JP3456489B2 - Container made of cyclic olefin resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a container formed from a cyclic olefin resin composition.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Conventionally used polyolefins are resins having excellent chemical resistance and solvent resistance, but they cannot be said to have sufficient transparency, heat resistance and rigidity.

Therefore, a method of adding a nucleating agent in order to improve the transparency, heat resistance and rigidity of the polyolefin,
Alternatively, a method of gradually cooling the melted polyolefin to increase the crystallinity is adopted, but the effect cannot be said to be sufficient.

Apart from such conventional polyolefins, a copolymer obtained by reacting ethylene with a bulky monomer is superior in various properties such as heat resistance to conventional polyolefins. It has been reported (for example, U.S. Pat. No. 883,372, JP-A-46-1491).
No. 0).

The present applicant uses a specific cyclic olefin as a bulky monomer, and a cyclic olefin random copolymer obtained by copolymerizing this cyclic olefin with ethylene is transparent, heat resistant, and We have found that it is a synthetic resin with excellent rigidity and have already filed an application (JP-A-60-168708, 61-120816, 61-115912, 61-).
115916, 61-271308, 61-272216, 62-25240
No. 6, 62-252407).

Further, the above-mentioned cyclic olefin random copolymer is not only excellent in transparency, heat resistance and rigidity, but also
It was found that it has a high water vapor barrier property and is suitable for a container that requires water retention.

However, the impact strength may be insufficient depending on the application. Therefore, the present applicant has previously disclosed a method of improving the impact strength by adding an elastomer to the cyclic olefin-based copolymer or forming a crosslinked structure (for example, JP-A-2-167318, the same). 3-122157, 4-
170454, 3-072546, 3-72547, 3-52939,
No. 4-226147, No. 5-9350, No. 3-281646, No. 1-318052
Nos. 3-122148 and 4-353540).

According to the method disclosed in the above publication, the impact strength is certainly improved, but there is a problem that the transparency of the molded body is lost.

[0009]

OBJECT OF THE INVENTION It is an object of the present invention to provide a container formed from a composition containing a cyclic olefin resin as described above and having excellent transparency and impact resistance.

[0010]

SUMMARY OF THE INVENTION The container according to the present invention has a softening temperature of 50 to 100 ° C. as measured by [A] thermal mechanical analyzer and a glass transition point (Tg).
At least one cyclic olefin resin selected from the group consisting of the following [A-1], [A-2], [A-3] and [A-4] at 40 to 90 ° C ; 99 to 50 parts by weight And [B] the density at 23 ° C. is 0.94 to 0.98 g / c
It is characterized by comprising a cyclic olefin resin composed of 1 to 50 parts by weight of an m ³ ethylene polymer.

[A-1] An ethylene / cyclic olefin random copolymer obtained by copolymerizing ethylene with a cyclic olefin represented by the following general formula [I] or [II]. [A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the following formula [I] or [II].

[A-3] A hydride of the above-mentioned [A-2] ring-opening polymer or copolymer. [A-4] A graft modified product of the above [A-1], [A-2] or [A-3].

[0013]

[Chemical 3]

[I] In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a And R ^b each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, which hydrocarbon group may be substituted with halogen, and R ^{15 to} R ¹⁸ are , May be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and An alkylidene group may be formed with R ¹⁸ .

[0015]

[Chemical 4]

[II] In the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2,
The R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, an atom or a group selected from the group consisting of hydrocarbon groups and alkoxy groups, the hydrocarbon group may be substituted by halogen, R ⁹ Alternatively, the carbon atom to which 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 through an alkylene group having 1 to 3 carbon atoms. Good, and n = m
When = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring.

The container of the present invention obtained by shaping a cyclic olefin resin composition comprising a cyclic olefin resin and a specific ethylene resin into a predetermined shape as described above is excellent in transparency and High impact strength.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The container according to the present invention will be specifically described below. The container according to the present invention is formed by shaping a composition comprising a cyclic olefin resin [A] and an ethylene polymer [B] into a predetermined shape.

First, each component of the cyclic olefin resin composition forming the container according to the present invention will be described. Cyclic olefin resin [A] The cyclic olefin resin [A] used in the present invention is
[A-1] A random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II], [A-2] a cyclic olefin represented by the following formula [I] or [II] Ring-opening polymer or copolymer, [A-3] above [A-2] hydride of ring-opening polymer or copolymer, or [A-4] above [A-
1], [A-2] or [A-3] graft-modified product.

The cyclic olefin resin [A] used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.05 to 10 dl / g, preferably 0.3.
~ 2.0 dl / g, more preferably 0.4-1.2 dl / g
Is.

The cyclic olefin resin [A] is
The softening temperature (TMA) measured by a thermal mechanical analyzer is 10 to 120 ° C (glass transition point (Tg)
Is usually 0 to 110 ° C., more preferably 20 to 110 ° C. (Tg: 10 to 100 ° C.),
More preferably 50 to 100 ° C. (Tg: 40 to 90)
℃). TMA of cyclic olefin resin [A] is 1
When the temperature is lower than 0 ° C, the heat resistance of the product tends to decrease, which is not preferable, and when the TMA exceeds 120 ° C, the transparency of the product tends to decrease, which is not preferable.

Further, the crystallinity of the cyclic olefin resin [A] measured by the X-ray diffraction method is usually 0 to
It is 20%, preferably 0 to 2%. Here, first, the cyclic olefin represented by the formula [I] or [II] used when forming the cyclic olefin resin as described above will be described.

[0023]

[Chemical 5]

[I] 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 each independently represent the following atom or hydrocarbon group, and when q is 0, each bond is bonded to form a 5-membered ring. Form.

In the above formula [I], R ^{1 to} R ¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.

Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C3-C15 cycloalkyl group, or 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. Further, these alkyl groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Cycloalkyl groups include cyclohexyl
Examples of the aromatic hydrocarbon group include
Examples thereof include a phenyl group and a naphthyl group. Furthermore
In the above formula [I], R¹⁵And R¹⁶And R¹⁷And R
¹⁸And R¹⁵And R ¹⁷And R¹⁶And R¹⁸And R¹⁵And R¹⁸
Or, or R¹⁶And R¹⁷And are respectively combined (mutually
, May form a monocycle or a polycycle,
Moreover, the monocycle or polycycle formed in this way is double
It may have a bond. A monocycle formed here or
Specific examples of the polycyclic structure include the following structures.
You can

[0028]

[Chemical 6]

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

[0030]

[Chemical 7]

[II] In the 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 each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group. Here, the halogen atom has the same meaning as the halogen atom in the above formula [I].

As the hydrocarbon group, each independently, an alkyl group having 1 to 20 carbon atoms and 1 to 1 carbon atoms.
There may be mentioned 20 halogenated alkyl groups, cycloalkyl groups having 3 to 15 carbon atoms or aromatic hydrocarbon groups. 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. Further, these alkyl groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include:
Examples thereof include an aryl group and an aralkyl group, and specific examples thereof include 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.
Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and R
^The carbon atom to which ¹³ is bonded or the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. That is, when the above 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 cooperate with each other. Methylene group (-CH
_2- ), ethylene group (-CH ₂ CH _2- ) or propylene group (-CH ₂ C
It forms an alkylene group in any of H ₂ CH _2- ).

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. In this case, examples of the monocyclic or polycyclic aromatic ring include R ¹⁵ and R when n = m = 0.
Mention may be made of the groups described below in which ¹² further forms an aromatic ring.

[0037]

[Chemical 8]

Here, q has the same meaning as q in the formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] include bicyclo [2.
2.1] Hept-2-ene derivative, tetracyclo [4.4.0.
1 ^2,5 .1 ^7,10 ] -3-Dodecene derivative, hexacyclo [6.6.
1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives,
Octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8 .0
^12,17 ] -5-dococene derivative, pentacyclo [6.6.1.
1 ^3,6 .0 ^2,7 .0 ^9,14] -4-hexadecene derivative, heptacyclo-5-eicosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4.3.0.1 ^{2, 5]-3-decene} derivative, Tricyclo [4.3.0.1 ^2,5 ] -3-undecene derivative,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3-pentadecene derivatives, pentacyclo [8.7.0.1.3.6.1 ^10,17 .1 ^12,15 .0
^2,7 .0 ^11,16] -4-eicosene derivatives, Nonashikuro [10.9.
1.1 ^4,7 .1 ^13,20 .1 ^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19 ] -5-
Pentacocene derivative, pentacyclo [8.4.0.1 ^2,3 .
1 ^9,12 .0 ^8,13] -3-hexadecene derivative, pentacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12,17] -5- heneicosene derivatives , Nonashikuro [10.10.1.1 ^5,8 .1 ^14,21 .1
^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives, 1,4-methano -1,4,4a, 9a- tetrahydrofluorene derivatives, 1, 4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct and the like can be mentioned.

In the following, the above formula [I] or [II]
More specific examples of the cyclic olefin represented by are shown below.

[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29]

[0061]

[Chemical 30]

[0062]

[Chemical 31]

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.

These cyclic olefins can be used alone or in combination of two or more. The cyclic olefin-based 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, 61-120816, 61-120816.
-115912, 61-115916, 61-271308, 61-2722
It can be produced by appropriately selecting the conditions according to the method proposed by the present applicant in publications such as No. 16, No. 62-252406 and No. 62-252407. [A-1] Ethylene / Cyclic Olefin Random Copolymer [A-1] The ethylene / cyclic olefin random copolymer has a constitutional unit derived from ethylene of usually 52 to 9
It contains 0 mol%, preferably 55-80 mol%, and usually 10-48 mol%, preferably 20-45 mol% of structural units derived from cyclic olefins. The ethylene composition and cyclic olefin composition are
Measured by ¹³ C-NMR.

In this [A-1] ethylene / cyclic olefin random copolymer, the structural units derived from ethylene and the structural units derived from cyclic olefin as described above are randomly arranged and bonded, It has a substantially linear structure. The fact that this copolymer is substantially linear and does not have a substantially gel-like crosslinked structure means that when this copolymer is dissolved in an organic solvent, this solution contains insoluble components. Can be confirmed by not. For example, when measuring the intrinsic viscosity [η] as described below,
It can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

In the [A-1] ethylene / cyclic olefin random copolymer used in the present invention, the above formula [I]
Alternatively, at least a part of the cyclic olefin represented by [II] is considered to constitute the repeating unit represented by the following formula [III] or [IV].

[0067]

[Chemical 32]

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

[0069]

[Chemical 33]

[IV] In the above formula [IV], n, m, p, q and R ^{1 to} R ¹⁹ have the same meanings as in formula [II].

The [A-1] ethylene / cycloolefin random copolymer used in the present invention is a structural unit derived from another copolymerizable monomer, if necessary, within a range not impairing the object of the present invention. May have.

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- with 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 -1H-indene and other cycloolefins, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene, 5-n-butyl-2-norbornene, 5-isobutyl -2-norbornene, 5,6-dimethyl-2-norbornene, 5-chloro-2-norbornene and
Norbornenes such as 5-fluoro-2-norbornene, 1,4
-Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl
Non-conjugated dienes such as -1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene may be mentioned.

These other monomers can be used alone or in combination. [A-1] Ethylene
In the cyclic olefin random copolymer, the constitutional unit derived from the other monomer as described above is usually 20
It may be contained in an amount of not more than mol%, preferably not more than 10 mol%.

The [A-1] ethylene / cyclic olefin random copolymer used in the present invention comprises ethylene and a compound of the formula [I].
Alternatively, it can be produced by the production method disclosed in the above publication using a cyclic olefin represented by [II]. Among these, this copolymerization 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 [A-1] ethylene / cyclic olefin random copolymerization. It is preferred to produce a polymer.

In this copolymerization reaction, a solid group IVB metallocene catalyst can be used. Where solid IV
The Group B metallocene catalyst is a catalyst composed of a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound, and an organoaluminum compound to be blended if necessary. Here, the group VI transition metal is zirconium, titanium or hafnium, and these transition metals have at least one ligand containing a cyclopentadienyl skeleton. here,
Examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group which may be substituted with an alkyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group. These groups may be bonded via another group such as an alkylene group. The ligand other than the ligand containing a cyclopentadienyl skeleton is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or the like.

Further, as the organoaluminum oxy compound and the organoaluminum compound, those generally used for the production of olefin resins can be used. Such solid IVB metallocene catalysts are described, for example, in JP-A-61-221206, JP-A-64-106 and JP-A-2-73112. [A-2] Ring-opening polymer or copolymer of cyclic olefin In the ring-opening polymer or ring-opening copolymer of cyclic olefin, at least a part of the cyclic olefin represented by the above formula [I] or [II] Is considered to constitute a repeating unit represented by the following formula [V] or [VI].

[0077]

[Chemical 34]

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

[0079]

[Chemical 35]

[VI] where n, m, p, q and R in the above formula [VI]
^{1 to} R ¹⁹ have the same meanings as in formula [II].

Such a ring-opening polymer or a ring-opening copolymer can be produced by the production method disclosed in the above-mentioned publication. For example, the ring-opening polymerization of the cyclic olefin represented by the above formula [I] is carried out. It can be produced by polymerization or copolymerization in the presence of a catalyst.

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 polymer or copolymer The hydrogenation product of the [A-3] ring-opening polymer or copolymer used in the present invention is a ring-opening polymer obtained as described above. Alternatively, it can be obtained by hydrogenating the copolymer [A-2] in the presence of a conventionally known hydrogenation catalyst.

In the hydride of the [A-3] ring-opening polymer or copolymer, at least a part of the cyclic olefin represented by the formula [I] or [II] is represented by the following formula [VII]
Alternatively, it is considered to have a repeating unit represented by [VIII].

[0084]

[Chemical 36]

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

[0086]

[Chemical 37]

[VIII] In the above formula [VIII], n, m, p, q, R ¹
~ R ¹⁹ has the same meaning as in formula [II]. [A-4] Graft-modified product The graft-modified product of the cyclic olefin resin is the above-mentioned [A-
1] Ethylene / Cyclic Olefin Random Copolymer, [A-
2] A ring-opened polymer or copolymer of a cyclic olefin, or a graft-modified product of a hydride of the [A-3] ring-opened polymer or copolymer.

Examples of the modifier include unsaturated carboxylic acids such as maleic anhydride, derivatives of these acid anhydrides or alkyl esters of unsaturated carboxylic acids, and the like.

The modification ratio of the graft-modified cycloolefin resin used in the present invention is usually 10 mol% or less. Such a graft modified product of a cyclic olefin-based resin can be produced by blending a cyclic olefin-based resin with a modifying agent so as to have a desired modification ratio and then graft-polymerized. It can also be produced by preparing and then mixing this modified product with an unmodified cyclic olefin resin.

In the present invention, as the cyclic olefin resin [A], any of the above [A-1], [A-2], [A-3] and [A-4] may be used. It is also possible to use these in combination. [B] Ethylene-based Polymer The ethylene-based copolymer [B] used in the present invention is either a homopolymer of ethylene or a copolymer of ethylene and at least one α-olefin.

The α-olefin constituting the ethylene / α-olefin copolymer has 3 to 2 carbon atoms.
There may be mentioned 0 α-olefins. 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-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc., and mixtures thereof Can be mentioned. Of these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1
-Pentene, 1-octene, 1-decene and the like are preferable.

In the ethylene / α-olefin copolymer as described above, the content of α-olefin is usually 20 mol% or less, preferably 15 mol% or less, although it varies depending on the kind of α-olefin.

The density of the ethylene polymer used in the present invention is 0.94 to 0.98 g / cm ³ , preferably 0.95 to 0.98 g / cm ³ , and more preferably 0.9.
It is 6 to 0.98 g / cm ³ . Ethylene polymer [B]
If the density is out of the above range, the transparency of the product tends to decrease.

An ethylene polymer having a crystallinity of 30% or more, preferably 50% or more, which is measured by an X-ray diffraction method, is used. High density polyethylene is particularly preferred in the present invention.

The ethylene polymer used in the present invention may be graft-modified with a modifier.
Examples of the modifier include unsaturated carboxylic acids such as maleic anhydride, derivatives of these acid anhydrides or alkyl esters of unsaturated carboxylic acids, and the like.

The modification ratio of this graft-modified ethylene polymer is usually 10 mol% or less. Such a modified ethylene polymer can be produced by blending the ethylene polymer with a modifier so as to have a desired modification ratio and graft-polymerizing it, or preparing a modified product with a high modification ratio in advance. Then, the modified product and an unmodified ethylene-based polymer may be mixed and diluted so as to have a desired modification ratio, to produce the composition. Cyclic olefin resin composition The container of the present invention is formed by shaping the cyclic olefin resin composition comprising [A] cyclic olefin resin and [B] ethylene polymer into a predetermined shape as described above. .

The cyclic olefin resin composition used here is 99 to 50 parts by weight, preferably 88 to 70 parts by weight, of [A] cyclic olefin resin. More preferably 9
5 to 80 parts by weight and 1 to 50 parts by weight of the [B] ethylene polymer.
By weight, preferably 2 to 30 parts by weight, more preferably 5 to 20 parts by weight.

The total amount of the cyclic olefin resin [A] and the ethylene polymer [B] is 100 parts by weight. Further, this cyclic olefin resin composition is another component within a range not impairing the object of the present invention, for example, a crosslinking agent, a crosslinking aid, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent. , An antifogging agent, a lubricant, a dye, a pigment, a mineral oil-based softener, a petroleum resin, a wax and the like may be contained.

For example, a stabilizer added as an optional component is tetrakis [methylene-3- (3,5-di-t-butyl).
-4-Hydroxyphenyl) propionate] methane, β-
(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxazamide bis [ethyl-3-
Phenolic antioxidants such as (3,5-di-t-butyl-4-hydroxyphenyl) propionate; fatty acid metal salts such as zinc stearate, calcium stearate, calcium 1,2-hydroxystearate; glycerin monostearate Examples thereof include polyhydric alcohol fatty acid esters such as glycerin distearate, petaerythritol monostearate, petaerythritol distearate and petaerythritol tristearate. These may be blended alone or in combination. Examples of the combined use of these additives include the combination of tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane with zinc stearate or calcium stearate. be able to.

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

It is also possible to contain a polymeric material such as polyamide or polyester in an amount within the range where the transparency of the molded article is not impaired. This cyclic olefin-based resin composition is, for example, a method of simply kneading the cyclic olefin-based resin [A] and the ethylene-based polymer [B], or at least the cyclic olefin-based resin [A] and the ethylene-based polymer [B]. It can be manufactured by adopting a method of kneading while forming a crosslinked structure in either one.

As a specific method for forming a crosslinked structure, a method using an organic peroxide, or a functional group such as a carboxyl group, an acid anhydride group, a hydroxyl group or an epoxy group is previously added to the component [A] and / or the component [B]. After producing a resin composition using a group introduced, a carboxyl group, a compound having an amino group or a hydroxyl group for the acid anhydride group, a compound having a carboxyl group or an acid anhydride group for the hydroxyl group, Examples of the method include crosslinking the epoxy group with a compound having an amino group or an acid anhydride group.

Examples of organic peroxides used herein include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexane peroxide; 1,1-bis (t-butylperoxy) cyclohexane and 2,2-bis.
Peroxyketals such as (t-butylperoxy) octane; t-butylhydroperoxide, cumene hydroperoxide and 2,5-dimethylhexane-2,5-dihydroxyperoxide, 1,1,3,3- Hydroperoxides such as tetramethylbutyl hydroperoxide; di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5 -Dialkyl peroxides such as di (t-butylperoxy) hexyne-3; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; t-butylperoxyacetate, t-butylperoxybenzoate and 2,5 There may be mentioned peroxyesters such as -dimethyl-2,5-di (benzoylperoxy) hexane.

These organic peroxides are usually added in an amount of 0.01 to 100 parts by weight of the resin in the resin composition.
To 1 part by weight, preferably 0.05 to 0.5 part by weight.

When forming a crosslinked structure using the above organic peroxide, it is preferable to use a compound having two or more polymerizable unsaturated compounds. Examples of the compound having two or more polymerizable unsaturated compounds used herein include a diene compound, and examples of the diene compound include divinylbenzene, vinyl acrylate, vinyl methacrylate, triallyl isocyanurate. , Diallyl phthalate, ethylene dimethacrylate and trimethylolpropane trimethacrylate. Among these, it is particularly preferable to use an aromatic diene compound and further divinylbenzene.

The compound having two or more polymerizable unsaturated compounds, preferably a diene compound, is usually 1 part by weight or less, preferably 0 part by weight, relative to 100 parts by weight of the resin in the resin composition of the present invention. Used in an amount of 0.1 to 0.5 parts by weight. By thus forming a crosslinked structure in the composition, the mechanical properties of the molded product are improved.

The cyclic olefin resin composition can be prepared by applying a conventionally known method. In particular,
A method of mechanically blending the cyclic olefin resin [A], the ethylene polymer [B], and optionally the above-mentioned other components with an extruder, a kneader, a roll, or the like, an appropriate good solvent for each of these components, For example, hexane, heptane,
A method of dissolving in a solvent such as decane, cyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, etc., or separately dissolving and then mixing, and removing the solvent, and a method combining these methods. And so on. Manufacturing of Container The container according to the present invention is formed by shaping the cyclic olefin resin composition obtained by the above method into a predetermined shape.

That is, a container having a desired shape can be produced by employing various molding methods such as injection molding and blow molding of the heat-melted cyclic olefin resin composition. For example, as the molded body (or container) of the present invention, a molded body manufactured by a direct blow molding method, a container manufactured by an injection blow molding method, a container manufactured by an injection molding method, and an extrusion molding method are obtained. Examples thereof include containers using tubes.

Specifically, eye drops bottles, vials, syringes and other such medicinal containers, cosmetic containers, paint and poster color containers, culture bottles, pens, and other tubes molded as described above. An example is a container.

[0110]

As described above, the container of the present invention is obtained by shaping a cyclic olefin resin composition comprising a specific cyclic olefin resin and an ethylene polymer having a specific density into a desired shape. To be This cyclic olefin resin composition is excellent in heat resistance, rigidity and moisture resistance,
Particularly, it has excellent transparency and impact resistance. Therefore, the container of the present invention is transparent and has a characteristic that it is not easily damaged even if an impact is applied to the container such as dropping.

[0111]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. [Creation of test pieces] Toshiba Machine Co., Ltd. injection molding machine IS-55
Molding was performed using an EPN and a predetermined mold for making test pieces. After molding, the test piece was left standing at 23 ° C. for 48 hours and then subjected to measurement. [Creation of blow bottle] ASB manufactured by Nissei ASB Co., Ltd.
A biaxially stretched blow bottle having an internal volume of 500 ml was molded using an injection blow molding machine at 50 TH. [Evaluation method] (1) Softening temperature (TMA) The thermal deformation behavior of a sheet having a thickness of 1 mm was measured using a Thermal Mechanical Analyzer manufactured by DuPont. 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 entered the sheet by 0.635 mm was taken as TMA.

(2) Glass transition temperature It was measured at a temperature rising rate of 10 ° C./min using a DSC-20 manufactured by SEIKO Denshi Kogyo Co., Ltd.

(3) Bending test According to ASTM D790, using a 1/8 inch thick injection test piece, cross head speed of 20 mm / min, 23
The test was conducted at 0 ° C. to measure the flexural modulus and flexural strength.

(4) Izod impact strength: Measured at 23 ° C. according to ASTM D790 using an injection test piece having a thickness of 1/8 inch.

(5) Light transmittance According to ASTM D1003, measurement was carried out at 23 ° C. using a 2 mm-thick emission square plate.

(6) Blow bottle drop impact impact test A blow bottle filled with water was dropped from the estimated breaking height and the height of the next bottle was set to 30 cm or 10 cm depending on the presence or absence of cracks.
Up and down, 30 pieces were dropped to obtain 50% breaking height.

[0117]

Example 1 [A] component had an ethylene content of 78 mol%, an MFR of 3 measured under the conditions of 260 ° C. and 2160 g.
The intrinsic viscosity [η] measured in decalin at 135 ° C. for 9 g / 10 min is 0.60 dl / g, and the softening point temperature (hereinafter abbreviated as TMA) measured by a thermal mechanical analyzer is 9
Ethylene at 0 ° C (Tg, 80 ° C) and tetracyclo [4.4.
80 parts by weight of a random copolymer with 0.1 ^{2,5.1 7,10} ] dodecene-3 (hereinafter abbreviated as TCD-3), a density of 0.968 g / cm ³ , 190 ° C., 2160 g as a [B] component. 20 parts by weight of a polyethylene homopolymer having an MFR of 5.5 g / 10 min measured under the conditions were kneaded and pelletized by a twin-screw extruder set at 250 ° C.

Then, the pellets were injection-molded into predetermined test pieces, and their physical properties were measured.

[0119]

Example 2 Instead of the polyethylene of the component [B] used in Example 1, the density was 0.956 g / cm ³ , 190 ° C., 216.
Test pieces were obtained in the same manner as in Example 1 except that polyethylene having 1-butene as a comonomer whose MFR measured at 0 g was 0.1 g / 10 min was used.

[0120]

Example 3 Instead of polyethylene as the component [B] used in Example 1, the density was 0.930 g / cm ³ , 190 ° C., 216.
Test pieces were obtained in the same manner as in Example 1 except that linear low density polyethylene having 4-methyl-1-pentene as a comonomer was used with an MFR measured at 0 g of 1.3 g / 10 min. .

[0121]

Comparative Example 1 The same cyclic olefin resin (component [A]) as that used in Example 1 was injection molded as it was, and the physical properties were measured.

[0122]

Comparative Example 2 Instead of the polyethylene of the component [B] used in Example 1, the density was 0.910 g / cm ³ , 190 ° C., 216.
Test pieces were obtained in the same manner as in Example 1 except that linear low-density polyethylene having 4-methyl-1-pentene as a comonomer was used at an MFR of 3.0 g / 10 minutes measured at 0 g. .

[0123]

Comparative Example 3 Instead of the component [A] used in Example 1,
The ethylene content was 66 mol%, the MFR measured under the conditions of 260 ° C. and 2160 g was 8.5 g / 10 min, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.61 dl / g, TM
The same operation as in Example 1 was carried out except that an ethylene / TCD-3 random copolymer having A of 150 ° C. was used to obtain a test piece.

[0124]

Example 4 The cyclic olefin resin composition prepared by the same method as in Example 1 was blow-molded by the above method to obtain a blow bottle. Table 2 shows the results of the drop impact test of this blow bottle.

[0125]

Comparative Example 4 The [A] component (cyclic olefin resin) used in Example 1 was blow-molded to obtain a blow bottle. Table 2 shows the results of the drop impact test of this blow bottle.

[0126]

[Table 1]

[0127]

[Table 2]

Claims (2)

(57) [Claims] 1. A glass having a softening point temperature of 50 to 100 ° C. measured by a thermal mechanical analyzer.
The following [A-1] and [A-1] having a transition point (Tg) of 40 to 90 ° C.
-2], [A-3] and at least one cyclic olefin resin selected from the group consisting of [A-4]; 95 to 50 parts by weight, and [B] the density at 23 ° C is 0.94 to 0. .98 g /
A container characterized by shaping a cyclic olefin resin composition composed of 5 to 50 parts by weight of an ethylene polymer of ³ cm ³ into a desired shape; [A-1] ethylene and the following formula [I] Or ethylene obtained by copolymerizing with a cyclic olefin represented by [II]
Cyclic olefin random copolymer; [However, in the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are respectively Independently, it represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, which hydrocarbon group may be substituted with halogen, and R ^{15 to} R ¹⁸ are bonded to each other to form a single bond. May form a ring or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ are alkylidene groups. May be formed. ]; [Chemical 2] [However, in the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2,
The R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, an atom or a group selected from the group consisting of hydrocarbon groups and alkoxy groups, the hydrocarbon group may be substituted by halogen, R ⁹ Alternatively, the carbon atom to which 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 through an alkylene group having 1 to 3 carbon atoms. Good, and n = m
When = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ] [A-2] Ring-opening polymer or copolymer of cyclic olefin represented by the above formula [I] or [II], [A-3] [A-2] Ring-opening polymer or copolymer Combined hydride and [A-4] The graft-modified product of [A-1], [A-2] or [A-3]. 2. The container according to claim 1, wherein the ethylene polymer [B] is high density polyethylene.