JP2000119474A - Cycloolefin resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cycloolefin resin composition which has a small birefringence and a low glass transition temperature by compounding a cycloolefin resin with a specified amount of a compound for reducing glass transition temperature. SOLUTION: A cycloolefin resin selected from among (A) random copolymers of ethylene and a monomer represented by formula I or II, (B) ring-opening (co)polymers of a monomer represented by formula I or II, (C) hydrogenation products of polymer B, and (D) graft modification products of polymers A, B, and C is compounded with 0.1-30 wt.% compound for reducing glass transition temperature, giving a resin composition which has a glass transition temperature at least 5 deg.C lower than that of the cycloolefin resin and gives a molded item having a birefringence equivalent to that of the resin. In the formulas, n, k, p, and q are each 0 or 1; m is an integer; r and s are each 0-2; R1 to R18, Ra, and Rb are each H, halogen, a hydrocarbon group, or the like; and R21 to R39 are each H, halogen, a hydrocarbon group, alkoxy, or the like. The compound for reducing glass transition temperature is an org. compound having a mol.wt. of 100-10,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cyclic olefin resin composition and its use, and more particularly, to a cyclic olefin resin composition comprising a cyclic olefin resin and a glass transition temperature reducing compound, and a use of the composition. Things.

[0002]

BACKGROUND ART As materials for optical components such as substrates for optical recording media and lenses, resin materials such as polycarbonate, polymethyl methacrylate (PMMA), and cyclic olefin resins have been conventionally used. Among these resins, the cyclic olefin-based resin is excellent in that it has smaller birefringence than polycarbonate, has lower water absorption than PMMA, and has less change in physical properties due to moisture.

In recent years, a resin material having even smaller birefringence has been required due to an increase in recording density and a reduction in the wavelength of laser light used. As a method of reducing the birefringence of a cyclic olefin-based resin, a method of increasing the polarization density of electrons in the direction perpendicular to the main chain in the plane direction has conventionally been adopted. However, when the birefringence is further reduced by such a method, a problem that the glass transition temperature increases and the moldability is impaired may occur.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has a low birefringence and a low glass transition temperature even with a large bulky monomer content. It is an object to provide a composition and an optical component comprising the composition.

[0005]

SUMMARY OF THE INVENTION The cyclic olefin resin composition according to the present invention comprises (A) the following (A-1), (A-2), (A-3) and (A-3)
4) A composition comprising at least one cyclic olefin-based resin selected from the group consisting of: and (B) a glass transition temperature reducing compound, wherein the (B) glass transition temperature reducing compound is the (A) cyclic 0.1 for olefin resin
-30% by weight, the glass transition temperature of the composition is lower than the glass transition temperature of the cyclic olefin resin (A) by 5 ° C. or more, and the birefringence of a molded article obtained by molding the composition. Is characterized by being equivalent to the birefringence of a molded article obtained by molding the cyclic olefin resin (A); (A-1) ethylene and represented by the following general formula (I) or (II) (A-2) a ring-opened polymer or copolymer of a cyclic olefin represented by the following general formula (I) or (II), (A-3) a hydride of the above (A-2) ring-opening polymer or copolymer, and (A-4) a graft modification of the above (A-1), (A-2) or (A-3) object;

[0006]

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Wherein n is 0 or 1, m is 0 or a positive integer, k is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and R ^{15 to} R ¹⁸
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 ¹⁶ , or R ¹⁷ R ¹⁸ may form an alkylidene group. )

[0008]

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[0009] (wherein, p and q is 0 or an integer of 1 or more, r and s is 0, 1 or 2, R ²¹ ~
R ³⁹ is independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and the carbon atom to which R ²⁹ (or R ³⁰ ) is bonded. And the carbon atom to which R ³³ or R ³¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when r = s = 0, R ³⁵ and R ³² Alternatively, R ³⁵ and R ³⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ).

The glass transition temperature of the (A) cyclic olefin resin is usually 70 ° C. or higher. The (B) glass transition temperature reducing compound has a molecular weight of, for example, 100 to 10
000, which is an organic compound compatible with the (A) cyclic olefin-based resin.

An injection-molded article according to the present invention is characterized by comprising the cyclic olefin resin composition. The optical component according to the present invention is characterized by being made of the cyclic olefin-based resin composition. As optical components,
There are lenses, substrates for optical recording media, prisms, reflectors, and the like.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the cyclic olefin resin composition according to the present invention and its use will be specifically described.

The cyclic olefin resin composition according to the present invention is a composition comprising (A) a cyclic olefin resin and (B) a glass transition temperature reducing compound.

(A) Cyclic Olefin Resin (A) The cyclic olefin resin used in the present invention is (A)
-1) Ethylene obtained by copolymerizing ethylene with a cyclic olefin represented by the following general formula (I) or (II)
Cyclic olefin random copolymer (A-2) Ring-opened polymer or copolymer of cyclic olefin represented by the following general formula (I) or (II), (A-3) Ring-opening (A-2) A hydride of a polymer or a copolymer, and (A-4) (A-1), (A-
2) or at least one cyclic olefin resin selected from the group consisting of the graft-modified products of (A-3).

First, the cyclic olefin represented by the general formula (I) or (II), which is a monomer used for preparing the cyclic olefin resin used in the present invention, will be described.

The cyclic olefin used for preparing the cyclic olefin resin has the following general formula (I) or (I)
I).

[0017]

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In the above general formula (I), n is 0 or 1, m is 0 or a positive integer, and k is 0 or 1. When k is 1, R ^a and R ^b are each independently the following atom or hydrocarbon group, and k is 0
In the case of the above, each bond is 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, a bromine atom or an iodine atom.

Examples of the hydrocarbon group independently include an alkyl group usually 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. Is a cyclohexyl group, and the aromatic hydrocarbon group is a phenyl group, a naphthyl group or the like. These hydrocarbon groups may be substituted with a halogen atom.

Further, in the above formula (I), R ^{15 to} 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. Specific examples of the monocyclic or polycyclic rings formed here are shown below.

[0022]

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In the above examples, the carbon atoms numbered 1 or 2 are the carbon atoms to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) are bonded in the general formula (I), respectively. Is shown.

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.

[0025]

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In the general formula (II), p and q are 0 or a positive integer, and r and s are 0, 1 or 2. R ^{21 to} R ³⁹ 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 above formula (I). Further, as the hydrocarbon group, each independently an alkyl group having 1 to 20 carbon atoms,
Examples thereof include a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, as the alkyl group, 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;
Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. Can be mentioned. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

These hydrocarbon groups and alkoxy groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Here, the carbon atom to which R ²⁹ and R ³⁰ are bonded and the carbon atom to which R ³³ is bonded or the carbon atom to which R ³¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. And may be bonded via That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ²⁹ and R ³³ , or the groups represented by R ³⁰ and R ³¹ together, The alkylene group forms any one of a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —), and a propylene group (—CH ₂ CH ₂ CH ₂ —).

Further, when r = s = 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. In this case, as the monocyclic or polycyclic aromatic ring, for example, the following r = s = 0
In the above, there can be mentioned groups in which R ³⁵ and R ³² further form an aromatic ring.

[0030]

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Here, q has the same meaning as q in formula (II). The cyclic olefin represented by the general formula (I) or (II) as described above is more specifically exemplified below.

Examples of the cyclic olefin forming the cyclic olefin resin (A) include:

[0033]

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(In the above formula, the numbers 1 to 7 indicate the position numbers of carbon atoms) and the compound is substituted with a hydrocarbon group. Derivatives can be mentioned.

The hydrocarbon groups include 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- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenylyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthryl), 5 And groups such as 6,6-diphenyl.

Still other derivatives include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-
Tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10
Bicyclo [2.2.1]-such as a-hexahydroanthracene
A 2-heptene derivative 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
- tricyclo [4.3.0.1 ^2,5] -3- decene derivatives such as methyl tricyclo [4.3.0.1 ^2,5] -3- decene, tricyclo [4.4.0.1 ^2,5] -3- undecene, 10-methyl Tricyclo [4.4.0.1 ^2,5 ] -3-undecene and other tricyclo [4.4.
0.1 ^2,5 ] -3-undecene derivatives,

[0038]

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Tetracyclo [4.4.0.1 ^2,5 .1 represented by the [0039]
^7,10 ] -3-dodecene (in the above formula, the numbers 1 to 12 indicate the position numbers of carbon atoms), derivatives thereof substituted with a hydrocarbon group, and hydrogen atoms in which at least a part of the other atoms is another atom Can be mentioned.

Here, as a hydrocarbon group or a substituent atom,
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, 9.1
1,12-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-Propilidene-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- (biphenylyl), 8- (β-naphthyl), 8- (α-
Groups or atoms such as naphthyl), 8- (anthryl), and 5,6-diphenyl.

[0041] Furthermore, - tetracyclo such (cyclopentadiene acenaphthylene adduct) and adduct of cyclopentadiene [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives, 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 derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene and derivatives thereof, pentacyclo [6.6.1.1 ^{3 , 6.0} 2,7.0 ^9,14 ]
-4-hexadecene and its derivatives, 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-eicosene and its derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .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] -5-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, Nonashikuro ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .0} 2, ¹⁰ .
0 ^3,8 .0 ^12,21 .0 ^14,19] such as 5-pentacosene and its derivatives.

The specific examples of the cyclic olefin represented by the general formula (I) or (II) which can be used in the present invention are as described above. Japanese Patent Application Laid-Open No. Hei 7-
No. 145213, paragraph numbers [0032] to [005].
4], and those exemplified herein can be used as the cyclic olefin in the present invention.

The cyclic olefin represented by the above general formula (I) or (II) can be produced by a Diels-Alder reaction between cyclopentadiene and an olefin having a corresponding structure.

These cyclic olefins can be used alone or in combination of two or more. The cyclic olefin resin (A) used in the present invention can be prepared by using the cyclic olefin represented by the general formula (I) or (II) described above, for example, in JP-A-60-168708 and JP-A-6-168708.
1-1120816, 61-115912, 61
-115916, 61-271308, 61-
Nos. 272216, 62-252406 and 62
According to a method proposed by the present applicant in a gazette such as 252407 or the like, it can be produced by appropriately selecting conditions.

(A-1) The ethylene / cyclic olefin random copolymer is a copolymer in which ethylene and the above-mentioned cyclic olefin are bonded at random, and usually contains 20 to 95 mol% of a structural unit derived from ethylene. , Preferably 30 to
In a proportion of 90 mol%, the structural unit derived from the cyclic olefin is usually 5 to 80 mol%, preferably 1 to 80 mol%.
It is contained at a ratio of 0 to 70 mol%. The composition ratio of the constituent units derived from ethylene and the constituent units derived from the cyclic olefin is measured by ¹³ C-NMR.

In the (A-1) ethylene / cyclic olefin random copolymer, the structural units derived from ethylene and the structural units derived from the cyclic olefin are randomly arranged and bonded, It has a substantially linear structure. The fact that the copolymer is substantially linear and does not have a substantially gel-like cross-linked structure means that when the 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, this copolymer is 135
It can be confirmed by complete dissolution in decalin at ° C.

In the (A-1) ethylene / cyclic olefin random copolymer used in the present invention, at least a part of the cyclic olefin represented by the above general formula (I) or (II) has the following general formula (III) ) Or (IV).

[0048]

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

[0050]

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In the above general formula (IV), p, q, r,
s and R ^{21 to} R ³⁹ have the same meaning as in formula (II). The (A-1) ethylene / cyclic olefin random copolymer used in the present invention has a structural unit derived from another copolymerizable monomer as necessary within a range not to impair the purpose of the present invention. May be.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic olefin. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 3-hexene, 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, 1-octene , 1-decene, 1-
Linear or branched α-olefins having 3 to 20 carbon atoms such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cyclobutene;
Cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene and cyclooctene, 3a, 5,6,7
cycloolefins such as a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, Non-conjugated dienes such as dicyclopentadiene and 5-vinyl-2-norbornene can be mentioned.

These other monomers can be used alone or in combination. (A-1) In the ethylene / cyclic olefin random copolymer, the constituent unit derived from the other monomer as described above is usually contained in an amount of 20 mol% or less, preferably 10 mol% or less. Is also good.

The (A-1) ethylene / cyclic olefin random copolymer used in the present invention is disclosed in the above publication using ethylene and the cyclic olefin represented by the general formula (I) or (II). It can be manufactured by the manufacturing method described above. Among these, this copolymerization is carried out in a hydrocarbon solvent, and the (A-1) ethylene / cyclic olefin random copolymer is used as a catalyst using a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent. It is preferred to produce a polymer.

In this copolymerization reaction, a solid Group 4 metallocene catalyst can also be used. Here, the solid group 4 metallocene-based catalyst is a catalyst comprising a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organic aluminum oxy compound, and an organic aluminum compound optionally added. Here, the transition metal of Group 4 is zirconium, titanium or hafnium, and these transition metals have a ligand containing at least one cyclopentadienyl skeleton. Here, examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group which may be substituted by an alkyl group. These groups may be bonded via another group such as an alkylene group. The ligand other than the ligand having a cyclopentadienyl skeleton is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a halogen, or the like.

Further, as the organoaluminum oxy compound and the organoaluminum compound, those usually used for producing an olefin resin can be used. Such solid group 4 metallocene catalysts are described, for example, in JP-A-61-221206, JP-A-64-106, and JP-A-2-173112.

(A-2) In the ring-opened polymer or ring-opened copolymer of a cyclic olefin, the compound represented by the general formula (I) or (II)
It is considered that at least a part of the cyclic olefin represented by the formula (1) constitutes a repeating unit represented by the following general formula (V) or (VI).

[0058]

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

[0060]

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In the above general formula (VI), p, q, r,
s and R ^{21 to} R ³⁹ have the same meaning as in the above formula (II). Such a ring-opening polymer or ring-opening copolymer can be produced by the production method disclosed in the above-mentioned gazette,
For example, it can be produced by polymerizing or copolymerizing the cyclic olefin represented by the general formula (I) in the presence of a ring-opening polymerization catalyst.

Examples of such a ring-opening polymerization catalyst include a catalyst comprising a halide, nitrate or acetylacetone compound of a metal such as ruthenium, rhodium, palladium, osmium, indium or platinum, and a reducing agent.
Alternatively, a catalyst comprising a halide or acetylacetone compound of a metal such as titanium, palladium, zirconium or molybdenum and an organoaluminum compound can be used.

The hydride of the ring-opening polymer or copolymer (A-3) used in the present invention can be obtained by synthesizing the ring-opening polymer or copolymer (A-2) obtained as described above. By hydrogenation in the presence of a hydrogenation catalyst.

In the hydride of the ring-opening polymer or copolymer (A-3), the compound represented by the general formula (I) or the compound represented by the general formula (I
It is considered that at least a part of the cyclic olefin represented by I) has a repeating unit represented by the following general formula (VII) or (VIII).

[0065]

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In the general formula (VII), n, m, k
And R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meaning as in the above formula (I).

[0067]

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In the general formula (VIII), p, q,
r, s and R ^{21 to} R ³⁹ have the same meaning as in the above formula (II). (A-4) The graft modified product of the cyclic olefin resin is
The ethylene / cyclic olefin random copolymer (A-1)
A graft modified product of the above-mentioned ring-opened polymer or copolymer of the cyclic olefin (A-2), or a graft-modified product of the above-mentioned hydride of the ring-opened polymer or copolymer (A-3). is there.

As the modifier, unsaturated carboxylic acids are usually used. Examples of the unsaturated carboxylic acids used here include (meth) acrylic acid, maleic acid,
Fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and endocis
Unsaturated carboxylic acids such as -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^™ ), and
Derivatives of these unsaturated carboxylic acids, for example, unsaturated carboxylic anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic imides and ester compounds of unsaturated carboxylic acids can be mentioned.

Specific examples of the unsaturated carboxylic acid derivatives include maleic anhydride, citraconic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

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

The modification rate of the graft-modified cycloolefin resin used in the present invention is desirably 10 mol% or less. Such a graft modified product of a cyclic olefin-based resin can be produced by blending a modifier with a cyclic olefin-based resin so as to have a desired modification rate and graft-polymerizing the same, or a modified product having a high modification rate in advance. And then mixing this modified product with an unmodified cyclic olefin-based resin.

In order to obtain a graft-modified product of a cyclic olefin resin from a cyclic olefin resin and a modifier, conventionally known methods for modifying a polymer can be widely applied.
For example, a graft-modified product is obtained by a method of adding a modifier to a molten cyclic olefin-based resin and performing graft polymerization (reaction), or a method of adding a modifier to a solvent solution of the cyclic olefin-based resin and performing a graft reaction. be able to.

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, (A-1), (A-2), (A-3) and (A-4)
Can be used alone, or they can be used in combination. Of these, the ethylene / cyclic olefin random copolymer (A-1) is preferably used.

Such a cyclic olefin resin (A) has a melt flow rate (MFR; ASTM D123).
8, 260 ° C, under a 2.16 kg load) is 0.01 to 2
It is preferably in the range of 00 g / 10 min, preferably 0.1 to 100 g / 10 min.
It is preferably 70 ° C. or higher, and the crystallinity measured by X-ray diffraction is usually 0 to 20%,
Preferably it is 0 to 2%.

The glass transition temperature of the cyclic olefin resin (A) is usually 70 ° C. or higher, preferably 90 to 17 ° C.
It is in the range of 0 ° C. Glass transition temperature reducing compound The glass transition temperature reducing compound used in the present invention has a molecular weight of 100 to 10,000, preferably 150 to 500.
0, more preferably 200 to 3000 organic compounds, for example, hydrocarbon compounds such as chain hydrocarbon compounds and cyclic hydrocarbon compounds, and esters, ethers, amines, amides, imides, and the like derived from the hydrocarbon compounds. Fatty acids, aromatic compounds and the like can be mentioned. These compounds may be artificially synthesized or natural products, or components extracted or purified therefrom or derivatives thereof.

Specific examples of the glass transition temperature reducing compound include liquid paraffin, wax, fatty acid ester, fatty acid amide, higher alcohol, terpene resin and the like. More specifically, sorbitan distearate, pentaerythritol diester Stearate, paraffin wax, fatty acid amide (oleylamide, stearylamide, ethylenebisstearylamide, palmitylamide, etc.), low molecular weight polypropylene, polyethylene wax, neopentyl polyol fatty acid ester, fatty acid monoglyceride, fatty acid diglyceride, pentaerythritol fatty acid ester ( Examples of the fatty acid group include a lauryl group, a myristyl group, a palmityl group, a behenyl group, and an isostearyl group.

Compounding Agent The cyclic olefin-based resin composition according to the present invention may contain, if necessary, an ultraviolet absorber and / or a heat stabilizer.

Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, nickel compounds, hindered amine compounds and the like.
Specifically, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-butylphenyl) -5-chlorobenzotriazole, 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) sevicate and the like can be mentioned.

Specific examples of the heat stabilizer include tetrakis [methylene-3- (3.5-di-t-butyl-4-hydroxyphenyl) propionate] methane and β- (3,5-di-t-butyl-4).
-Hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl)
Phenolic antioxidants such as -4-hydroxyphenyl) propionate; distearylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol-pentaerythritol diphosphite, bis (2,4-di-t -Butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-
And phosphorus-based stabilizers such as (butylphenyl) phosphite.

These ultraviolet absorbers and heat stabilizers can be used alone or in combination of two or more. Further, the cyclic olefin-based resin composition according to the present invention includes an antistatic agent, a flame retardant, a slip agent, an antiblocking agent, an anti-fogging agent, a lubricant, a dye, a pigment, an organic or inorganic material, as long as the object of the present invention is not impaired. And the like can be blended.

Composition The cyclic olefin resin composition according to the present invention can be produced, for example, by the following method. (1) A method of mechanically blending or melt-mixing (A) a cyclic olefin-based resin, (B) a glass transition temperature-reducing compound, and other components to be added as required using a tumbler, an extruder, a kneader, or the like. When an extruder is used, (A) the cyclic olefin-based resin and (B) the glass transition temperature reducing compound may be mixed before being supplied to the extruder. Before melting, (B) the glass transition temperature reducing compound may be injected into the extruder, and after (A) the cyclic olefin resin is melted in the extruder, (B) the glass transition temperature reducing compound is injected into the extruder. You may. (2) Using (A) a cyclic olefin resin in a suitable good solvent (eg, hexane, heptane, decane, cyclohexane,
Hydrocarbon solvents such as benzene, toluene and xylene)
(B) a method of adding a glass transition temperature-reducing compound and optionally other components to a solution obtained by dissolving the solvent, and then removing the solvent. (3) applying a temperature and / or pressure to (A) a powder or a pellet of a cyclic olefin-based resin in (B) a glass transition temperature-reducing compound or (B) vapor of a glass transition temperature-reducing compound; A method of impregnating (B) a glass transition temperature reducing compound into a cyclic olefin resin. (4) A method in which the above methods (1) to (3) are combined.

The cyclic olefin-based resin composition is usually obtained as pellets by the above-mentioned method, but a method using an extruder can also directly produce films, sheets and the like.

The cyclic olefin resin composition according to the present invention comprises (A) at least one selected from the group consisting of (A-1), (A-2), (A-3) and (A-4). Consisting of a kind of cyclic olefin resin and (B) a glass transition temperature reducing compound,
(B) The glass transition temperature reducing compound is contained in an amount of 0.1 to 30% by weight, preferably 0.3 to 10% by weight, based on the cyclic olefin resin (A).

The glass transition temperature of this cyclic olefin resin composition is usually in the range of 70 to 170 ° C. The glass transition temperature of the cyclic olefin resin composition is the same as the glass transition temperature (Tg) of the cyclic olefin resin (A).
_(A) ) lower than 5 ° C., preferably (Tg _(A) -5
C.) to (Tg _(A) -60 C.).

The cyclic olefin resin composition according to the present invention can be used as a material for various molded articles such as injection molded articles, extruded molded articles, blow molded articles, fibers, films and sheets. As a method for molding an injection molded product, an extrusion molded product, a blow molded product, a fiber, a film, a sheet, and the like, a conventionally known production apparatus and production conditions can be adopted.

The use of the cyclic olefin resin composition according to the present invention is not particularly limited, but it can be suitably used as a material for optical components such as lenses, substrates for optical media, prisms, and reflectors. fθ
Lenses such as lenses; substrates for optical recording media such as CDs, DVDs, MDs, and MOs; and laser optical system applications such as optical fiber and other components that transmit laser light.

[0089]

The cyclic olefin resin composition according to the present invention has a low birefringence and a low glass transition temperature, so that it has excellent moldability, and the obtained molded article is suitable for optical applications.

[0090]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0091]

[Comparative Example 1] were obtained using a Ziegler catalyst, ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^{7,1 0]} -3- dodecene (hereinafter simply referred to as "tetracyclododecene".) And (E.TD (1)) (tetracyclododecene unit content: 38 mol%, MFR: 40 g / 10 min, T
g: 135 ° C.) and melt-kneading at a cylinder temperature of 270 ° C. using a twin-screw extruder (TEX-44) to obtain a cyclic olefin-based resin pellet.

The obtained pellets were subjected to a cylinder temperature of 270 using an injection molding machine (IS-50, manufactured by Toshiba Corporation).
130mm × 120m under the condition of ℃, mold temperature 115 ℃
m, a square plate having a thickness of 3 mm was formed.

After visually observing the appearance of the obtained molded article,
The retardation (double pulse, light source wavelength: 630 nm) at the center of the square plate was measured. Further, the glass transition temperature of the composition was measured by DSC manufactured by PERKIN ELMER.
7 was measured. In addition, the stress optical coefficient was measured using a dynamic birefringence measuring device. Table 1 shows the results.

[0094]

Example 1 A cyclic olefin system was prepared in the same manner as in Comparative Example 1 except that sorbitan distearate was added to E · TD (1) in an amount of 0.6% based on E · TD (1). A pellet of the resin composition was produced, and a square plate was formed from the pellet. Table 1 shows the results.

[0095]

Comparative Example 2 A random copolymer of ethylene and tetracyclododecene (E ·
Production of cyclic olefin resin pellets in the same manner as in Comparative Example 1 except that TD (2)) (tetracyclododecene unit content: 46 mol%, MFR: 10 g / 10 min, Tg: 165 ° C.) Then, a square plate was formed from the pellets. Table 1 shows the results.

[0096]

Example 2 A cyclic olefin resin composition was prepared in the same manner as in Comparative Example 1 except that E.TD (2) and sorbitan distearate in an amount of 4% based on E.TD (2) were used. A pellet of the product was produced, and a square plate was formed from the pellet. Table 1 shows the results.

[0097]

Comparative Example 3 A random copolymer of ethylene and tetracyclododecene obtained using a Ziegler catalyst (tetracyclododecene unit content: 36 mol%, MFR: 40)
g / 10 min, Tg: 130 ° C.), except that a pellet of a cyclic olefin-based resin was produced in the same manner as in Comparative Example 1, and a square plate was formed from the pellet. Table 1 shows the results.

[0098]

[Table 1]

Continued on the front page F term (reference) 4J002 AE032 BB101 BK001 BK002 BN031 EA016 EC066 EH016 EP006 FD050 FD070 GP00 GP01

Claims (9)

[Claims] (A) The following (A-1), (A-2), (A-3) and
A composition comprising at least one cyclic olefin-based resin selected from the group consisting of (A-4) and (B) a glass transition temperature-reducing compound, wherein the (B) glass transition temperature-reducing compound is (A) A) 0.1% for cyclic olefin resin.
The composition is contained in an amount of 1 to 30% by weight, the glass transition temperature of the composition is lower than the glass transition temperature of the cyclic olefin resin (A) by 5 ° C. or more, and the molded article obtained by molding the composition has a (A-1) a cyclic olefin-based resin composition characterized in that the refraction is equivalent to the birefringence of the molded article obtained by molding the cyclic olefin-based resin (A); Or an ethylene / cyclic olefin random copolymer obtained by copolymerizing with a cyclic olefin represented by (II) (A-2) Ring opening of a cyclic olefin represented by the following general formula (I) or (II) Polymer or copolymer, (A-3) hydride of the above (A-2) ring-opening polymer or copolymer, and (A-4) the above (A-1), (A-2) or ( A-3) a graft-modified product; Wherein n is 0 or 1, m is 0 or a positive integer, k is 0 or 1, and R ^{1 to} R ¹⁸ and R
^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group; R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring; The polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. ) Wherein p and q are 0 or an integer of 1 or more;
And s is 0, 1 or 2, and R ^{21 to} R ³⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group,
An alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ²⁹ (or R ³⁰ ) is bonded and the carbon atom to which R ³³ or R ³¹ is bonded are directly or It may be bonded via an alkylene group having 1 to 3 carbon atoms, and when r = s = 0, R ³⁵ and R ³² or R ^32
35 and R ³⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ). 2. The cyclic olefin resin composition according to claim 1, wherein the (A) cyclic olefin resin has a glass transition temperature of 110 ° C. or higher. 3. The cyclic olefin according to claim 1, wherein the (B) glass transition temperature reducing compound has a molecular weight of 100 to 10,000 and is an organic compound compatible with the (A) cyclic olefin resin. -Based resin composition. 4. An injection-molded article comprising the cyclic olefin-based resin composition according to any one of claims 1 to 3. 5. An optical component comprising the cyclic olefin resin composition according to claim 1. 6. A lens comprising the cyclic olefin resin composition according to claim 1. 7. A substrate for an optical recording medium, comprising the cyclic olefin-based resin composition according to claim 1. 8. A prism comprising the cyclic olefin resin composition according to any one of claims 1 to 3. 9. A reflector comprising the cyclic olefin resin composition according to claim 1. Description: