JPH09176396A - Cyclic olefin-based resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition capable of stably retaining excellent transparency especially even in an environmental change, excellent in low birefingent, containing a prescribed olefin-based resin and a compound containing both hydrophilic and hydrophobic groups in a specific ratio.

SOLUTION: This composition comprises (A) 100 pts.wt. of a cyclic olefinbased resin selected from (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 and (iii) a hydrogenated substance of the component (ii) and has ≥80°C softening point (TMA) and 0.05-10dl/g intrinsic viscosity [η] (at 135°C in decalin) and (B) 0.001-10 pts.wt. of a compound containing both hydrophilic and hydrophobic groups (preferably a hydroxyalkyl- containing amine such as 2-hydroxyethyl-2-hydroxydodecylamine or an amide compound).

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is excellent in transparency, heat resistance, moisture resistance, chemical resistance, solvent resistance, moldability, electrical properties, mechanical strength, low birefringence, etc. Relates to a cyclic olefin-based resin composition that can maintain excellent transparency 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.

[0003] The present applicant has also studied such a cyclic olefin-based resin. In particular, amorphous cyclic olefin-based resins such as a copolymer of ethylene and a cyclic olefin have been converted to α-olefin (co) polymers. Compared with various properties, such as transparency, low birefringence, moisture resistance (low water absorption), heat resistance, chemical resistance, solvent resistance, precision molding processability, dielectric properties, etc. , And have excellent 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 conventional techniques, the present inventor studied a cyclic olefin resin composition whose transparency does not decrease even when the environment such as temperature and humidity changes. A cycloolefin resin composition containing a compound having a hydrophilic group and a hydrophobic group in a specific ratio satisfies the above-mentioned characteristics, and is suitable for use in optical applications and container applications where transparency is required. The inventors have found that they can be achieved and completed the present invention.

[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 the following [A] (1) [A-1], [A-2] and [A-3],
(2) Softening point temperature (TMA) is 80 ° C or higher, and (3) Intrinsic viscosity [η] (in decalin at 135 ° C) is 0.05 to 10 dl.
/ G of a cyclic olefin resin and [B] a compound having a hydrophilic group and a hydrophobic group in the same molecule, and the hydrophilic group and the hydrophobic group are 100 parts by weight of the cyclic olefin resin [A]. The compound [B] having a group is contained in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight.

[A-1] ethylene and the following formula [I] or [I
A random copolymer with a cyclic olefin represented by I];

[0009]

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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. ),

[0011]

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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-opened polymer or copolymer of the cyclic olefin represented by the formula [I] or [II], and [A-3] a hydride of the ring-opened polymer or copolymer [A-2].

In the present invention, [B] a compound having a hydrophilic group and a hydrophobic group in the same molecule, the hydrophilic group has a hydroxyalkyl group having 1 or more carbon atoms and the hydrophobic group is an alkyl group having 6 or more carbon atoms. It is preferable that the amine compound or the amide compound is As the application of the cyclic olefin resin composition according to the present invention as described above, a plastic lens, an optical recording medium, a container, a transparent sheet or a transparent board is particularly suitable.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The cyclic olefin resin composition according to the present invention will be specifically described below. The cyclic olefin resin composition according to the present invention comprises a cyclic olefin resin [A] derived from a bulky cyclic olefin as shown below, and a compound [B] having a hydrophilic group and a hydrophobic group in the same molecule. It is characterized by being formed from. The cyclic olefin resin used in the present invention will be shown.

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

[0016]

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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 usually having 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.

[0021]

[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.

[0023]

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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 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.

[0027]

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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.

[0029]

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(In the above formula, the numbers 1 to 7 represent the position number of carbon.) And a derivative obtained by substituting the bicyclo [2.2.1] -2-heptene 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.

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] 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.

[0033]

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(In the above formula, the numbers 1 to 12 represent the carbon position numbers) 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 other derivatives include 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 the Diels-Alder reaction of cyclopentadiene and olefins having a corresponding structure.

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-6-168708.
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 ethylene / cycloolefin random copolymer [A-1] used in the present invention, at least a part of the cycloolefin 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.

[0042]

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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].

[0044]

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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 specifically, propylene, 1-butene, 1-pentene, 1-hexene, 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 / cycloolefin random copolymer [A-1] can also be produced by using a solid Group IV metallocene catalyst. The solid group IV metallocene catalyst is a transition metal compound (metallocene compound) containing a ligand having at least one cyclopentadienyl skeleton.
And an organic aluminum oxy compound and, if necessary, an organic aluminum compound. Here, the group IV transition metal is 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].

[0051]

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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].

[0053]

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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] Hydride of Ring-Opening (Co) polymer [0056] The hydride of 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

[0058]

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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].

[0060]

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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]. In the present invention, as the cyclic olefin resin [A], the above-mentioned [A-
Any one of 1], [A-2] and [A-3] may be used alone, two or more of the same species may be used, or a combination of these may be used.

Among these, ethylene / cyclic olefin random copolymer [A-1] is preferably used as the cyclic olefin resin [A]. The crystallinity of the cyclic olefin resin measured by the X-ray diffraction method is 0 to 2
It is desirable that it is 0%, preferably 0 to 2%. The softening point temperature (TMA) of the cyclic olefin resin [A] used in the present invention is 80 ° C. or higher, preferably 90 to 2
The temperature is 50 ° C, more preferably 100 to 200 ° C. The glass transition temperature (Tg) is 60 to 230 ° C, preferably 70 to 210 ° C. [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] Having a hydrophilic group and a hydrophobic group in the same molecule
The compound The cyclic olefin resin composition according to the present invention contains a compound [B] having a hydrophilic group and a hydrophobic group in the same molecule (hereinafter also referred to as component [B]). Since the cyclic olefin resin composition contains the compound [B] having a hydrophilic group and a hydrophobic group in the same molecule as described above, the cyclic olefin resin composition is changed from a high temperature and high humidity atmosphere to a normal temperature and normal humidity atmosphere. Excellent transparency can be maintained even when the environment changes.

Specific examples of the hydrophilic group as described above include hydroxy group, hydroxyalkyl group having 1 or more carbon atoms, hydroxyl group, carbonyl group, ester group, amino group,
Amide group, ammonium salt, thiol, sulfonate,
Examples thereof include phosphates and polyalkylene glycol groups, and the amino group may be primary, secondary, or tertiary. Specific examples of the hydrophobic group include an alkyl group having 6 or more carbon atoms which may have an aromatic group, a silyl group having an alkyl group having 6 or more carbon atoms, and a fluoroalkyl group having 6 or more carbon atoms. . Specific examples of the alkyl group include hexyl, heptyl, octyl, nonyl, decyl, undecenyl, dodecyl, tridecyl, tetradecyl, myristyl, stearyl, lauryl, palmityl and cyclohexyl. A phenyl group etc. are mentioned as an aromatic group. The component [B] may have at least one hydrophilic group and at least one hydrophobic group in the same molecule, and may have two or more groups.

More specific examples of the compound [B] having a hydrophilic group and a hydrophobic group in the same molecule include, for example, myristyldiethanolamine, 2-hydroxyethyl-2-hydroxydodecylamine and 2-hydroxyethyl. -
2-hydroxytridecylamine, 2-hydroxyethyl-2
-Hydroxytetradecylamine, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, di-2-
Hydroxyethyl-2-hydroxydodecylamine, alkyl (C8-18) benzyldimethylammonium chloride, ethylenebisalkyl (C8-18) amide, stearyldiethanolamide, lauryldiethanolamide, myristyldiethanolamide, palmityldiethanolamide , And so on. Of these, amine compounds or amide compounds having a hydroxyalkyl group are preferably used. In the present invention,
You may use these compounds in combination of 2 or more types.

Cycloolefin Resin Composition The cycloolefin resin composition according to the present invention is a compound [B] having a hydrophilic group and a hydrophobic group in the same molecule, relative to 100 parts by weight of the cyclic olefin resin [A]. ] From 0.01 to
It is contained in an amount of 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.3 to 3 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-based resin composition according to the present invention contains a cyclic olefin-based resin derived from a bulky cyclic olefin and a compound having a hydrophilic group and a hydrophobic group in the same molecule at a specific ratio, and has a high temperature. Excellent transparency can be maintained even when the environment changes from a high humidity atmosphere to a room 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. In addition, the compound [B] having a hydrophilic group and a hydrophobic group in the same molecule is not contained, and an additive other than the component [B], for example, tetrakis [methylene-3- (3,3 Even if it contains a stabilizer such as 5-di-t-butyl-4-hydroxyphenyl) propionate] methane, the transparency of the cyclic olefin resin composition may decrease due to environmental 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

As the stabilizer, for example, 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. For example, silica, diatomaceous earth or 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 parts such as spherical lenses, aspherical lenses, Fresnel lenses, prisms, light guide plates, CDs, MDs, DVDs, etc. 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, containers, transparent sheets and boards are particularly preferable.

[0074]

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.

[0075]

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.

[0076]

Examples 1 to 8 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 (hereinafter TCD-3) 1
00 parts by weight and, as the component [B], the components shown in Table 1 were added in the amounts (parts by weight) shown in Table 1, and tetrakis [methylene-3- (3,5- Di-t-butyl
4-hydroxyphenyl) propionate] methane to 0.
6 parts by weight were added, and the mixture was 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 resin composition was injection-molded into a square plate having a thickness of 3 mm by using an injection molding machine (IS-55EPN manufactured by Toshiba Machine). This square plate is 80 ℃,
After leaving it under high temperature and high humidity of 90% RH for 48 hours, it was taken out in normal temperature and normal humidity. Transparency before and after test (light transmittance)
Was evaluated.

[0077]

Comparative Example 1 Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane was added in an amount of 2.6 parts by weight without adding the component [B]. A square plate was molded and tested in the same manner as in Example 1 except for the above.
The results are shown in Table 1.

[0078]

COMPARATIVE EXAMPLE 2 Without adding the component [B], tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane was added in an amount of 0.1 part by weight. A square plate was molded and tested in the same manner as in Example 1 except for the above.
The results are shown in Table 1.

[0079]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display location C08L 101: 00) (72) Inventor Toshiyuki Hirose 6-1, 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 6-12 Waki, Waki-cho, Kuga-gun, Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Junji Tan 1-2-6, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Co., Ltd.

Claims (7)

[Claims] 1. [A] (1) The following [A-1], [A-2] and [A-3]
(2) Softening point temperature (TMA) is 80 ° C or higher, and (3) Intrinsic viscosity [η] (in decalin at 135 ° C)
Is from 0.05 to 10 dl / g, and [B] is a compound having a hydrophilic group and a hydrophobic group in the same molecule, and the cyclic olefin resin [A] is 100 parts by weight. , 0.01 with a compound [B] having a hydrophilic group and a hydrophobic group.
10 to 10 parts by weight of the cyclic olefin resin composition; [A-1] Random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II] ; [Chemical 1] (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]
Alternatively, a ring-opening polymer or copolymer of a cyclic olefin represented by [II], and [A-3] a hydride of the above ring-opening polymer or copolymer [A-2]. 2. [B] A compound having a hydrophilic group and a hydrophobic group in the same molecule, wherein the hydrophilic group of the compound is a hydroxyalkyl group and the hydrophobic group is an alkyl group having 6 or more carbon atoms, or It is an amide compound, The cyclic olefin resin composition of Claim 1 characterized by the above-mentioned. 3. The compound [B] having a hydrophilic group and a hydrophobic group is contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the cyclic olefin resin [A]. The cyclic olefin resin composition according to claim 1 or 2. 4. A plastic lens comprising the cyclic olefin resin composition according to claim 1. 5. A container comprising the cyclic olefin resin composition according to claim 1. 6. A transparent sheet or board made of the cyclic olefin resin composition according to claim 1. 7. An optical recording medium comprising the cyclic olefin resin composition according to claim 1.