JPH09176397A - Cyclic olefin-based resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compound containing a prescribed cyclic olefin-based resin and a prescribed rubber in a specific ratio, and capable of stably retaining excellent transparency especially even in an environmental change.

SOLUTION: This composition comprises (A) 100 pts.wt. of a cyclic olefin- based resin which is selected from among (i) a random copolymer of ethylene and a cyclic olefin of formula I ((n) and (q) are each 0 or 1; (m) is 0 or a positive integer; R¹ to R¹⁸, R^a and R^b are each H, a halogen, etc.) or formula II ((p) and (q) are each 0 or a positive integer; (m) and (n) are each 0-2; R¹ to R¹⁹ are each H, a hydrocarbon, etc.), (ii) a ring opening polymer or copolymer of the cyclic olefin of formula I or formula II, (iii) a hydrogenated substance of the component (ii) and (iv) a graft modified substance of the component (i), the component (ii) or the component (iii) and has ≥70°C softening point and 0.05-10dl/g intrinsic viscosity at 135°C in decalin, and (B) 0.01-10 pts.wt. of a rubber having ≤98 rubber hardness specified JIS A. The difference, ND[B]- n_d[A] in refractive indexes nD[A] and nD[B] of the component A and the component B is ≤0.015.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention is excellent in transparency, heat resistance, moisture resistance, chemical resistance, solvent resistance, moldability, electrical properties, mechanical strength, low birefringence, etc. TECHNICAL FIELD The present invention relates to a cyclic olefin resin composition capable of maintaining excellent transparency even when changed and its use.

[0002]

BACKGROUND OF THE INVENTION Polycarbonates, poly (methyl methacrylate), polyethylene terephthalate, etc. have been known as resins having excellent transparency. Although this polycarbonate is excellent in rigidity, heat resistance, heat aging resistance, and impact resistance, it is inferior in chemical resistance, has a large birefringence when used by molding on an optical substrate, and further has a water absorption rate (water resistance). There is a problem that it cannot be said that the sex) is sufficiently small. Although polymethylmethacrylate has excellent mechanical properties, it has a problem of poor chemical resistance, heat resistance, and weather resistance. Polyethylene terephthalate has excellent heat resistance and mechanical properties. It is vulnerable to strong acids or alkalis and is susceptible to hydrolysis. Further, polyolefin has been known as a resin having excellent transparency, and a cyclic olefin resin derived from a bulky cyclic olefin has been proposed as a polyolefin having a good balance of rigidity and transparency. For example, as a random copolymer of this bulky cyclic olefin and ethylene, a copolymer of ethylene and 2,3-dihydroxydicyclopentadiene (US Pat. No. 2,883,37
No. 2), or a copolymer of ethylene and 5-ethylidene norbornene has been proposed.

The applicant of the present invention also studied such a cyclic olefin resin, and found that an amorphous cyclic olefin resin such as a copolymer of ethylene and a cyclic olefin was converted into an α-olefin (co) polymer. Compared to various characteristics, it has excellent electrical properties such as transparency, low birefringence, moisture resistance (low water absorption), heat resistance, chemical resistance, solvent resistance, precision molding processability, and dielectric characteristics. It has been found to have excellent properties, mechanical properties, and rigidity. Therefore, the cyclic olefin-based resin is considered to be used for various wide-ranging uses, and particularly by utilizing its excellent transparency, it can be used for optical uses, medical / pharmaceutical containers, food containers, and the like. It is considered.

However, in the process of studying the application of such a cyclic olefin resin, the cyclic olefin resin becomes cloudy when the environment changes, for example, from a high temperature and high humidity atmosphere to a normal temperature and normal humidity atmosphere. It has been found that there is a problem that the transparency or the light transmittance may be deteriorated. Therefore, the transparency does not decrease due to environmental changes, excellent transparency can be stably maintained, and the advent of a cyclic olefin resin that can be suitably used for each of the above applications is desired. It was

In view of the above-mentioned prior art, the present inventor studied a cyclic olefin resin composition whose transparency does not decrease even with environmental changes in temperature and humidity. The aromatic olefin-conjugated diene block copolymer or hydrogenated product selected so that the difference in the refractive index with the resin is within a specific range, the cyclic olefin-based resin composition containing a specific proportion of the above is The present invention has been completed by finding that it can be suitably used for optical applications and container applications where the above properties are satisfied and transparency is required.

[0006]

The object of the present invention is transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, various mechanical properties, precision moldability, moisture resistance (low water absorption). It is an object of the present invention to provide a cyclic olefin resin composition capable of stably maintaining excellent transparency even when the environment changes, and a use of the cyclic olefin resin composition.

[0007]

SUMMARY OF THE INVENTION The cyclic olefin resin composition according to the present invention is selected from [A] (1) [A-1], [A-2], [A-3] and [A-4] below. (2) The softening point temperature (TMA) is 70 ° C. or higher, and (3) the intrinsic viscosity [η] (in 135 ° C. decalin) is 0.0.
A cyclic olefin resin having a viscosity of 5 to 10 dl / g and a rubber having a rubber hardness of 98 or less specified by [B] JISA and having a refractive index n _D [A] of the cyclic olefin resin [A]. , The refractive index of the rubber [B] is n _D [B]
, The difference in refractive index | n _D [B] −n _D [A] | is 0.015 or less, and the rubber [B] is 0 with respect to 100 parts by weight of the cyclic olefin resin [A]. .01-
It is characterized in that it is contained in an amount of 10 parts by weight. [A-1] Random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II];

[0008]

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(In the formula [I], n is 0 or 1, and m is
Is 0 or a positive integer; q is 0 or 1;
^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group optionally substituted with halogen, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. And the monocyclic or polycyclic ring may have a double bond, and may form an alkylidene group with R ¹⁵ and R ¹⁶ or with R ¹⁷ and R ^18. You may. ),

[0010]

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(In the formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ¹
To R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group which may be substituted with halogen, and a carbon atom to which R ⁹ or R ¹⁰ is bonded and R ¹³ are bonded to each other. May be directly or via an alkylene group having 1 to 3 carbon atoms, or may be bonded to the carbon atom to which R ¹¹ is bonded. When n = m = 0, R ¹⁵ and R ¹² or R ^{12 15} and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ), [A-
2] A ring-opening polymer or copolymer of the cyclic olefin represented by the above formula [I] or [II], [A-3] a hydride of the above ring-opening polymer or copolymer [A-2], and [A-4] Above [A-
1], [A-2] or [A-3] graft modified product.

The rubber [B] is preferably an aromatic vinyl / conjugated diene block copolymer or a hydrogenated product thereof. As a use of the cyclic olefin resin composition according to the present invention as described above, a plastic lens, a container, a transparent sheet or a transparent board is particularly suitable.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The cyclic olefin resin composition according to the present invention will be specifically described below. In the cyclic olefin resin composition according to the present invention, the difference in refractive index between the cyclic olefin resin [A] derived from a bulky cyclic olefin as shown below and the cyclic olefin resin [A] falls within a specific range. Aromatic vinyl selected to be
It is characterized by being formed from a conjugated diene block copolymer or its hydrogenated product [B]. The cyclic olefin resin used in the present invention will be shown.

In the present invention, as the cyclic olefin resin, a random copolymer of [A-1] ethylene and a cyclic olefin represented by the following formula [I] or [II], and [A-2] the following formula [I ] Or [II] a ring-opening polymer or copolymer of a cyclic olefin, [A-3] a hydride of the above ring-opening polymer or copolymer [A-2], or [A-4] above [A-1], [A-2]
Alternatively, a graft modified product of [A-3] is used. The cyclic olefin represented by the formula [I] or [II] which forms the cyclic olefin resins [A-1] to [A-4] will be described below. Cyclic olefin

[0015]

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In the above formula [I], n is 0 or 1,
m is 0 or a positive integer, and q is 0 or 1.
When q is 1, R ^a and R ^b are each independently the following atoms or hydrocarbon groups. When q is 0, each bond is bonded to form a 5-membered ring. Form.

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.

As the hydrocarbon group, an alkyl group having usually 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group can be mentioned each independently. 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 a phenyl group, a naphthyl group, etc. are mentioned as an aromatic hydrocarbon group.
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 (cooperate with each other) to form a monocycle or polycycle, and the monocycle or polycycle thus formed may have a double bond. Specific examples of the monocyclic or polycyclic rings formed here are shown below.

[0020]

[Chemical 6]

In the above exemplification, the carbon atoms numbered 1 or 2 are respectively R ¹⁵ in the formula [I].
The carbon atom to which (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is attached 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.

[0022]

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In the above formula [II], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ 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 or 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; a cycloalkyl group includes a cyclohexyl group; an aromatic hydrocarbon group; Examples thereof 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. 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 ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are either directly or having 1 to 10 carbon atoms.
And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ , or the groups represented by R ¹⁰ and R ^{11 work} together to form a methylene group It forms an alkylene group of any of (-CH _2- ), an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH ₂ CH ₂ CH _2- ). Furthermore, when n = m = 0, R ¹⁵ and R ¹²
Alternatively, R ¹⁵ and R ¹⁹ 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, n = m =
When it is 0, a group in which R ¹⁵ and R ¹² further form an aromatic ring can be mentioned.

[0026]

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

[0028]

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(In the above formula, the numbers 1 to 7 represent the position number of carbon.) And a derivative of bicyclo [2.2.1] -2-heptene substituted with a hydrocarbon group. Examples of the hydrocarbon group 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- (biphenyl), 5- (β-naphthyl), 5- (α
-Naphthyl), 5- (anthracenyl), 5,6-diphenyl and the like.

Still other derivatives include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-
Tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a
-Bicyclo [2.2.1] such as hexahydroanthracene
2-heptene derivatives and the like.

Tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-
Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives such as methyltricyclo [4.3.0.1 ^2,5 ] -3-decene and 5-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene; Tricyclo [4.4.0.1
^2,5 ] -3-undecene, 10-methyltricyclo [4.4.0.1
^2,5 ] -3-undecene and other tricyclo [4.4.0.1 ^2,5 ] -3
-Undecene derivative.

[0032]

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(In the above formula, the numbers 1 to 12 represent the position number of carbon.) And derivatives thereof in which a hydrocarbon group is substituted. Examples of this hydrocarbon group include 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-1
1,12-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), 5,6-diphenyl and the like.

Still another derivative is an adduct of (cyclopentadiene-acenaphthylene adduct) with cyclopentadiene. 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 derivatives thereof. Pentacyclo [6.5.1.1
^3,6 .0 ^2,7 .0 ^9,13] 4,10 penta octadecadienoic Penta cyclopentadiene octadecadienoic compound such. Pentacyclo [8.4.
0.1 ^{2,5.1 9,12} .0 ^8,13 ] -3-Hexadecene and its derivatives. Pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene, and derivatives thereof. Hexacyclo [6.6.1.
1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene and derivatives thereof. Heptacyclo [8.7.0.1 ^2,9 .1 ^4,7 .1 ^11,17 .0
^{3,8 12,16} ] -5-Eicosene and its derivatives. Heptacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .0} 3,8 .0 12,17] -5-
Hen eicosene, 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 a derivative thereof. 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] -5-pentacosene and derivatives thereof. Nonacyclo [10.10.1.1 ^5,8 .1
^14,21 .1 ^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -6-hexacosenoic, and its derivatives, and the like.

Specific examples of the cyclic olefin represented by the general formula [I] or [II] are shown above, but more specific structural examples of these compounds are described in Japanese Patent Application No. 5-1964.
No. 75, paragraph numbers [0032] to [005]
4]. The cyclic olefin resin used in the present invention is
Two or more units derived from the above cyclic olefin may be contained.

The cyclic olefin represented by the above general formula [I] or [II] can be produced by subjecting cyclopentadiene and olefins having a corresponding structure to a Diels-Alder reaction.

The cyclic olefin resin used in the present invention can be prepared by using the cyclic olefin represented by the above formula [I] or [II], for example, JP-A-60-168708 and JP-A-60-168708.
1-120816, 61-115912, 61-115916, 61-271
No. 308, No. 61-272216, No. 62-252406 and No. 62-2524
According to a method proposed by the present applicant in a publication such as No. 07, it can be produced by appropriately selecting conditions.

[A-1] Ethylene / Cyclic Olefin Random
Copolymer [A-1] A random copolymer of ethylene and a cyclic olefin has a unit derived from ethylene of usually 5 to 95 mol%,
The amount of the units derived from cyclic olefins is usually 5 to 95 mol%, preferably 20 to 80 mol%, preferably 20.
It is contained in an amount of ˜80 mol%. The ethylene composition and the cyclic olefin composition can be measured by ¹³ C-NMR.

In this [A-1] ethylene / cyclic olefin random copolymer, the units derived from ethylene and the units derived from cyclic olefin as described above are randomly arranged and bonded to each other, and are substantially linear. It has a shape-like 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 measuring the intrinsic viscosity [η], it can be confirmed by completely dissolving this copolymer in decalin at 135 ° 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 formula [I] or [II] is represented by the following formula [III] or [III]: IV] is considered to constitute the repeating unit.

[0041]

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In the formula [III], n, m, q, R ¹ to
R ¹⁸ and R ^a and R ^b have the same meaning as in formula [I].

[0043]

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In the formula [IV], n, m, p, q and R ^{1 to} R ¹⁹ have the same meanings as in the formula [II]. Further, the [A-1] ethylene / cyclic olefin random copolymer as described above has a unit derived from another copolymerizable monomer as needed as long as the object of the present invention is not impaired. It may specifically contain a unit derived from another monomer in an amount of usually 20 mol% or less, preferably 10 mol% or less.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic olefins, and specific examples include propylene, 1-butene, 1-pentene, 1-hexene and 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, 1-octene , 1-decene, 1-
Α- having 3 to 20 carbon atoms such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene
Olefin, 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. The ethylene / cyclic olefin random copolymer [A-1] may contain two or more kinds of units derived from the above-mentioned other monomers.

The ethylene / cycloolefin random copolymer [A-1] can be produced by the production method disclosed in the above publication using ethylene and the cycloolefin represented by the formula [I] or [II]. it can. Of these,
The copolymerization reaction is carried out in a hydrocarbon solvent, and a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent is used as a catalyst for ethylene.
It is preferable to produce the cyclic olefin random copolymer [A-1].

The ethylene / cyclic olefin random copolymer [A-1] can also be produced by using a solid Group IVA metallocene catalyst. This solid group IVA metallocene catalyst comprises a transition metal compound (metallocene compound) containing at least one ligand having a cyclopentadienyl skeleton, an organoaluminumoxy compound, and optionally an organoaluminum compound. It is formed. Where IV
Group transition metals are zirconium, titanium or hafnium. 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 with 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 usually an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or the like.

As the organoaluminum oxy compound and the organoaluminum compound, those usually used for the production of olefin polymers can be used. Such a solid group IVB metallocene catalyst is described in detail in, for example, JP-A-61-221206, JP-A-64-106, and JP-A-2-173112.

[A-2] Ring-opening (co) polymer of cyclic olefin Ring-opening polymer or ring-opening copolymer of cyclic olefin [A-2]
In the formula, at least a part of the unit derived from the cyclic olefin represented by the formula [I] or [II] is considered to be represented by the following formula [V] or [VI].

[0050]

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In the formula [V], n, m, q and R ¹
To R ¹⁸ and R ^a and R ^b have the same meanings as in formula [I].

[0052]

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In the formula [VI], n, m, p, q and R ^{1 to} R ¹⁹ have the same meanings as in the formula [II]. Such a ring-opened (co) polymer can be produced by the production method disclosed in the above-mentioned gazette. For example, a cyclic olefin represented by the above formula [I] is polymerized or polymerized in the presence of a ring-opening polymerization catalyst. It can be produced by copolymerization.

As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide selected from ruthenium, rhodium, palladium, osmium, indium or platinum, a nitrate or an acetylacetone compound and a reducing agent, or titanium, A catalyst composed of a halide of a metal selected from palladium, zirconium, molybdenum or the like or an acetylacetone compound and an organoaluminum compound can be used.

[A-3] Hydrogenation product of ring -opening (co) polymer A hydrogenation product of a ring-opening (co) polymer [A-3] is a ring-opening polymer or ring-opening copolymer [A-3] as described above. A-2] is hydrogenated in the presence of a conventionally known hydrogenation catalyst.

In the hydride [A-3] of this ring-opening (co) polymer, at least a part of the units derived from the formula [I] or [II] is represented by the following formula [VII] or [VIII]. It is believed that

[0057]

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In the formula [VII], n, m, q and R
^{1 to} R ¹⁸ and ^Ra and ^Rb have the same meaning as in formula [I].

[0059]

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In the formula [VIII], n, m, p, q, R
^{1 to} R ¹⁹ have the same meaning as in formula [II]. [A-4] Graft-modified product The cycloolefin-based resin graft-modified product is the above-mentioned ethylene / cycloolefin random copolymer [A-1], a cyclic olefin ring-opening (co) polymer [A-2], Or ring opening (co)
It is a graft modified product [A-3] of a hydride of a polymer.

As the modifier, unsaturated carboxylic acids are usually used. Specifically, (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Unsaturated carboxylic acids such as endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^TM ), and derivatives of these unsaturated carboxylic acids such as unsaturated carboxylic anhydrides and unsaturated Examples thereof include carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and ester compounds of unsaturated carboxylic acids. Specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, citraconic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

Among these modifiers, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic acid 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. The modification ratio of the graft-modified product [A-4] of the cyclic olefin resin used in the present invention is usually preferably 10 mol% or less.

Cyclic olefin resin [A-1], [A-2] or
In order to obtain a graft-modified product of a cyclic olefin resin from [A-3] and a modifier, conventionally known polymer modification methods can be widely applied. For example, a method in which a modifier is added to a molten cycloolefin resin [A-1], [A-2] or [A-3] and graft polymerization (reaction) is performed, or a cycloolefin resin [A-1 ], [A-2] or [A-3] is a graft modified product obtained by a method of adding a modifying agent to a solvent solution and carrying out a graft reaction. Such a grafting reaction is usually performed at a temperature of 60 to 350 ° C. The graft reaction can be performed in the presence of a radical initiator such as an organic peroxide and an azo compound.

A modified product having a modification ratio as described above can be directly obtained by a graft reaction between an unmodified cyclic olefin resin and a modifying agent, and can also be preliminarily improved by a graft reaction between the cyclic olefin resin and a modifying agent. It can also be obtained by preparing a modified product having a modification ratio and then diluting the modified product with an unmodified cyclic olefin resin so as to obtain a desired modification ratio.

In the present invention, the cyclic olefin resin [A]
As above [A-1], [A-2], [A-3] and [A-4]
Any of these may be used alone, two or more of the same species may be used, and these may be used in combination. Among these, as the cyclic olefin resin [A],
Ethylene / cyclic olefin random copolymer [A-1] is preferably used. The crystallinity of the cyclic olefin resin measured by X-ray diffractometry is 0 to 20%, preferably 0 to 2%. The softening point temperature (TMA) of the cyclic olefin resin [A] used in the present invention is
It is 70 ° C. or higher, preferably 90 to 250 ° C., and more preferably 100 to 200 ° C. Glass transition temperature (Tg) is 60 to 230 ° C., preferably 70 to 210 ° C.
It is desirable that [A] Intrinsic viscosity of cyclic olefin resin [η] (135
(In decalin at 0 ° C.) is 0.05 to 10 dl / g, preferably 0.08 to 5 dl / g.

[B] The rubber hardness defined by JISA is 9
8 or less rubber Cyclic olefin resin composition according to the present invention, JIS A
And a rubber having a rubber hardness of 98 or less (hereinafter also referred to as component [B]). When the refractive index of the rubber [B] is n _D [B] and the refractive index of the cycloolefin resin [A] is n _D [A], the difference in refractive index | n _D
[B] -n _D [A] | is 0.015 or less, preferably 0.1.
The aromatic vinyl / conjugated diene block copolymer or its hydrogenated product [B] having a molecular weight of 012 or less, more preferably 0.010 or less is used. By containing such a rubber, the cyclic olefin resin composition can retain excellent transparency even when the environment changes from a high temperature and high humidity atmosphere to a normal temperature and normal humidity atmosphere. .

In the present invention, as such a rubber, for example, an aromatic vinyl / conjugated diene block copolymer or a hydrogenated product thereof can be exemplified. Specific examples of the aromatic vinyl forming the aromatic vinyl / conjugated diene block copolymer or hydrogenated product thereof include styrene, α-methylstyrene, p-methylstyrene and the like. Examples of the conjugated diene include butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene and the like. The aromatic vinyl / conjugated diene block copolymer and hydrogenated product [B] thereof used in the present invention contain 5 to 80% by weight, preferably 15 to 70% by weight of the unit derived from the aromatic vinyl as described above. More preferably, it is desirable to contain 40 to 70% by weight. In particular, from the aromatic vinyl / conjugated diene block copolymer or hydrogenated product [B] thereof containing a unit derived from aromatic vinyl in an amount of 40 to 70% by weight, a cyclic olefin resin composition having excellent transparency is obtained. An object can be formed. The content of the unit derived from aromatic vinyl is a value measured by a conventional method such as infrared spectroscopy and NMR spectroscopy. Specific examples of such an aromatic vinyl-conjugated diene block copolymer or its hydrogenated product [B] include styrene-
Butadiene block copolymer (SB) and its hydrogenated product (SEB), styrene-butadiene-styrene block copolymer (SBS) and its hydrogenated product (SEB)
S; styrene / ethylene / butylene / styrene block copolymer), styrene / isoprene block copolymer (SI) and hydrogenated products thereof (SEP), styrene /
Examples thereof include isoprene / styrene block copolymer (SIS) and hydrogenated products thereof (SEPS; styrene / ethylene / propylene / styrene block copolymer). As the aromatic vinyl / conjugated diene block copolymer or hydrogenated product thereof [B] such as SEBS,
More specifically, Kraton G16
50, G1652, G1657, G1701 (manufactured by Shell Chemical Co., Ltd., trade name), Tuftec (manufactured by Asahi Kasei Co., Ltd.,
Product names) and SEPS include Septon 2104 and the like. In the present invention, the aromatic vinyl / conjugated diene block copolymer or its hydrogenated product [B] is SE
BS (hydrogenated SBS) and SEPS (hydrogenated SIS) are particularly preferably used. Aromatic vinyl used in the present invention
The conjugated diene block copolymer or its hydrogenated product [B] is a thermoplastic elastomer composed of an aromatic vinyl block unit and a conjugated diene rubber block unit (or its hydrogenated rubber block unit). In such a block copolymer, the aromatic vinyl block unit which is a hard segment exists as a bridging point of the rubber block unit which is a soft segment to form a physical crosslink (domain). The number average molecular weight of the aromatic vinyl / conjugated diene block copolymer or hydrogenated product thereof used in the present invention as described above is 500 to 2,000,000.
It is desirable that it is preferably 10,000 to 1,000,000. The number average molecular weight (Mn) is determined by gel permeation chromatography (G) of the aromatic vinyl / conjugated diene block copolymer and its hydrogenated product [B].
PC; o-dichlorobenzene, 140 ° C). In the present invention, these compounds may be used in combination of two or more kinds.

Cyclic Olefin Resin Composition The cyclic olefin resin composition according to the present invention contains the above aromatic vinyl / conjugated diene block copolymer or 100 parts by weight of the cyclic olefin resin [A]. The hydrogenated product [B] is 0.01 to 10 parts by weight, preferably 0.5 parts by weight or more and less than 5 parts by weight, more preferably 0.5 parts by weight.
˜2 parts by weight.

Such a cyclic olefin resin composition has transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, various mechanical properties, precision moldability, Excellent moisture resistance (low water absorption). In particular, the cyclic olefin resin composition according to the present invention is a cyclic olefin resin derived from a bulky cyclic olefin and an aromatic vinyl / conjugated diene block copolymer having a small difference in refractive index between the cyclic olefin resin or the cyclic olefin resin or Since the hydrogenated substance is contained in a specific ratio, excellent transparency can be maintained even when the environment changes from a high temperature and high humidity atmosphere to a normal temperature and normal humidity atmosphere. It has been found by the present inventors that the cyclic olefin resin composition having such a composition can maintain excellent transparency even when the environment changes.

The cycloolefin resin composition according to the present invention as described above may optionally contain other components in addition to [A] and [B] as long as the object of the present invention is not impaired. Often, additives other than [B], for example, stabilizers such as heat stabilizers and weather stabilizers, crosslinking agents, crosslinking aids, antistatic agents, slip agents, antiblocking agents, antifog agents,
It may contain lubricants, dyes, pigments, mineral oil-based softeners, petroleum resins, waxes and the like.

Specifically, as a stabilizer contained as an optional component, for example, tetrakis [methylene-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate]
Methane, β- (3,5-di-t-butyl-4-hydroxyphenyl)
Alkyl propionate, 2,2'-Ogizamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl)
Examples thereof include phenolic antioxidants such as propionate, and fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 1,2-hydroxystearate. These may be used in combination, for example, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate or calcium stearate may be used in combination. You can also

Examples of the stabilizer include distearyl pentaerythritol 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-
Phosphorus stabilizers such as di-t-butylphenyl) -4,4'-biphenylene diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite can also be used. it can.

The cyclic olefin resin composition may optionally contain an organic filler or an inorganic filler as long as the object of the present invention is not impaired. Examples thereof include silica, diatomaceous earth and alumina. , Titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide,
Magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder , Molybdenum sulfide, etc. may be contained.

The cyclic olefin resin composition according to the present invention is obtained by molding the above cyclic olefin resin composition into a desired shape by a known molding method. For example, a cyclic olefin resin composition is molded into a lens, a container, a tray, a sheet, or a film by a molding method such as an injection molding method, an injection blow molding method, a direct blow molding method, a T-die extrusion method, an inflation method, or a pressing method. It can be molded into a shape.

Specific applications of the cyclic olefin resin composition according to the present invention include optical components such as spherical lenses, aspherical lenses, Fresnel lenses, prisms, light guide plates, CDs, MDs, DVDs, and the like. Optical recording media such as MO and PD, transparent boards, vials, prefilled syringes, pharmaceutical / medical containers such as analysis cells, wide-mouth containers,
Examples include shampoo containers, coffee containers, seasoning containers, beverage containers and other daily sundries / food containers, and transparent sheets. Among these, plastic lenses, optical recording media, containers, transparent sheets and boards are particularly preferable.

[0076]

As described above, the cyclic olefin resin composition according to the present invention has transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties. The excellent transparency, precision moldability, moisture resistance (low water absorption), etc. are maintained, and excellent transparency can be stably maintained even when the environment changes. Such a cyclic olefin resin composition according to the present invention is particularly useful as an optical molded product, a container, a transparent sheet, a board and the like.

[0077]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.
In the present invention, various physical properties were measured or evaluated by the following methods. (1) Softening temperature (TMA) Using a Thermo Mechanical Analyzer manufactured by DuPont,
It was measured by the thermal deformation behavior of a 1 mm thick sheet. A quartz needle was placed on the sheet, a load of 49 g was applied, the temperature was raised at a rate of 5 ° C./min, and the temperature at which the needle penetrated 0.635 mm into the sheet was taken as TMA. (2) Light transmittance The light transmittance at 600 nm was measured using a spectrophotometer. (3) Refractive index Measured according to ASTM D542.

[0078]

Examples 1 to 3 As the component [A], the softening temperature (TM
A) is 150 ° C. and the intrinsic viscosity [η] is 0.6 dl / g
A random copolymer of ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecene-3 (abbreviated as Et-TCD)
100 parts by weight of the above-mentioned Et-TC as component [B]
The difference in refractive index from _D | n _D [B] −n _D [A] | is 0.00
8 styrene / ethylene / propylene / styrene block copolymer (SEPS) (trade name: Septon 210)
4) was added in an amount (parts by weight) shown in Table 1, supplied to a twin-screw extruder having a cylinder temperature set to 250 ° C., and melt-kneaded to obtain a cyclic olefin resin composition. The obtained cyclic olefin-based resin composition is injected into an injection molding machine (TOSHIBA MACHINE IS
-55 EPN) and injection-molded into a square plate having a thickness of 3 mm. Put this square plate under high temperature and high humidity of 80 ° C and 90% RH for 48 hours.
After leaving it for a period of time, it was taken out in normal temperature and normal humidity. The transparency (light transmittance) before and after the test was evaluated.

[0079]

Comparative Example 1 A square plate was formed in the same manner as in Example 1 except that the component [B] was not added and only Et-TCD was used.
Tested. The results are shown in Table 1.

[0080]

Comparative Example 2 A square plate was molded and tested in the same manner as in Example 1 except that the amount of the component [B] was 11 parts by weight. The results are shown in Table 1.

[0081]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 21:00) (72) Inventor Toshiyuki Hirose 1-6, Waki, Waki-cho, Kaku-gun, Yamaguchi Prefecture No. 2 In Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Yozo Yamamoto 6 1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Masayoshi Yamaguchi Yamaguchi Mitsui Petrochemical Industry Co., Ltd., 6-1-2 Waki, Waki-cho, Kuga-gun, Japan

Claims (6)

[Claims] 1. [A] (1) is selected from the following [A-1], [A-2], [A-3] and [A-4], and (2) has a softening point temperature (TMA). 70 ° C
And (3) a cyclic olefin resin having an intrinsic viscosity [η] (in decalin at 135 ° C) of 0.05 to 10 dl / g, and [B] a rubber having a rubber hardness of 98 or less specified by JISA. And the refractive index of the cyclic olefin resin [A] is n _D [A]
And the refractive index of the rubber [B] is n _D [B], the difference in refractive index | n _D [B] −n _D [A] | is 0.015.
The following is contained, and the cyclic olefin resin composition is characterized by containing the rubber [B] in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the cyclic olefin resin [A]; [A-1] A random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II]; (In the 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 ^a and R ^b are each independently hydrogen. An atom, a halogen atom or a hydrocarbon group optionally substituted by halogen, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring; It may have a double bond, and R ¹⁵ and R ¹⁶ or R ^15
17 and R ¹⁸ may form an alkylidene group. ), Embedded image (In the formula [II], p and q are 0 or a positive integer,
m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group optionally substituted by halogen,
The carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. 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. ), [A-2] above formula [I]
Or a ring-opening polymer or copolymer of a cyclic olefin represented by [II], [A-3] the above ring-opening polymer or copolymer [A-
2] hydride, and [A-4] above [A-1], [A-2] or [A
-3] graft-modified product. 2. The cyclic olefin resin composition according to claim 1, wherein the rubber [B] is an aromatic vinyl / conjugated diene block copolymer or a hydrogenated product thereof. 3. A plastic lens comprising the cyclic olefin resin composition according to claim 1. 4. A container comprising the cyclic olefin resin composition according to claim 1 or 2. 5. A transparent sheet or board comprising the cyclic olefin resin composition according to claim 1. 6. An optical recording medium comprising the cyclic olefin resin composition according to claim 1.