JPH08332701A - Aroma retention packing material and container - Google Patents

Abstract

PURPOSE: To provide aroma retention to strawberry essence by forming at least one layer out of cyclic olefin-based resin selected from among graft modified substance of polymer such as random copolymer consisting of ethylene and particular cyclic olefin, the ring-opening polymer or copolymer of the cyclic olefin and these hydride. CONSTITUTION: This is a layered product whose one layer at least is formed out of a cyclic resin [A] layer of olefin series selected from among graft modified substance of [A-1], 9146/28]A-2], [A-3] of random copolymer consisting of [A-1] ethylene and cyclic olefin expressed by a formula I or II, [A-2] the ring-opening polymer or copolymer of the cyclic olefin expressed by the formula I or II, and [A-3] the hydride of the ring-opening polymer or copolymer [A-2]. (n) shown in the equation I is 0 or 1, (m) is 0 or positive integer, (q) is 0 or 1, R<1> -R<18> , R<a> , R<b> is a hydrocarbon radical which may be substituted with hydrogen atom or halogen, R<15> -R<18> may be formed with ring which may have double bonding, (p), (q) shown in the formula II is 0 or positive integer, (m), (n) is 0-2, R<1> -R<19> is hydrocarbon or alkoxy radical which may be substituted with hydrogen atom or halogen.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aroma retaining packaging material and a container capable of preserving these aroma contents with excellent aroma retaining property without impairing the aroma of foods, cosmetics and the like.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as materials for forming packaging materials and containers for foods and cosmetics, polyolefins such as polyethylene and polypropylene, ethylene-vinyl alcohol copolymer, vinylidene chloride, polyethylene terephthalate, polyamide, polyacrylonitrile. Alternatively, composite materials of these and other materials are widely used.

By the way, citrus juice, vegetable juice,
Beverages such as coffee, foods such as natto and curry, frozen foods, cosmetics, and bath salts are also important commercial values for their flavors. For this reason, packaging materials or containers that store such fragrant contents are
It is necessary to form a material which is excellent in transparency and moldability, is excellent in moisture resistance, heat sealability and the like, can suppress the alteration of the contents, and is excellent in aroma retention. Such an aroma retaining material is required not only to have an excellent gas barrier property capable of highly blocking an aroma component, but also to be non-adsorptive to the aroma component. For this reason, among the above resins, polyolefins are inferior in gas barrier property and show adsorbability for aroma components, and therefore polyolefins are not usually used alone as a fragrance retaining material.

Generally, as such a fragrance retaining material,
(a) Polyester such as polyethylene terephthalate,
Polyamide, ethylene-vinyl alcohol copolymer, polycarbonate, high-barrier resin such as polyacrylonitrile, (b) vapor-deposited film obtained by vapor-depositing aluminum, silica, etc. in a thin film on a film such as polyester or polyolefin, and (c) aluminum foil A composite laminate with a resin is known.

However, the high-barrier resin (a) as described above has a blocking selectivity for aroma component species, and cannot evenly show aroma retention for various contents. For example, polyethylene terephthalate is inferior in aroma retention to ester-based aroma components such as strawberry essence. Also, since the ethylene-vinyl alcohol copolymer is produced by saponifying an ethylene / vinyl acetate copolymer, the ethylene-vinyl alcohol copolymer itself has an odor (aldehyde odor, residual acetic acid odor, etc.).
May be emitted.

The vapor-deposited film (b) usually has a vapor-deposited layer which is an extremely thin thin film having a thickness of about 400 Å, and is easily cracked by impact during use, resulting in deterioration in aroma retention. There is.

Further, the composite laminate (c) of aluminum foil and resin has the best gas barrier property, but the cost is high, it is not suitable for recycling, and it causes a problem of waste treatment. Substitution with other materials is desired.

[0008] In view of the above-mentioned prior art, the present inventor has researched materials such as packaging materials or containers having excellent aroma retaining property. As a result, cyclic olefin resins derived from cyclic olefins having a specific structure are The present invention has been completed by discovering that, unlike known polyolefins, it has excellent fragrance retaining properties, and also exhibits fragrance retaining properties against strawberry essence, which polyethylene terephthalate cannot do.

[0009]

It is an object of the present invention to provide an aroma retaining packaging material and a container capable of preserving these aroma contents with excellent aroma retaining properties without impairing the aroma properties of foods, cosmetics and the like. Has a purpose

[0010]

SUMMARY OF THE INVENTION At least one layer of the fragrance retaining packaging material and container according to the present invention has the following [A-1], [A-2] and [A-3].
And a cyclic olefin resin [A] selected from [A-4]
It is formed of a laminate of layers.

[A-1] Ethylene and the following formula [I] or [I
I] an ethylene / cyclic olefin random copolymer obtained by copolymerizing with a cyclic olefin;

[0012]

Embedded image

(In the formula [I], n is 0 or 1, and m is
Is 0 or a positive integer, q is 0 or 1, and R
^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a 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 R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. May be. ),

[0014]

[Chemical 4]

(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 which may be substituted with a halogen or an alkoxy group, wherein the carbon atom to which R ⁹ or R ¹⁰ is bonded and R ¹³ are bonded to each other. To the carbon atom to which R ¹¹ is bonded or directly to the carbon atom to which R ¹¹ is bonded through an alkylene group having 1 to 3 carbon atoms, and 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 above-mentioned fragrance retaining packaging material and container are
It is preferably formed from a laminate having a cyclic olefin resin [A] layer as the innermost layer of the packaging material or the container. Further, the above-mentioned fragrance-wrapping packaging material and container are preferably formed from a laminate having an α-olefin (co) polymer layer or a gas barrier resin layer as the outermost layer of the packaging material or container.

The laminate forming the aroma retaining packaging material according to the present invention may have a heat seal layer together with the cyclic olefin resin [A] layer, and the heat seal layer is an α-olefin. It is preferably formed of a (co) polymer. Further, the heat seal layer may be formed of a gas barrier resin.

Cyclic olefin resin [A] as described above
The layer thickness may normally be 5 to 100 μm. The fragrance retaining packaging material and container according to the present invention are also excellent in fragrance retaining property of the fragrance component containing an ester compound as a main component.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The aroma retaining packaging material and container according to the present invention will be specifically described below. The aroma retaining packaging material and the container according to the present invention are formed of a laminate in which at least one layer is composed of a specific cyclic olefin resin [A] layer as described below.

The fragrance retaining packaging and container according to the present invention are
It is a packaging material such as a film or sheet or a pack formed from these, and a container such as a tray, a cup or a bottle, and the shape thereof is not particularly limited.

First, the laminated body forming the fragrance-wrapping packaging material and the container will be described below. The laminated body contains a layer made of the following cyclic olefin resin [A].

[A] Cyclic olefin resin In the present invention, as the cyclic olefin resin, [A-1] a random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II], A-2] Ring-opening polymer or copolymer of a cyclic olefin represented by the following formula [I] or [II], [A-3] The above ring-opening polymer or copolymer [A-3
-2] hydride, and [A-4] above [A-1], [A-2]
Alternatively, at least one selected from the graft modified products of [A-3] is used.

The softening temperature (TMA) of the cyclic olefin resin [A] used in the present invention measured by a thermal mechanical analyzer is 60 ° C. or higher, preferably 70 ° C.
The glass transition point (Tg) is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 to 200 ° C.

The degree of crystallinity of the cyclic olefin resin [A] measured by the X-ray diffraction method is 0 to 20%, preferably 0 to 2%. The intrinsic viscosity [η] of the cyclic olefin resin [A] measured in decalin at 135 ° C. is 0.05 to 10 dl / g, preferably 0.3.
˜2.0 dl / g, more preferably 0.4 to 1.2 dl / g.

The cyclic olefin represented by the formula [I] or [II] which forms the cyclic olefin resin [A] will be described. Cyclic olefin

[0026]

Embedded image

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, and 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, there may be mentioned, independently of each other, an alkyl group usually having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and a cycloalkyl group. Examples thereof include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl 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 (cooperatively with each other) to form a monocycle or polycycle, and the monocycle or polycycle thus formed has a double bond. Good. Specific examples of the monocycle or polycycle formed here are shown below.

[0031]

[Chemical 6]

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

[0034]

[Chemical 7]

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, an alkyl group having 1 to 20 carbon atoms,
Examples thereof include halogenated alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specifically, as the alkyl group,
Examples include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and cycloalkyl groups include cyclohexyl group and 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, a phenylethyl group and the like.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group.
These hydrocarbon group and alkoxy group 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.
It may be bonded via the alkylene group of 3. 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, It forms an alkylene group of any one of a methylene group (-CH _2- ), an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH ₂ CH 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, as the monocyclic or polycyclic aromatic ring, for example, n = m = 0 as shown below.
In this case, a group in which R ¹⁵ and R ¹² further form an aromatic ring can be mentioned.

[0040]

Embedded image

Here, q has the same meaning as q in the formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] are shown below.

[0042]

[Chemical 9]

(In the above formula, the numbers 1 to 7 indicate 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) ,Five-
(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-
Examples include 2-heptene derivatives.

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.

[0046]

[Chemical 10]

(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-11,12-dimethyl,
5,8,9,10-Tetramethyl, 8-ethylidene, 8-ethylidene-
9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8-n-propylidene- 9-
Ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl,
8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9
-Dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl),
8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl), 5,6-diphenyl and the like can be mentioned.

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.

[0049] pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13]
-3-Pentadecene and its derivatives. Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4,10- penta octadecadienoic Penta cyclopentadiene octadecadienoic compound such.

[0050] 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.

[0051] 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 .0 12,16] -5- eicosene, and derivatives thereof.

[0052] heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .0
^3,8 .0 ^12,17] -5-heneicosene, and a derivative thereof.
Octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8 .0
^12,17 ] -5-Dococene and its derivatives.

[0053] 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. 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]} -6-hexacosenoic,
And derivatives thereof.

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] of the initial description
Examples of the structure of the cyclic olefin shown in [4] can be given.

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 may 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
The copolymer [A-1] ethylene / cyclic olefin random copolymer 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 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], 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, 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].

[0060]

[Chemical 11]

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].

[0062]

[Chemical 12]

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 may have a unit derived from another copolymerizable monomer, if necessary, within a range not impairing the object of the present invention. Good.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic 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-
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 -1 H-indene and other cycloolefins, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2 -Non-conjugated dienes such as norbornene can be mentioned. It may be a combination of these.

The ethylene / cycloolefin random copolymer [A-1] contains a unit derived from the above-mentioned other monomer in an amount of usually 20 mol% or less, preferably 10 mol% or less. May be.

The ethylene / cyclic olefin random copolymer [A-1] is produced by the production method disclosed in the above publication using ethylene and the cyclic olefin represented by the formula [I] or [II]. You can 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 to produce an ethylene / cyclic olefin random copolymer [A- 1] is preferably produced.

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 of Cyclic Olefin or
Copolymer Cyclic olefin ring-opening polymer or ring-opening copolymer [A-2]
Then, it is considered that at least a part of the units derived from the cyclic olefin represented by the above formula [I] or [II] is represented by the following formula [V] or [VI].

[0070]

[Chemical 13]

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

[0072]

Embedded image

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-opening (co) polymer can be produced by the production method disclosed in the above-mentioned publication. For example, a cyclic olefin represented by the above formula [I] is polymerized in the presence of a ring-opening polymerization catalyst. Alternatively, 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 of Ring-Opening Polymer or Copolymer
Things ring-opening (co) polymer hydride [A-3] is preferably a ring-opening polymer or ring-opening copolymer as described above and [A-2], hydrogen in the presence of a known hydrogenation catalyst Can be obtained.

Hydride of this ring-opening (co) polymer [A-3]
Then, at least a part of the units derived from the formula [I] or [II] is considered to be represented by the following formula [VII] or [VIII].

[0077]

[Chemical 15]

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

[0079]

Embedded image

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 graft modified product of the cyclic olefin resin is the above-mentioned ethylene / cyclic olefin random copolymer [A-1], a cyclic olefin ring-opening polymer or copolymer [A-2], or a ring-opening (copolymer). ) Graft-modified polymer hydride [A-
3].

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 kinds.

The modification ratio of the graft-modified product of the cyclic olefin resin used in the present invention is usually preferably 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 order to obtain a graft-modified product of a cyclic olefin resin from a cyclic olefin resin and a modifier, conventionally known polymer modification methods can be widely applied.
For example, a graft-modified product is obtained by a method such as adding a modifier to a molten cyclic olefin resin for graft polymerization (reaction), or adding a modifier to a solvent solution of the cyclic olefin resin for graft reaction. be able to.

Such a graft reaction is usually carried out at 60 to 3
It is carried out at a temperature of 50 ° C. The graft reaction can be carried out 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 obtained directly by a graft reaction between a cyclic olefin resin and a modifying agent, and a modified product having a high modification ratio can be obtained in advance by a graft reaction between the cyclic olefin resin and a modifying agent. It is also possible to obtain the modified product by 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] is used.
As the above, any of the above [A-1], [A-2], [A-3] and [A-4] can be used alone, or can be used in combination. Of these, ethylene / cyclic olefin random copolymers [A-
1] is preferably used.

Cycloolefin [A] Layer The cycloolefin resin [A] layer can be formed by extrusion molding the above-mentioned cycloolefin resin [A]. The cyclic olefin [A] layer may be stretched after extrusion molding.

The cyclic olefin resin layer is within a range not impairing the object of the present invention.
Polymers, polyamides, polyesters, ethylene-vinyl alcohol copolymers, other polymers such as polyvinyl chloride, polyvinylidene chloride, EPR, EPDM, SBS, S
It may contain an elastomer such as EBS, SIS or SEPS which improves impact strength.

Among the other polymers, α, which is excellent in transparency,
-Olefin (co) polymers, specifically α-olefin (co) polymers which will be described later as the other layer are preferable, but particularly high density polyethylene (HDPE), low density linear polyethylene (LLDPE), etc. Is preferably used.

The cyclic olefin resin layer contains these other polymers or elastomers in an amount of 0.5 to 40% by weight, preferably 1 to 40% by weight, based on the cyclic olefin resin [A].
It may be contained in an amount of 20% by weight, more preferably 3 to 10% by weight.

Further, the cyclic olefin resin layer is a UV absorber, a heat stabilizer, a weather stabilizer, a light stabilizer, an antistatic agent, a slip agent, an antiblocking agent, as long as the object of the present invention is not impaired. Anti-fog agents, nucleating agents, lubricants, dyes, pigments, natural oils, synthetic oils that absorb only light of a specific wavelength,
It may contain an additive such as a wax or a transparent filler.

When the cyclic olefin resin layer contains other components as described above, the cyclic olefin resin [A] is dry-blended with other components when the cyclic olefin resin layer is formed. Alternatively, the cyclic olefin resin [A] and other components may be melt-kneaded and pelletized in advance, and the pellets may be supplied to the molding machine. Further, the cyclic olefin resin [A] and other components may be separately or collectively dissolved in a solvent and mixed, and the solvent may be removed and then supplied to a molding machine.

In the laminate for forming the fragrance-wrapping packaging material and the container according to the present invention, the thickness of the layer made of the above cyclic olefin resin [A] is not particularly limited, but usually 5 to 100 μm, It is preferably 15 to 50 μm.

In the present invention, the other resin [B] as described above is used.
The layer may contain other components such as the additives and rubber components shown in the layer [A] within a range not impairing the object of the present invention.

Fragrance retaining packaging and container The flavor retaining packaging and container according to the present invention are formed from a laminate having at least one cyclic olefin resin [A] layer as described above.

As the resin forming the other layers of this laminate, any known resin may be used without particular limitation as long as it can form a laminate together with the above cyclic olefin resin [A].

For example, an α-olefin (co) polymer having 2 to 20 carbon atoms can be used. This carbon number 2-2
Specific examples of the α-olefin of 0 include ethylene, 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-
Examples thereof include ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

The α-olefin (co) polymers are those α
-Even if it is an olefin homopolymer, two or more kinds of α-
It may be a copolymer of olefins. Further, the α-olefin (co) polymer may be a copolymer of these α-olefin and an unsaturated group-containing polar monomer.

As the unsaturated group-containing polar monomer,
1 carbon atom such as vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate
-8, preferably acrylic acid ester or methacrylic acid ester having 1 to 4 alkyl groups, acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate and the like.

Further, the α-olefin (co) as described above
The polymer is a compound containing other compounds such as cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene and 3a, 5,6,7a-tetrahydro-4,7-methano-
Cycloolefins such as 1H-indene, 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
Contains units derived from -1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, non-conjugated dienes such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene, and combinations thereof You may have.

Among these, ethylene (co) polymers,
Propylene (co) polymers are preferred. As the ethylene (co) polymer, specifically, ethylene containing a unit derived from ethylene in an amount of 80 mol% or more, preferably 90 mol% or more, and another α-olefin and / or unsaturated group-containing polar monomer A copolymer of ethylene or a homopolymer of ethylene is preferably used.

The density of this ethylene (co) polymer is 0.1
86 to 0.98 g / cm ³ preferably 0.90 to 0.94 g /
cm ³ is desirable, and melt flow rate M
FR (190 ° C) is 0.05 to 100 g / 10 minutes, preferably 0.5 to 50 g / 10 minutes, and the Vicat softening point is 70.
˜120 ° C., preferably 75 to 110 ° C.

As such an ethylene (co) polymer,
More specifically, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDP)
E), ethylene-vinyl acetate copolymer (EVA), EE
Examples include A, EAA, EMAA, and ionomers.

As the propylene (co) polymer, the unit derived from propylene is 70 mol%, preferably 80
A copolymer of propylene contained in an amount of mol% or more and another α-olefin and / or an unsaturated group-containing polar monomer or a propylene homopolymer is preferably used.

The density of this propylene (co) polymer is
0.83 g / cm ³ or more, preferably 0.89 to 0.92 g / cm
³ , the melting point (Tm) is 120 to 170 ° C., preferably 120 to 145 ° C., and the melt flow rate MFR.
(190 ° C.) is 0.01 to 100 g / 10 minutes, preferably 0.1.
05-50g / 10min, Vicat softening point is 100-
170 ° C., preferably 110 to 160 ° C.

More specific examples of such a propylene (co) polymer include polypropylene (PP). In addition, the other layer of the laminate is composed of amorphous polyester (A-PET), amorphous polyamide (A-PA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polyamide (P).
It can also be formed using a gas barrier resin such as A), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyacrylonitrile (PAN), or polycarbonate (PC).

The above-mentioned other resins can be used in combination of two or more kinds. For example, even if one layer other than the cyclic olefin resin [A] is formed from a composition containing two or more kinds of other resins. It is also possible to form a plurality of respective resin layers.

The laminate for forming the aroma retaining packaging material and the container according to the present invention is composed of two or more layers including the cyclic olefin resin [A] layer. In the present invention, this cyclic olefin resin [A] layer may form the innermost layer of the packaging material and the container.

When the laminate is composed of three or more resin layers, the other resin layers may be the same kind of resin layer or different resin layers. For example, a cyclic olefin resin [ Both layers of the layer A] may be formed of the same or different resins. Further, two or more different resin layers may be provided on one surface of the cyclic olefin resin [A] layer, for example, on the outer layer side of the packaging material and the container. The laminate composed of three or more resin layers may be composed of, for example, another resin layer / cycloolefin resin [A] layer / other resin layer, and further, one surface of the [A] layer. The other resin [B] layer on the side and / or both sides may be formed of four or more layers formed of two or more layers.

Among the aroma retaining packaging materials and containers according to the present invention formed from such a laminate, the laminate forming the aroma retaining packaging material has a heat seal layer as another layer. Is preferred.

The heat seal layer can be formed by a conventionally known heat seal material. For example, among the above-mentioned other resins, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDP).
E), linear low density polyethylene (LLDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), EEA, EAA, EMAA, ionomers and other α-olefin (co) polymers. be able to. Furthermore, the heat seal layer can be formed of a gas barrier resin such as amorphous polyester (A-PET), amorphous polyamide (A-PA), ethylene-vinyl alcohol copolymer (EVOH).

Among these, when heat seal strength and gas barrier property are required, amorphous polyester (A-PET), amorphous polyamide (A-PA), ethylene-vinyl alcohol copolymer (EVOH). ) And the like are preferably used.

Since such a heat-sealing layer is provided as the innermost layer of the fragrance-wrapping material and comes into contact with the contents, its thickness is preferably as thin as possible within the range where heat-sealing strength can be obtained. Specifically, the thickness of the heat seal layer is
It is usually 5 to 100 μm, preferably 10 to 70 μm, and more preferably 15 to 50 μm.

The fragrance-wrapping packaging material and container according to the present invention are formed of a laminate having the α-olefin (co) polymer layer or the gas barrier resin layer as exemplified above as the outermost layer. It is preferable.

Among the α-olefin (co) polymers forming the outermost layer, linear low density polyethylene (LLDP)
E), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE)
Are preferred.

The outermost layer is provided as a protective layer for the cyclic olefin resin layer, and the thickness thereof is not particularly limited as long as it can prevent the cyclic olefin resin layer from being damaged by an external impact. This outermost layer may be stretched.

The laminate comprising the cyclic olefin resin [A] and another resin can be formed by widely utilizing conventionally known lamination methods. For example, a packaging material such as a film or a sheet may be formed by a multi-layer T-die method, a multi-layer inflation method, a co-extrusion molding method such as an extrusion lamination method, a wet or dry lamination method, a multi-layer blow method, a two-color molding method, a sandwich molding method, It is formed by a known multilayer stacking method such as a stamping molding method. Further, such a molding method may be combined with a stretching process (eg, biaxial tubular, biaxial tenter).

In the present invention, the cyclic olefin resin [A]
It is preferable to coextrude the resin with other resin to form a laminate. Also, an adhesive layer may be provided between the cyclic olefin resin [A] layer and the other resin layer. A wide variety of known adhesives can be used as this adhesive, but maleic anhydride-modified polyolefin resin (for example, Admer;
Mitsui Petrochemical Co., Ltd., Modic; Mitsubishi Chemical Co., etc.), low (non) crystalline soft copolymers of unsaturated polyolefins, ethylene / acrylic acid ester / maleic anhydride terpolymer (Bondaine) Sumika Chemical Industries, Ltd.) or an adhesive resin composition containing them can be used.

A more specific structural example of such a laminate will be shown. In the following examples, COC is a cyclic olefin resin [A], other resin abbreviations are the resins shown above, and the laminate structure is shown as outer layer / COC / inner layer.

LLDPE / COC PET / COC PA / COC LLDPE / COC / LLDPE PP / adhesive / COC / adhesive / PP PA / adhesive / COC / LLDPE PA / EVOH / adhesive / COC / LLDPE PET / adhesive / LLDPE / COC / Adhesive / AP
ET PET / Adhesive / LLDPE / COC / Adhesive / EVO
H etc.

In the present invention, the film-shaped or sheet-shaped packaging material as described above preferably has a heat seal layer on the inner layer side of the cyclic olefin resin layer. The cyclic olefin resin layer may be the innermost layer. Further, it may have a polyolefin layer and / or a gas barrier layer on the outer layer side.

The thickness of the laminate forming such a film-like or sheet-like wrapping material may vary depending on the intended use, etc., but is usually 5 to 250 μm, preferably 10 to 15 μm.
It is desirable that the thickness is 0 μm, more preferably about 20 to 100 μm.

For containers such as tubes and bottles, the laminate obtained by extrusion molding as described above may be blow-molded into a desired shape, or a laminated container may be directly formed by multi-layer blow molding or injection molding. You can also

Among the fragrance-wrapping materials and containers according to the present invention, the laminate forming the container has a cyclic olefin resin layer as the innermost layer of the container and an α-olefin (co) polymer layer as the outer layer and It is preferred to have / or a gas barrier layer.

The thickness of the laminate for forming such a container such as a tube or a bottle is appropriately 25 to 1500 μm, preferably 50 to 100, though it varies depending on the application.
It is preferably about 0 μm.

The fragrance retaining packaging material and container according to the present invention as described above have a low blocking selectivity for aroma component species,
It is excellent in aroma retention for various fragrance components. In particular, the scent-preserving packaging material and container according to the present invention are also excellent in scent-preserving property with respect to scent components mainly containing an ester compound such as strawberry essence.

[0129]

INDUSTRIAL APPLICABILITY The fragrance retaining packaging material and container according to the present invention can preserve these fragrant contents with excellent fragrance retaining properties without impairing the fragrance properties of foods, cosmetics and the like. The fragrance-wrapping material and the container according to the present invention have little blocking selectivity with respect to aroma component species and exhibit excellent fragrance-keeping properties with respect to various contents.

[0130]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

Fragrance Retaining Evaluation Method 0.2 cc of each test fragrance was impregnated into absorbent cotton of a predetermined size. Heat-seal (four-sided seal) between the inner layers of each film so that the inner dimensions are 50 x 50 mm.
The absorbent cotton impregnated with the above-mentioned fragrance was inserted into the bag thus prepared and hermetically sealed. The bag is then placed in a 100 ml glass bottle, which is closed with a lid. This glass bottle is 25 ℃
It was left to stand under normal temperature conditions, and after a predetermined number of days, the lid was opened and an odor sensory test in a glass bottle was conducted.

In the odor sensory test, the same panelists each time evaluated the presence / absence of perfume scent detection, and the low fragrance detection after a long period was used as an index of aroma retention. The results were evaluated according to the following criteria. Evaluation criteria ○: No fragrance is detected, △: Slight scent is detected, ×: Smell is detected, XX: Smell is detected very strongly. Here, the following four types of essences (Kobayashi fragrance) are used. (Manufactured by K.K.) was used.

Strawberry essence, orange essence (IIM-9135), apple essence (HF-13979),
(MT-1939), vanilla essence

[0134]

Example 1 LLDPE (9 μm) was prepared using the following materials.
m) / COC (23 μm) / LLDPE (8 μm).

COC is a random copolymer of ethylene and tetracyclododecene (MFR (260
℃) = 30g / 10 minutes, softening temperature (TMA) = 90 ℃)
(“Apel” APL6509T (manufactured by Mitsui Petrochemical Industry Co., Ltd.) was used.

As LLDPE, linear low-density polyethylene (MFR value (190 ° C.) = 2.1 g / 10 minutes, density = 0.920 g / cm ³ ) (Ultzex Uz2021L
(Mitsui Petrochemical Industry Co., Ltd. product)) was used.

The three-layer coextruded film was formed by the coextrusion T-die cast film processing method under the following conditions. Extruder: 65 mmφ, 50 mmφ, 50 mmφ (merging method: feed block method) T-die: coat hanger type (die opening width 800 m
m, die slit gap 0.7 mm) Resin processing temperature: 250 ° C, film take-up speed: 30 m /
min With respect to the three-layer film obtained above, the fragrance retaining property of each fragrance essence was evaluated by the above method. The results are shown in Table 1.

This three-layer film showed very good aroma retention for any type of perfume essence.

[0139]

[Comparative Example 1] A biaxially oriented polypropylene film (25 μm thickness: OP # 25U-1) was used as an aroma retaining property evaluation film.
The fragrance retaining property was evaluated in the same manner as in Example 1 by using (commercially available product of Tohcello Co., Ltd.). The results are shown in Table 1.

[0140]

Comparative Example 2 As an evaluation film, a PVDC-coated biaxially oriented polypropylene film (25 μm thickness: VOP #
Using 25.OLD (manufactured by Tohcello Co., Ltd.), the aroma retaining property was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0141]

Comparative Example 3 As the evaluation film, a highly moisture-proof modified polypropylene film YB-22 (22 μm thickness: a commercial product manufactured by Toray Industries, Inc.) was used, and the aroma retaining property was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0142]

COMPARATIVE EXAMPLE 4 In Example 1, polyethylene terephthalate PET-G 6738 (amorphous PET, density =
PET monolayer having a thickness of 30 μm in the same manner as in Example 1 except that only 1.27 g / cm ³ , glass transition temperature = 81 ° C., Vicat softening point = 82 ° C. (manufactured by Eastman Kodak Co., Ltd.) was used. I got a film.

Using this single layer film, the aroma retaining property was evaluated in the same manner as in Example 1. The results are shown in Table 1. This film showed better aroma retention than the other Comparative Examples 1 to 3, and was inferior in aroma retention to strawberry essence.

[0144]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08F 210/14 MJS 7107-4J C08F 210/14 MJS 255/00 MQG 255/00 MQG 283/14 MQW 283/14 MQW C08G 61/08 NLG C08G 61/08 NLG (72) Inventor Mariko Kawakubo 9 Kitatone, Sowa-cho, Sarushima-gun, Ibaraki Tohcello Co., Ltd. R & D Center (72) Inventor Uno Ayako Ibaraki 9 Tohokune, Sowa-cho, Sarushima-gun, In the research and development center of East Cello Co., Ltd. (72) Inventor Yasushi Amata 3-5-2 Kasumigaseki, Chiyoda-ku, Tokyo Mitsui Petrochemical Co., Ltd.

Claims (8)

[Claims] 1. At least one of the following [A-1] and [A-2]
, [A-3] and [A-4], a fragrance-wrapping material and a container formed from a laminate comprising a cyclic olefin resin [A] layer; [A-1] ethylene and the following formula [I: ] Or [II] or a cyclic olefin represented by [II], wherein the ethylene / cyclic olefin random copolymer is obtained; (In the 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 each independently hydrogen. Atom, a halogen atom or a hydrocarbon group optionally substituted with halogen, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring, and the monocyclic ring or the polycyclic ring is It may have a double bond, and is R ¹⁵ and R ¹⁶ , or R
¹⁷ and R ¹⁸ may form an alkylidene group. ), [Chemical formula 2] (In the formula [II], p and q are 0 or a positive integer,
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 optionally substituted with a halogen or an alkoxy group,
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 through an alkylene group having 1 to 3 carbon atoms. Or 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] The ring-opening polymer or copolymer of the cyclic olefin represented by the above formula [I] or [II], [A-3] The above ring-opening polymer or copolymer [A-2 ], And [A-4] a graft-modified product of [A-1], [A-2] or [A-3] above. 2. The fragrance-wrapping packaging material and container according to claim 1, wherein the packaging material or container comprises a laminate having the cyclic olefin resin [A] layer as an innermost layer. 3. A fragrance-wrapping packaging material according to claim 1, which is a laminate having an α-olefin (co) polymer layer or a gas barrier resin layer as the outermost layer of the packaging material or container. And container. 4. The aroma retaining packaging material according to claim 1, comprising a laminate having a heat seal layer together with the cyclic olefin resin [A] layer. 5. The heat seal layer comprises an α-olefin (co).
The aroma retaining packaging material according to claim 4, which is made of a polymer. 6. The aroma retaining packaging material according to claim 4, wherein the heat seal layer is made of a gas barrier resin. 7. The cyclic olefin resin [A] layer has a thickness of 5
It is -100 micrometers, The fragrance preservation packaging material and container in any one of Claims 1-6 characterized by the above-mentioned. 8. The aroma retaining packaging material and container according to any one of claims 1 to 7, wherein the aroma component contains an ester compound as a main component.