified products thereof can be used alone as the polymer before the hydrogenation treatment, Two or more or two or more different groups can be used in combination.

The cyclic olefin polymer according to the present invention comprises
The glass transition temperature (Tg) measured by DSC (heating rate 10 ° C./min) is preferably from 60 to 230 ° C., and more preferably from 70 to 210 ° C.

The cyclic olefin polymer is amorphous or low-crystalline and has a crystallinity, as measured by X-ray diffraction, of usually 20% or less, preferably 10%.
Or less, more preferably 2% or less.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is preferably 0.01 to 20 dl / g,
It is more preferably 0.05 to 10 dl / g, and still more preferably 0.08 to 5 dl / g.

Temperature 260 according to ASTM D1238
° C, melt flow index (MF) measured at a load of 2.16 kg
R) is generally 0.1 to 200 g / 10 min, preferably 1 to 100 g / 10 min, and more preferably 3 to 60 g.
/ 10 minutes.

The softening point is usually 30 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further more preferably 90 to 250 ° C., particularly as the softening point (TMA) measured by a thermomechanical analyzer. Is 100 to 200 ° C. Here, the measurement of the softening point was performed based on the thermal deformation behavior of a sheet having a thickness of 1 mm using a Thermo Mechanical Analyzer manufactured by DuPont. That is, a quartz needle with a load of 49 g is placed on the sheet and placed at 5 ° C /
The temperature was raised at a speed of minute and the temperature at which the needle penetrated 0.635 mm into the sheet was defined as the softening point (TMA).

Among the above-mentioned cyclic olefin-based polymers, α-olefin / cyclic olefin random copolymer is obtained by hydrogenation treatment, has a softening point (TMA) of 80 ° C. or more, and has an intrinsic viscosity [η Is preferably 0.05 to 10 dl / g.

Further, those obtained by hydrogenating an ethylene / tetracyclododecene copolymer or an ethylene / norbornene copolymer are preferred.

In the hydrogenation treatment in the present invention, it is preferable to hydrogenate the above-mentioned polymer before treatment in a solvent containing a cyclic saturated hydrocarbon as a main component in the presence of a hydrogenation catalyst. As a solvent for the polymer before treatment, cyclohexane,
Examples include n-hexane, decalin, cycloheptane, cyclopentane, n-heptane, n-octane and the like. These can be used alone or in combination of two or more.

Among these, cyclohexane and n-hexane are preferable, and a solvent containing cyclohexane at 50% by weight or more is particularly preferable.

As the hydrogenation catalyst metal, Pt, Rh,
Pd, Cu, Y, Fe, Ru, W, Zn and the like can be mentioned. Preferably, Raney nickel, palladium on activated carbon, and Wilkinson complex are used.

The hydrogenation may be carried out, for example, by dissolving the polymer before treatment in 1 to 30% by weight, preferably 3 to 20% by weight, in the solvent for hydrogenation in an amount of 0.5 to 1% based on the polymer.
A catalyst (as a metal) having a concentration of 0% by weight is added, and the reaction is carried out at a reaction temperature of 20 to 200 ° C, preferably 40 to 120 ° C, and a hydrogen partial pressure of 0.1 to 20 MPa, preferably 0.5 to 10 MPa. The reaction time is appropriately selected according to the required degree of hue improvement, and is usually selected from 5 minutes to 12 hours, preferably from 5 minutes to 6 hours. After the reaction, the catalyst is removed by filtration or the like.

In the present invention, a resin composition obtained by further blending another resin with the above-mentioned cyclic olefin polymer, if necessary, can be used. Other resins are added within a range that does not impair the purpose of the present invention.

Here, other resins which can be added to the cyclic olefin polymer are exemplified below. (1) Polymers derived from hydrocarbons having one or two unsaturated bonds Specifically, for example, polyethylene, polypropylene, polymethylbutene-1, poly4-methylpentene-1, polybutene-1 and Examples include polyolefins such as polystyrene. These polyolefins may have a crosslinked structure. (2) Halogen-containing vinyl polymer Specific examples include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, and chlorinated rubber.

(3) Polymers derived from α, β-unsaturated acids and derivatives thereof Specifically, polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, or copolymers with the monomers constituting the above polymers Polymers such as acrylonitrile / butadiene / styrene copolymer, acrylonitrile / styrene copolymer, acrylonitrile / styrene
Styrene / acrylate copolymers and the like can be mentioned.

(4) Polymers Derived from Unsaturated Alcohols and Amines, or Acyl Derivatives or Acetals of Unsaturated Alcohols Specifically, polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, polyvinyl benzoate, polymaleic acid Examples thereof include vinyl, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, and a copolymer with a monomer constituting the polymer, for example, an ethylene / vinyl acetate copolymer.

(5) Polymer Derived from Epoxide Specific examples include a polymer derived from polyethylene oxide or bisglycidyl ether. (6) Polyacetal Specifically, polyoxymethylene, polyoxyethylene,
Examples of the comonomer include polyoxymethylene containing ethylene oxide. (7) Polyphenylene oxide (8) Polycarbonate (9) Polysulfone (10) Polyurethane and urea resin

(11) Diamine and dicarboxylic acid and / or
Or polyamides and copolyamides derived from aminocarboxylic acids or the corresponding lactams, specifically nylon 6, nylon 66, nylon 11,
Nylon 12 and the like. (12) Polyesters derived from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or corresponding lactones Specific examples include polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate, and the like.

(13) Polymer having a crosslinked structure derived from aldehyde and phenol, urea or melamine Specific examples thereof include phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin and the like. (14) Alkyd resin Specific examples include glycerin / phthalic acid resin.

(15) Unsaturated polyester resins and halogen-containing modified resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and obtained using vinyl compounds as crosslinking agents. (16) Natural Polymers Specific examples include cellulose, rubber, protein, and derivatives thereof such as cellulose acetate, cellulose propionate, and cellulose ether.

(17) Soft Polymer For example, a soft polymer containing a cyclic olefin component, an α-olefin-based copolymer, an α-olefin-diene-based copolymer, an aromatic vinyl-based hydrocarbon / conjugated diene-based soft copolymer. Examples include a polymer, a soft polymer or a copolymer comprising isobutylene or isobutylene / conjugated diene.

Further, the above-mentioned cyclic olefin polymer is
Other optional components may be blended as long as the objects of the present invention are not impaired.Examples include weather stabilizers, stabilizers such as heat stabilizers, crosslinking agents, crosslinking assistants, antistatic agents, and flame retardants. , Slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, mineral oil softener, petroleum resin, natural oil,
Synthetic oils, waxes, organic or inorganic fillers and the like are added as required.

Examples of the ultraviolet absorbers of the weather stabilizer which are blended as such optional components include benzophenone compounds, benzotriazole compounds, nickel compounds and hindered amine compounds.
2 ', 4,4'-tetrahydroxybenzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3'-t-butyl-5'-butylphenyl) benzotriazole, nickel salt of bis (3,5-di-t-butyl-4-hydroxybenzoylphosphonic acid ethyl ester, bis (2,2 ', 6,6 '-Tetramethyl-4-piperidine) sebacate and the like.

Examples of the stabilizer contained as an optional component include tetrakis [methylene-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxazamide bis [ethyl-3- (3, Phenolic antioxidants such as 5-di-t-butyl-4-hydroxyphenyl) propionate; and fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 1,2-hydroxystearate. These can be used in combination. For example, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is used in combination with zinc stearate or calcium stearate. Can be.

As the stabilizer, for example, distearylpentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol-pentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis
(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol-A-pentaerythritol diphosphite, tris (2,4-di-
(t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphite, bis (2,
Phosphorus stabilizers such as 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite can also be used. These stabilizers can be used alone or in combination of two or more.

Examples of the organic or inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, Calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica,
Examples include asbestos, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, and the like.

As a method for mixing the cyclic olefin polymer of the present invention with other resin components, additives and the like, a method known per se can be applied. For example, there is a method of simultaneously mixing the components.

The cyclic olefin polymer thus obtained has an improved hue and has a light transmittance at 400 nm of 85% or more, preferably 87%, at 400 nm as measured by a spectrophotometer using a molded product having a thickness of 3 mm. %, More preferably 89% or more.

This polymer has high transparency and is excellent in low birefringence, heat resistance, mechanical properties, precision moldability, moisture resistance (low water absorption), etc. It is preferably used for a transparent sheet or a transparent board, an optical recording medium and the like.

Specific applications include plastic lenses such as spherical lenses, aspherical lenses, and Fresnel lenses,
Optical components such as prisms, light guide plates, reflectors, and optical fibers; optical recording media such as CD, MD, DVD, MO, and PD; transparent boards; test tubes, vials, ampules,
Pharmaceuticals such as tablet bottles, prefilled syringes, disposable syringes, analysis cells, infusion bags, blood collection tubes, etc.
Medical containers; wide-mouth containers; shampoo containers, coffee containers, seasoning containers, beverage containers, and other daily miscellaneous / food containers; transparent sheets. Among these, plastic lenses, containers, transparent sheets and boards, and optical recording media are particularly preferred.

[0089]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The measurement of the light transmittance in this example was performed using a spectrophotometer, and the sample was measured at a cylinder temperature of 270 ° C. and a mold temperature of 115 ° C. using an injection molding machine (IS-50 manufactured by Toshiba Machine Co., Ltd.). Press-formed 130mm x 120mm
A square plate of 3 mm (thickness) was used.

(Example 1) Glass transition temperature (Tg) 14
A random copolymer of ethylene and tetracyclododecene having an intrinsic viscosity [η] of 0.5 dl / g at 0 ° C. was dissolved in cyclohexane to adjust the concentration to 15% by weight. Solution 3
1.3 g of a Raney nickel catalyst (nickel content: 40% by weight) was added to 00 g, hydrogen partial pressure was 3 MPa, and temperature was 100 ° C.
For 4 hours. After filtering the catalyst, the reaction solution was added into acetone to precipitate a polymer. A sheet having a thickness of 3 mm was press-formed using this polymer, and the light transmittance at 400 nm was measured. Table 1 shows the results.

Example 2 A hydrogenation treatment was performed in the same manner as in Example 1, except that 3 g of palladium supported on activated carbon was used as a catalyst for the hydrogenation reaction in terms of the amount of palladium. A sheet having a thickness of 3 mm was press-formed using the obtained polymer, and the light transmittance at 400 nm was measured. Table 1 shows the results.

(Comparative Example) For comparison, the ethylene / tetracyclododecene random copolymer, which is the polymer before treatment used in Examples 1 and 2, was dissolved in cyclohexane to adjust the concentration to 15% by weight. 300 g of the solution was heated at a temperature of 100 ° C. for 4 hours without performing hydrogenation treatment,
After cooling, the mixture was added to acetone to precipitate a polymer. A sheet having a thickness of 3 mm was press-formed using the obtained polymer, and the light transmittance at 400 nm was measured. Table 1 shows the results.

[0093]

[Table 1]

[0094]

The cyclic olefin polymer according to the present invention is excellent in low birefringence, heat resistance, mechanical properties, precision moldability, moisture resistance (low water absorption), etc. Since it has extremely high transparency without any coloring, it can be used for optical molded products such as plastic lenses, various containers for medicine, medical care, food, etc., transparent sheets and boards, CD, MD, DVD, MO, PD, etc. It is suitably used as an optical recording medium.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 1/04 G02B 1/04 G11B 7/24 526 G11B 7/24 526M // C08L 23:08 C08L 23: 08 23:26 23:26 45:00 45:00 F term (reference) 4F071 AA14X AA15X AA20X AA21X AF30Y AG05 AG07 AH05 AH19 BC01 BC04 4J100 AA02P AA03P AA04P AA07P AA09P AA15P AA16P AA17Q AABAQAQAQAQ19AQAQAQAQAQAQAQQ BB07Q BC04Q BC33Q BC43Q BC44Q BC48Q BC49Q BC55H BC55Q CA04 CA31 DA62 HA03 HA53 HB13 HC29 HC30 HC36 HC54 HD22 JA33 JA35 JA36 JA58 5D029 KA12

Claims (8)

[Claims] 1. A molded product having a thickness of 3 mm, comprising a copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula (I) or (II): A cyclic olefin-based polymer having a light transmittance at 400 nm of 85% or more; (In the above formula (I), n is 0 or 1, m is 0 or an integer of 1 or more, q is 0 or 1, and R ¹ to
R ^18, R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ^{1 5} to R ¹⁸
In may form a monocyclic or polycyclic bonded to each other, and may be monocyclic or polycyclic have a double bond, also an R ^{1 5} and R ^{1 6} or R, ^{1 7} and with a R ^{1 8} may form an alkylidene group. ), Embedded image (In the above formula (II), p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹
Each independently hydrogen atom ^9, a halogen atom, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ and R ^{1 0} are attached, R ^{1 3} or with the carbon atom to which R ^{1 1} is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when the n = m = 0, and R ^{1 5} R
^{1 2} or R ^{1 5} and R ^{1 9} and may form a monocyclic or polycyclic aromatic ring bonded to each other. ). 2. An α-olefin / cyclic olefin random copolymer obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms with a cyclic olefin represented by the above formula (I) or (II). The cyclic olefin polymer according to claim 1, wherein the polymer is obtained by subjecting a pre-treatment polymer selected from the group consisting of: and a graft-modified product thereof to a hydrogenation treatment. 3. The cyclic olefin polymer according to claim 2, wherein the hydrogenation treatment is performed in a solvent containing a cyclic saturated hydrocarbon as a main component. 4. The cyclic olefin polymer according to claim 2, wherein the hydrogenation treatment is performed in a solvent containing 50% by weight or more of cyclohexane. 5. A plastic lens comprising the cyclic olefin polymer according to claim 1. 6. A container comprising the cyclic olefin polymer according to claim 1. 7. A transparent sheet or transparent board comprising the cyclic olefin polymer according to claim 1. 8. An optical recording medium comprising the cyclic olefin polymer according to claim 1.