JP3055353B2 - PTP or blister pack packaging sheet or film, package, and method of forming the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet or a film for use as a molding material for PTP packaging of pharmaceutical packaging and other blister pack packaging, PTP or blister pack packaging using the same, and formation of the packaging. About the method.

[0002]

2. Description of the Related Art Blister pack packaging is widely used for packaging daily necessities, miscellaneous goods, tablet medicines and the like. In this blister pack packaging, a thermoplastic resin sheet or film is vacuum- or pressure-formed so as to form a blister (bulge) having a contour substantially matching the shape of the package to be packaged. After packaging, a sealing material (backing paper) is covered, and the flange (flat portion) of the sheet or film and the sealing material are heat-sealed or bonded so that the packaged material inside can be checked through a blister. It was made. In particular, in the case of small packages such as tablets and capsules, a breakable sealing material such as aluminum foil is used so that the blister can be easily pressed and unpacked.
TP packaging (press through pack) is widely used.

[0003] The material (material) of the sheet or film used for such PTP or blister pack packaging is required to have transparency, moisture proofness, and vacuum or air pressure moldability, and particularly when packaging drugs such as tablets. Is required to have even higher moisture resistance.

Conventionally, polyvinyl chloride, polypropylene, and the like have been used as a material for such a sheet or film for PTP or blister pack packaging.
However, their moisture proof properties are insufficient, and the application of polyvinylidene chloride and the formation of multiple layers have attempted to improve the moisture proof properties.
Polyvinyl chloride has a problem of environmental pollution, and there is a need for alternative materials.Polypropylene is gradually replacing polypropylene, but polypropylene is poor in transparency and poor in vacuum or pressure forming, resulting in low productivity. There is a problem.

On the other hand, Japanese Patent Application Laid-Open No. Sho 61-292601 discloses a cyclic olefin wherein n in formula (1) is 0,
A cyclic olefin random copolymer comprising a copolymer with ethylene is described as an optical material. But,
Since this copolymer is generally extremely brittle, difficult to form into a sheet or film, and has poor vacuum moldability, it has not been suggested to use it as a PTP or blister pack packaging sheet or film.

[0006] Japanese Patent Application Laid-Open No. 2-196832 discloses 13
The intrinsic viscosity measured in decalin at 5 ° C is 0.01 to 10
dl / g, a softening temperature (TMA) of 70 ° C. or more, and a cyclic olefin in the case where n of general formula [1] described below is 0;
A sheet or film obtained by biaxially stretching a cyclic olefin random copolymer comprising a copolymer with ethylene is described. However, such a biaxially stretched sheet or film shrinks when the surface temperature becomes equal to or higher than the softening temperature (TMA) , and thus it is difficult to form the sheet or film by vacuum or air pressure forming at a temperature equal to or higher than the softening temperature (TMA) .

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sheet or film for packaging a PTP or blister pack having excellent moisture proof and transparency and excellent vacuum or pressure forming properties in order to solve the above problems. To provide. Another object of the present invention is to provide a PTP or blister pack package comprising the above-mentioned sheet or film and having excellent moisture resistance and transparency, and a method for forming the package.

[0008]

The present invention relates to the following sheet or film for packaging a PTP or blister pack, a PTP or blister pack package using the same, and a method for forming the same. (1) (a) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 10 dl.
/ G, a softening temperature (TMA) is the 50 to 200 ° C., the cycloolefin random copolymer comprising a copolymer of cyclic olefin and ethylene represented by the following general formula (1), or (b) said annular Unstretched amorphous polyolefin resin of graft-modified olefin random copolymer (a)
A sheet or film for packaging PTP or blister pack, comprising a sheet or a film.

Embedded image (In the formula [1], 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 a hydrogen atom, a halogen atom and a carbon atom. indicates an atom or group selected from the group consisting of hydrogen radical. the R ¹⁵ to R ¹⁸ may form a monocyclic or polycyclic bonded to each other, also R ¹⁵ and R ¹⁶ or R ^17,
And R ¹⁸ may form an alkylidene group. R ¹⁵
The monocyclic or polycyclic formed by to R ¹⁸ may have a double bond. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. (2) A PTP or blister pack package comprising a molded article obtained by forming a blister on the unstretched sheet or film according to (1) and a sealing material. (3) the molded body has a blister for accommodating an article to be packaged, and a flange formed around the blister;
The PTP or blister pack package according to the above (2), wherein the flange portion is fixed to the sealing material and sealed. (4) The PTP or blister pack package according to (2) or (3), wherein the sealing material is made of an aluminum foil or the unstretched sheet or film according to (1). (5) The sealing material is coated on an aluminum foil or backing paper. ( B ) Intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.01 to 10 dl / g and the softening temperature (TMA) is 50
(2) wherein a graft modified product of a cyclic olefin random copolymer (a ) composed of a copolymer of the cyclic olefin represented by the general formula [1] and ethylene at a temperature of 200 to 200 ° C. is laminated. Or the PTP or blister pack package according to (3). (6) The object to be packaged is accommodated in the blister made of the unstretched sheet or film according to the above (1) and accommodating the object to be packaged, and a molded blister having a flange formed around the blister. And a method of forming a package, wherein the flange portion of the molded body and the sealing material are fixed by heat sealing or an adhesive.

In the present invention, the sheet or film is not
A stretching, the amorphous polyolefin resin serving as its material, the cycloolefin random copolymer (a) graft modified product of a copolymer of your whistle (a) is (b). These will be described in detail below.

The cyclic olefin which is a component of the amorphous polyolefin resin of the above (a) and ( b ) is at least one kind selected from the group consisting of unsaturated monomers represented by the general formula [1]. It is a cyclic olefin. First, the cyclic olefin represented by the general formula [1] will be described. In the formula [1], 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, each independently usually has 1 to 1 carbon atoms.
Examples thereof include an alkyl group having 20 atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, 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 group in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group is 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 a phenyl group and a naphthyl group. Further, in the above formula [1], R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ represent R
R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are bonded to each other (together with each other) to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring thus formed may have a double bond. Specific examples of the monocyclic or polycyclic ring formed here include the following.

[0013]

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In the above examples, carbon atoms numbered 1 or 2 are each represented by R in formula [1].
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.

Preferred examples of the cyclic olefin represented by the general formula [1] include a cyclic olefin represented by the following general formula [1-1].

Embedded image (In the formula [1-1], n, m, and R ^{1 to} R ¹⁸ are the same as those in the formula [1].)

Further, as the cyclic olefin represented by the above formula [1], a compound represented by the following general formula [2] can be exemplified.

Embedded image (In the formula [2], h is 0 or a positive integer, j
And k are 0, 1 or 2. m, R ^{7 to} R ¹⁵ and R ^{17 to} R ¹⁸ represent the same as those in the formula [1]. R ¹⁹ ~R ²⁷
Each independently represents 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 is the same as the halogen atom in the formula [1]. Further, R ^19-
As the hydrocarbon group for R ²⁷ , each is usually an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic group. And a 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. ,
Examples thereof include groups in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group has been 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 an aryl group and an aralkyl group. Specific examples include a phenyl group, a tolyl group, a naphthyl group, and a benzyl group. And a phenylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Where R ¹⁷
And the carbon atom to which R ¹⁸ is bonded and the carbon atom to which R ²¹ is bonded or the carbon atom to which R ¹⁹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. You may. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ¹⁷ and R ²¹ or the groups represented by R ¹⁸ and R ¹⁹ cooperate with each other. Te, a methylene group (-CH ₂ -), ethylene group (-CH ₂ CH ₂ -) or trimethylene group (-
CH ₂ CH ₂ CH ₂ —) to form any alkylene group.

Further, when j = k = 0, R ²³ and R ²⁰ or R ²³ and R ²⁷ may combine with each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include R ²³ and R ²³ when j = k = 0.
^The following groups and the like in which ²⁰ further forms an aromatic ring can be mentioned.

[0021]

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In the above example, h represents the same as h in the formula [2]. Formulas [1] and [1-
As the cyclic olefin represented by 1) or [2],
Specifically, bicyclo [2.2.1] hept-2-ene derivatives, tetracyclo [4.4.1 .1 ^2,5. 1 ^7,10] -3-dodecene derivatives, hexacyclo [6.6. ^{1.1 3,6} . 1 ^{10,13 .0
2,7.} 0 ^9,14] -4-heptadecene derivatives, octacyclo [8.8.3 .1 ^2,9. 1 ^4,7. 1 ^{11, 18.} 1 ^13,16. 0 ^3,8. 0
^12,17 ] -5-docosene 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 [4.3.1 0.1 ^2,5] -3- decene derivatives, tricyclo [4.4.1 0.1 ^2,5] -3-undecene derivatives, pentacyclo [6.5.1 1.1 ^3,6. 0 ^2,7. 0 ^9,13] -4-
Pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [.. 7.4.1 0.1 ^2,5 1 ^9,12 0 ^8,13] -
3-pentadecene derivative, heptacyclo [8.7.0.1 ^3,6 .
1 ^{10, 17.} 1 ^{12, 15.} 0 ^2,7. 0 ^11,16] -4-eicosene derivatives, Nonashikuro [10. 9.1.4 1 ^4,7. 1 ^{13, 20.} 1 ^{15, 18.} 0
..... ^3,8 0 ^2,10 0 ^12,21 0 ^{14,1 9]} -5-pentacosene derivatives, pentacyclo [8.4.1 .1 ^2,5 1 ^9,12 0 ^8,13] - 3-
Hexadecene derivative, heptacyclo [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 derivatives, cyclopentadiene-acenaphthylene adducts and the like.

The formulas [1] and [1-1] described above will be described below.
Or a more specific example of the cyclic olefin represented by [2].

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The cyclic olefin represented by the above general formula [1], [1-1] or [2] is produced by subjecting cyclopentadiene and an olefin having a corresponding structure to a Diels-Alder reaction. can do.

(A) Cyclic Olefin Random Copolymer The cycloolefin random copolymer (a) contains the above-mentioned cycloolefin component and ethylene component as essential components. If necessary, other copolymerizable unsaturated monomer components may be contained as long as the object of the present invention is not impaired. Unsaturated monomers which may optionally be copolymerized include, for example, those having 3 carbon atoms.
Α-olefins of from 20 to 20, hydrocarbon-based monomers containing two or more carbon-carbon double bonds in one molecule, and cyclic olefins other than the cyclic olefins represented by the general formula [1]. it can.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, -Heptene, 1-octene, 1
-Nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

The above-mentioned carbon-carbon double bond has two
Specifically, the hydrocarbon monomer containing at least one
4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 4-methyl-1,5-hexadiene, 5-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, Chain non-conjugated dienes such as 7-methyl-1,6-octadiene; cyclohexadiene;
Dicyclopentadiene, methyltetrahydroindene,
2-norbornene, 5-vinyl-2-norbornene, 5
-Ethylidene-2-norbornene, 5-methylene-2-
Norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene, 4,9,5,8-dimethano-3a, 4,4
cyclic unconjugated dienes such as a, 5,8,8a, 9,9a-octahydro-1H-benzoindene; 2,3-diisopropylidene-5-norbornene; 2-ethylidene-3-
Isopropylidene-5-norbornene; 2-propenyl-2,2-norbornadiene; Of these, 1,4-hexadiene, 1,6
-Octadienes and cyclic non-conjugated dienes, especially dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2
-Norbornene, 1,4-hexadiene and 1,6-octadiene are preferred.

Specific examples of the cyclic olefin other than the cyclic olefin represented by the general formula [1] include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene,
-(2-methylbutyl) -1-cyclohexene, 2,
3,3a, 7a-tetrahydro-4,7-methano-1H
-Indene, 3a, 5,6,7a-tetrahydro-4,
7-methano-1H-indene and the like.

Such unsaturated monomers which may be optionally copolymerized can be used alone or in combination. Usually, the cyclic olefin-based random copolymer (a) is used as one monomer.
If it is 00%, it is used in an amount of less than 50 mol%. In the cyclic olefin-based random copolymer (a), the structural unit derived from the ethylene component is in the range of 40 to 85 mol%, preferably 50 to 75 mol%, and the structural unit derived from the cyclic olefin component is 15 to 60 mol%. , Preferably 20 to
The range of 50 mol% is appropriate, and the structural unit derived from the ethylene component and the structural unit derived from the cyclic olefin component form a substantially linear cyclic olefin-based random copolymer randomly arranged. The fact that the cyclic olefin-based random copolymer (a) is substantially linear and does not have a gel-like crosslinked structure means that this copolymer is 135
It can be confirmed by complete dissolution in decalin at ℃.

Cyclic olefin random copolymer (a)
Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 10 dl / g, preferably 0.05 to 5 dl.
/ G, softening temperature (TMA) measured with a thermal mechanical analyzer is 50 to 200 ° C., preferably 60
To 200 ° C, more preferably 70 to 150 ° C. Note that the softening temperature (TMA) has a diameter of 1.
A 0 mm quartz needle is placed, a load of 49 g is applied, the temperature is raised at 5 ° C./min, and the temperature at which the needle enters 0.635 mm.

Further, the cyclic olefin random copolymer (a) has an iodine value (g-iodine / 100 g copolymer) of 30 or less, preferably 25 or less, and a glass transition temperature (Tg) of usually 30 to 180 ° C. , Preferably 40-1
80 ° C., crystallinity measured by X-ray diffraction method is 0 to 1
A range of 0%, preferably 0 to 7%, particularly preferably 0 to 5% is desirable.

In the (a) cyclic olefin-based random copolymer used in the present invention, the above-mentioned formulas [1] and [1-
At least a part of the structural unit derived from the cyclic olefin represented by [1] or [2] is represented by the following structural formula [1-a], [1-1-a] or [2-a], respectively. .

[0054]

Embedded image (In the formulas [1-a] and [1-1-a], n, m,
q, R ^{1 to} R ^18, R ^a and R ^b represent the same as those in the formula [1]. In the formula [2-a], m, h, j, k, R ⁷
To R ¹⁵ and R ^{17 to} R ²⁷ are the same as those in the formula [2]. )

In the present invention, the above-mentioned cyclic olefin random copolymer (a) can be used alone, or the copolymer (a) has an intrinsic viscosity [η] measured in decalin at 135 ° C. Is 0.01 to 5 dl / g, preferably 0.02 to 3 dl / g, and the softening temperature (TMA) is 5
An amorphous polyolefin resin composition (hereinafter referred to as resin) mixed with a cyclic olefin-based random copolymer ( c ) in a range of less than 0 ° C, preferably less than -10 to + 50 ° C, and more preferably less than +10 to + 50 ° C. Composition A).

Cyclic olefin random copolymer ( c )
In addition to the above physical properties, the glass transition temperature (Tg) is usually -30 to + 60 ° C, preferably -20 to + 60 ° C.
+ 50 ° C., the crystallinity measured by the X-ray diffraction method is 0 to
10%, preferably 0 to 7%, particularly preferably 0 to 5%
It is desirable to use those in the range.

Cycloolefin random copolymer ( c )
The same as the cyclic olefin random copolymer (a) can be used except that the intrinsic viscosity, the softening temperature (TMA), and other physical property values are different from those of the cyclic olefin random copolymer (a). For example, those in which ethylene and a monomer other than the cyclic olefin represented by the general formula [1] are copolymerized, or a modified product can be used.

The mixing ratio of the cyclic olefin random copolymer (a) and the cyclic olefin random copolymer ( c ) in the resin composition A is 100 parts by weight of the above (a) and 0 ( c ) 0 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight.
3-7 parts by weight, particularly preferably 0.5-5 parts by weight, most preferably 1.2 parts by weight.

The unmodified cyclic olefin random copolymer (a) is obtained by mixing an ethylene component, a cyclic olefin component represented by the above general formula [1] and other monomer components to be copolymerized if necessary with a well-known Ziegler-based copolymer. It can be produced by polymerizing in the presence of a catalyst.

Examples of the Ziegler-based catalyst include (I) a catalyst comprising a complex containing at least magnesium, titanium and halogen and an organoaluminum compound, and (II) a catalyst comprising a vanadium compound and an organoaluminum compound. be able to. Among these, the latter (II) catalyst is preferred, and a catalyst comprising a soluble vanadium compound and an organoaluminum compound is particularly preferred.

Next, a specific method for producing a cyclic olefin random copolymer (a) using a catalyst comprising a soluble vanadium compound and an organoaluminum compound will be described. In the method for producing the cyclic olefin-based random copolymer (a), the soluble vanadium compound used as a catalyst component is a vanadium compound that is soluble in a hydrocarbon medium of a copolymerization reaction system. VO (OR) _{a Xb} or V (OR) _c X _d (where R is a hydrocarbon group, X is halogen, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3,
2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d
≦ 4. The vanadium compound represented by the formula (1) or an electron donor adduct thereof can be given as a typical example. More specifically, VOCl ₃ , VO (OC
_{2 H 5) Cl 2, VO} (OC 2 H 5) 2 Cl, VO (O-is
_{o-C 3 H 7) Cl} 2, VO (O-n-C 4 H 9) Cl 2, V
O (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , V
_{O (O-n-C 4} H 9) 3 , etc. can be exemplified.

As the organoaluminum compound, a compound having at least one Al-carbon bond in the molecule can be used. For example, (i) a compound represented by the general formula R ¹ _m Al (OR ² ) _n H _p X _q (where , R ¹ and R ² each represent a hydrocarbon group having usually 1 to 15, preferably 1 to 4, carbon atoms, which may be the same or different, X represents a halogen, and m represents 0 ≦
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3, and m + n + p + q = 3. Or (ii) the general formula M ¹ Al (R ¹ ) ₄ (where M ¹ is Li, Na or K, and R ¹ is the same as in the above (i)) And a complex alkylated product of a Group I metal and aluminum.

The organoaluminum compound belonging to the above (i) is represented by the general formula R ¹ _m Al (OR ² ) _3-m (where R ¹ and R ² are the same as in the above (i). .5 ≦ m ≦ 3.) General formula R ¹ _m AlX _3-m (where R ¹ is the same as in the above (i), X is halogen, m
Is preferably 0 <m <3. ) General formula R ¹ _m AlH _3-m (where R ¹ is the same as in the above (i). M is preferably 2)
≦ m <3. ) General formula R ¹ _m Al (OR ² ) _n X _q (where R ¹ and R ² are the same as in the above (i). X is a halogen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, m + n
+ Q = 3. ) Can be exemplified.

In the organoaluminum compound belonging to the above (i), more specifically, triethylaluminum,
Trialkylaluminums such as tributylaluminum and triisopropylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, and (R ¹ ) ^{_{.. 0 5 Al (oR 2}} ) 0 alkylaluminum partially alkoxylated with an average composition represented by ₅ or the like; diethylaluminum chloride, dibutyl aluminum chloride, and dialkylaluminum halides such as diethylaluminum bromide, ethylaluminum sesquichloride Alkyl aluminum chloride such as chloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, etc. Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as skihalide , ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; dialkyl aluminum hydride such as diethyl aluminum hydride and dibutyl aluminum hydride; ethyl aluminum dihydride Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as propylaluminum dihydride; partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide Aluminum can be exemplified.

Further, as a compound similar to the above (i),
Two or more aluminum atoms are linked via oxygen or nitrogen atoms.
Combined organoaluminum compounds can also be used
You. Such compounds include, for example, (C_TwoH_Five)_TwoAl
OAl (C_TwoH_Five)_Two, (C_FourH₉) _TwoAlOAl (C_FourH₉)
_Two, (C_TwoH_Five)_TwoAlN (C₆H_Five) Al (C_TwoH_Five)_TwoSuch
Can be exemplified. Compounds belonging to the above (ii) include L
iAl (C_TwoH_Five)_Four, LiAl (C₇H ₁₅)_FourFor example
it can. Among these, especially alkyl aluminum
Halide, alkyl aluminum dihalide or this
It is preferred to use these mixtures.

The copolymerization reaction is usually performed in a hydrocarbon medium. Examples of the hydrocarbon medium include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Monomers and the like can be exemplified.
It may be a mixed medium of more than one kind.

The copolymerization reaction is preferably carried out by a continuous method. The concentration of the soluble vanadium compound supplied to the copolymerization reaction system at that time is 10 times or less, preferably 7 to 1 times, more preferably 5 to 1 times, most preferably the concentration of the soluble vanadium compound in the copolymerization reaction system. Is in the range of 3 to 1 times. The ratio of aluminum atoms to vanadium atoms (Al / V) in the copolymerization reaction system is 2 or more, preferably 2 to 50, and particularly preferably 3 to 20.
The soluble vanadium compound and the organoaluminum compound are each usually supplied after being diluted with the hydrocarbon medium. Here, the soluble vanadium compound is desirably diluted to the above concentration range, but the method of preparing the organoaluminum compound at an arbitrary concentration of, for example, 50 times or less the concentration in the copolymerization reaction system and supplying it to the copolymerization reaction system is preferred. Adopted. The concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.01 to 5 gram atoms / l as vanadium atoms.
iter, preferably 0.05-3 gram atoms / lit
er.

In the copolymerization reaction, the copolymerization reaction can be carried out in the presence of an electron donor, if necessary, in addition to the respective catalyst components of the soluble vanadium compound and the organoaluminum compound. Examples of the electron donor include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxysilanes; ammonia, amines, and nitriles. And a nitrogen-containing electron donor such as isocyanate.

The copolymerization reaction is carried out at a temperature of -50 to 100 ° C, preferably -30 to 80 ° C, more preferably -20 to 60 ° C. The copolymerization reaction is usually carried out by a continuous method, in which case, ethylene, a cyclic olefin as a polymerization raw material, a copolymerizable component to be copolymerized as required, a soluble vanadium compound as a catalyst component, an organoaluminum compound, and a hydrocarbon The medium is continuously supplied to the copolymerization reaction system, and the copolymerization reaction mixture is continuously withdrawn from the copolymerization reaction system. The average residence time during the copolymerization reaction varies depending on the type of the polymerization raw material, the concentration of the catalyst component and the reaction temperature, but is usually in the range of 5 minutes to 5 hours, preferably 10 minutes to 3 hours. The pressure during the copolymerization reaction is usually more than 0 to 50
kg / cm ² G or less, preferably more than 0 and 20 kg / cm ² G
cm ² G or less, and optionally an inert gas such as nitrogen or argon may be present. Further, in order to adjust the molecular weight of the copolymer, a molecular weight regulator such as hydrogen may be appropriately present.

The ethylene / cyclic olefin molar ratio supplied to the copolymerization reaction is usually in the range of 99/1 to 1/99, preferably 98/2 to 2/98. The resulting copolymer solution obtained by the copolymerization reaction is a cyclic olefin-based random copolymer in a hydrocarbon medium. The concentration of the cyclic olefin random copolymer contained in the resulting copolymer solution is usually in the range of 2 to 20% by weight, preferably 2 to 10% by weight. The resulting copolymer solution is mixed with ketones such as acetone, methyl ethyl ketone and acetylacetone or alcohols such as methanol, ethanol and butanol, etc., usually at 0 to 100 ° C., preferably at 10 to 70 ° C.
C., particularly preferably at a temperature near the boiling point of ketones or alcohols, to bring them into contact under stirring to precipitate the cyclic olefin-based random copolymer (a). By separating the precipitated copolymer by a separation means such as filtration or centrifugation, a cyclic olefin-based random copolymer (a) is obtained.

Cyclic olefin random copolymer ( c )
Can also be produced in the same manner as the cyclic olefin random copolymer (a). A specific production method of the cyclic olefin random copolymer (a) is described in JP-A-60-16.
8708, JP-A-60-95905, JP-A-60-95906, and JP-A-61-120816
JP, JP-A-61-115912, JP-A-61-159912
JP-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-2
No. 52406, Japanese Patent Application Laid-Open No. 62-252407, and the like.

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

( B ) Graft-modified product In the present invention, instead of the cyclic olefin random copolymer (a ), a graft-modified product (b) of this copolymer (a ) is used.
May be used. Examples of the graft-modified product ( b ) include a graft-modified product using a modifying agent such as an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a derivative thereof.

The unsaturated carboxylic acids used for the modification include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.2.1] Hept-5-
Examples include ene-2,5-dicarboxylic acid (nadic acid, trademark) and methyl-endosis-bicyclo [2.2.1] hept-5-ene-2,5-dicarboxylic acid (methylnadic acid, trademark) and the like. Can be. Examples of the unsaturated carboxylic anhydride include maleic anhydride, citraconic anhydride, nadic anhydride, and methylnadic anhydride. Further, as unsaturated carboxylic acid derivatives, acid halide compounds of the above-mentioned unsaturated carboxylic acids (for example, maleyl chloride), imide compounds (for example, maleimide), ester compounds (for example, monomethyl maleate, dimethyl maleate and glycidyl maleate) And so on. Among these,
Maleic anhydride or nadic anhydride is preferred. Modifiers can be used alone or in combination.

The content of a modifier such as an unsaturated carboxylic acid contained in the graft-modified product ( b ) is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight. In the present invention, a mixture of a modified product and an unmodified product may be used. In this case, a mixture of the modified product and the unmodified product having a high modification rate in which the content of the modifying agent exceeds 10% by weight is used. As a whole, those having a modified content in the above range can also be used.

135 of such a graft-modified product ( b )
The intrinsic viscosity [η] and softening temperature (TMA) measured in decalin at 0 ° C. are in the same ranges as those of the unmodified product, and the iodine value, glass transition temperature and crystallinity are also the same as those of the unmodified product. It is preferable to use those in the same range.

Cycloolefin random copolymer (a )
In order to modify the unmodified product with a denaturing agent, for example, a method in which the unmodified product is melted and a modifying agent such as an unsaturated carboxylic acid is added to react the unmodified product, the unmodified product is suspended or dissolved in a solvent, and Various methods can be used, such as a method of adding a denaturant to a suspension or a solution, a method of dissolving both in a solvent, and a reaction, and a method of reacting both in a solid state such as powder.

By such a modification reaction, a modifier is graft-polymerized to the cyclic olefin random copolymer (a ) to obtain a modified product. Particularly limited in the graft position of the modifier to be grafted to the cycloolefin random copolymer (a) is not sufficient if bonded to any carbon atoms that constitute co-polymer (a).

In any of the above methods, the modifying agent (graft monomer) is efficiently reacted (graft polymerization).
In order to carry out the reaction, the graft reaction is preferably performed in the presence of a radical initiator. As the radical initiator, an organic peroxide, an organic perester, an azo compound or the like can be used.

The radical initiator is preferably used in an amount of usually 0.001 to 1 part by weight based on 100 parts by weight of the unmodified product. The reaction temperature of the graft reaction using the radical initiator or the graft reaction performed without using the radical initiator is usually preferably set in the range of 60 to 350 ° C.

In the present invention, the amorphous polyolefin resins (a) and ( b ) (hereinafter referred to as essential components) may be used in combination of two or more, and the cyclic olefin resin ( c ) may be used. In addition to the system-based random copolymer, a rubber component for improving impact strength is compounded as another component within a range that does not impair the purpose of the present invention, and other resin components, a heat stabilizer, and a weather stabilizer are included. , Light stabilizer, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, nucleating agent, lubricant, dye, pigment, natural oil, synthetic oil, wax or translucent that absorbs only light of a specific wavelength A filler and the like can be blended.

For example, as a stabilizer blended as an optional component, specifically, tetrakis [methylene-3 (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-tert-butyl-4-)
(Hydroxyphenyl) propionic acid alkyl ester,
2,2'-oxamidobis [ethyl-3 (3,5-di-
phenolic antioxidants such as t-butyl-4-hydroxyphenyl) propionate]; zinc stearate;
Fatty acid metal salts such as fatty acid calcium such as calcium stearate and calcium 12-hydroxystearate; fatty acid esters of polyhydric alcohols; and the like.

These may be blended alone, for example, tetrakis [methylene-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] methane and a combination of zinc stearate and glycerin monostearate. In the present invention,
It is preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol. As such a fatty acid ester of the polyhydric alcohol, a part of the alcoholic hydroxyl group of the trihydric or higher polyhydric alcohol is esterified. And polyhydric alcohol fatty acid esters.

Examples of such fatty acid esters of polyhydric alcohols include glycerin monostearate,
Glycerin fatty acid esters such as glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin dilaurate; pentaerythritol monostearate (p
entaerythritol mono star
ate), fatty acid esters of pentaerythritol such as pentaerythritol monolaurate, pentaerythritol distearate and pentaerythritol tristearate. These may be used alone or in combination with each other.

The phenolic antioxidant is used in an amount of less than 10 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the total of essential components.
It is desirable to use less than 2 parts by weight, more preferably less than 2 parts by weight. The fatty acid ester of the polyhydric alcohol is desirably used in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the total of essential components.

[0100] In the present invention, an unstretched sheet or film for PTP or blister pack packaging, non-rolled
Shrinkage due to heating during vacuum or pressure forming for elongation
And not. As its material, the amorphous using a polyolefin resin or a resin composition, but from the viewpoint of transparency and vacuum or pressure forming properties, the cycloolefin random copolymer and its modified product of said (a) (b ) Is preferred,
In terms of vacuum or air pressure moldability and heat sealability,
The modified product ( b ) is particularly preferred.

The sheet or film of the present invention is obtained by forming a sheet or film from the above-mentioned amorphous polyolefin resin or a composition comprising the above-mentioned amorphous polyolefin resin and other components as required. The thickness of the sheet or film is not particularly limited, but is not less than 150 μm, especially 250 μm
The above-mentioned ones are preferable, and if the thickness is about this level, sufficient moisture-proof properties can be obtained especially for a PTP or blister pack package of a drug that requires moisture-proof properties.

To form a sheet or film, T
A general sheet or film forming method such as a die method and an inflation method can be employed. The formed sheet or film is directly stretched without stretching.
Used as a sheet or film for TP or blister pack packaging. When such a sheet or film is uniaxially or biaxially stretched, the vacuum formability of the sheet or film is reduced, and the productivity is reduced, such as a reduction in molding speed and an increase in the defective rate. Used in The stretched sheet or film raises its surface temperature above the softening temperature (TMA) at the time of vacuum forming, so that the sheet or film shrinks and cannot be basically formed by pressure forming. Further, in order to improve the function, it can be used as a laminated film by laminating with a coat such as vinylidene chloride or another resin film.

The sheet or film of the present invention is excellent in moisture proof and transparency, and also excellent in vacuum or compressed air formability, and thus exhibits sufficient performance as a material for PTP or blister pack packaging. Such a sheet or film is formed by vacuum forming, pressure forming, etc.
Form a blister in a shape that matches the package
Use for packaging or blister pack packaging. The conditions of vacuum forming and pressure forming for blister formation may be the same as those of a conventional sheet or film, and the sheet surface temperature is 30 to
300 ° C, preferably 50 to 150 ° C, molding pressure 0.2
２０20 kg / cm ² G , preferably 0.2-10 kg / cm ² G
It can be molded under the condition of cm ² G.

Since the unstretched sheet or film of the amorphous polyolefin resin (a ) and the modified product ( b ) thereof are excellent in vacuum or air pressure moldability, when the blister is formed, the blister and the flange Edge is beautifully finished. Among these, the modified product ( b ) is particularly excellent in vacuum or compressed air formability and has a sharp edge, so that the pitch (interval) between blisters formed on one sheet or film can be reduced. Therefore, the number of blisters formed on one sheet or film can be increased.

The PTP or blister pack package of the present invention comprises a molded product obtained by forming a blister on the above-mentioned sheet or film by a method such as vacuum or pressure forming, and a sealing material. The molded product of the sheet or film has a contour almost conforming to the shape of the article to be packaged,
It has a blister for accommodating an article to be packaged, and a flange formed around the blister, and a sealant is fixed to the flange by heat sealing or an adhesive. In order to package with such a package, the object to be packaged is sealed between the blister of the molded body and the sealing material, and the flange portion and the sealing material are fixed to each other by fixing means such as heat sealing or an adhesive. I do.

As a sealing material, in the case of general blister pack packaging, a mount is usually used, but other materials may be used. In the case of PTP packaging, aluminum foil is usually used. However, in order to improve the moisture proof property and heat sealing property, the aluminum foil may be thinly coated with the amorphous polyolefin resin used in the present invention. The amorphous polyolefin sheet or film of the present invention can be used as a sealing material instead of aluminum foil.

Of the resins used in the present invention, (a )
Since the amorphous polyolefin resin has insufficient heat-sealing properties, it may be difficult to adhere by heat-sealing. On the other hand, the graft-modified product ( b ) has improved heat-sealing properties, so that adhesion by heat-sealing is easy. Therefore, when the graft-modified product ( b ) is used as at least one of the molded product and the sealing material, packaging by heat sealing becomes easy.

When the graft-modified product ( b ) is not used for any of the molded article and the sealing material, for example, a molded article made of the amorphous polyolefin resin of the above (a ) is used, and as the sealing material, a sheet of paper or When using aluminum foil, both can be packaged by bonding with an adhesive. Even in such a case, adhesion by heat sealing is facilitated by laminating the graft-modified product ( b ) or another heat-sealable resin layer on the backing paper or aluminum foil.

Next, the package and the packaging method of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing a state in which an article to be packaged is packaged by the package of the present invention. In FIG.
Reference numeral 1 denotes a package, which comprises a molded body 2 and a sealing material 3 and accommodates an article 4 to be packaged.

The molded article 2 is molded from the cyclic olefin-based random copolymer (a). A plurality of blisters 5 having a shape and a size capable of accommodating the packaged object 4 are formed. A flange portion 6 is formed in the portion. The sealing material 3 is obtained by previously laminating a heat-sealing resin layer 8 made of a graft-modified product ( b ) on an aluminum foil 7, and is used with the surface of the heat-sealing resin layer 8 facing the molded body 2. In such a package 1, the article to be packaged 4 is accommodated in a blister 5, and a flange 6 and a heat-sealable resin layer 8 facing the flange 6 are fixed by heat sealing and packaged.

[0111] In order to form such a package 1, the article 4 to be packaged is accommodated in the blister 5 of the compact 2 and the sealing material 3
And the flange portion 6 and the heat-sealable resin layer 8 facing the flange portion 6 are fixed by heat sealing. In the case where the molded body 2 is formed of the graft-modified product ( b ), the heat-sealable resin layer 8 can be omitted. Also in the case of using a heat sealing property without the sealing material as seal <br/> material 3 omits the heat sealable resin layer 8, the blister 5
And a flange portion 6 and the sealing material 3 is fixed by an adhesive.

Since the film or sheet of the present invention has good moisture resistance and transparency, its commercial value can be increased by using it as a packaging material for PTP and blister pack packaging. The articles to be packaged include arbitrary ones such as drugs, foods, daily necessities, and miscellaneous goods. In particular, when used in the packaging of drugs such as tablets and capsules, foods such as rice crackers, snacks and cookies, and hygroscopic articles such as tobacco and tea bags, moisture proofness and transparency are guaranteed.

[0113]

As described above, according to the PTP or blister pack packaging sheet or film of the present invention,
Unstretched sheet of a specific amorphous polyolefin resin as a material
Since a sheet or film is used, an extremely good sheet or film can be obtained as a PTP or blister pack packaging material having excellent moisture resistance and transparency, and also having excellent vacuum or pressure forming properties.

Further, according to the PTP or blister pack package of the present invention, since the PTP or blister pack package is packaged with the above-mentioned sheet or film, a PTP or blister pack package excellent in moisture proofness and transparency can be obtained.

Further, according to the method of forming a PTP or blister pack package of the present invention, a package is easily packaged using the above-mentioned sheet or film to form a package excellent in moisture proof and transparency. Can be.

[0116]

Next, an embodiment of the present invention will be described. Example 1 Ethylene and 8-ethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene (in the general formula [1], n = 0, m = 1, q = 0, R ^{7 to} R ¹⁴ and R ¹⁶
A cyclic olefin wherein R ¹⁸ is a hydrogen atom and R ¹⁵ is an ethyl group (hereinafter abbreviated as ETCD-3);
[Η] is 0.68 dl / g, and softening temperature (TMA) is 88.
A sheet having a sheet thickness of 0.25 mm was prepared from a raw material having a Tg of 70 ° C and a T-die molding method using a 30 mmφ extruder. Physical properties such as moisture-proof property and transparency of the obtained sheet were measured. Table 1 shows the results.

Example 2 A copolymer of ethylene and ETCD-3 in which [η] was 0.1.
77 dl / g, softening temperature (TMA) of 60 ° C., Tg of 4
A sheet having a sheet thickness of 0.25 mm was produced from a raw material of 5 ° C. by T-die molding using a 30 mmφ extruder. The physical properties such as moisture-proof property and transparency of the obtained sheet were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 A sheet having a sheet thickness of 0.25 mm was produced using polypropylene having an [η] of 3.0 dl / g as a raw material using the same apparatus as in Example 1, and physical properties such as moisture-proof property and transparency were measured. The measurement was carried out in the same manner as in Example 1 and compared with those in Examples. Table 1 shows the results.

Example 3 To 100 parts by weight of the copolymer of ethylene and ETCD-3 used in Example 1, 100 parts by weight of a maleic anhydride acetone solution was added in an amount of 1 part by weight of maleic anhydride, and peroxide ( Perhexin 25B; trade name, manufactured by NOF CORPORATION)
2 parts by weight were added uniformly. Next, the pellets were subjected to graft modification of maleic anhydride using a twin-screw extruder at a cylinder temperature of 230 ° C.

Ethylene / ETC before modification with maleic anhydride
95 parts by weight of the D-3 copolymer and 5 parts by weight of the maleic anhydride-modified ethylene / ETCD-3 copolymer pellets (graft amount of maleic anhydride 0.7 wt%) obtained above were mixed and carried out. A 0.25 mm sheet was prepared as in Example 1. The physical properties of the obtained sheet were measured in the same manner as in Example 1. Further, the heat sealing property between the sheet and the aluminum foil was examined. The heat sealability was evaluated by the heat seal strength under the following conditions. Table 1 shows the results.

(Measurement conditions for heat seal strength) Aluminum foil: thickness 100 μm (no surface treatment) Heat seal conditions: hot plate temperature 240 ° C., adhesion time 0.5
Seconds Adhesive strength measurement conditions: Heat-sealed ethylene / ETC
The D-3 sheet and the aluminum foil were cut into strips having a width of 20 mm, and T-peeled from the ends at a pulling speed of 50 mm / min to determine the peel strength.

[0122]

[Table 1]

From the results shown in Table 1, it can be seen that all of the examples have better vacuum formability, moisture proofness and transparency than those of the comparative example.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a state in which an object to be packaged is packaged by a package of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Packaged body 2 Molded body 3 Sealing material 4 Packaged object 5 Blister 6 Flange part 7 Aluminum foil 8 Heat sealing resin layer

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-180976 (JP, A) JP-A-4-23838 (JP, A)

Claims (6)

(57) [Claims] (A) An intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 10 dl / g and a softening temperature (TMA) of 50 to 200 ° C. The following general formula [1]:
Or an amorphous polyolefin of (b) a graft-modified product of the cyclic olefin random copolymer (a), which comprises a copolymer of a cyclic olefin and ethylene. unstretched sheet of resin
A sheet or film for packaging PTP or blister pack, comprising a sheet or a film. Embedded image (In the formula [1], 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 a hydrogen atom, a halogen atom and a carbon atom. indicates an atom or group selected from the group consisting of hydrogen radical. the R ¹⁵ to R ¹⁸ may form a monocyclic or polycyclic bonded to each other, also R ¹⁵ and R ¹⁶ or R ^17,
And R ¹⁸ may form an alkylidene group. R ¹⁵
The monocyclic or polycyclic formed by to R ¹⁸ may have a double bond. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. ) 2. A PTP or blister pack package, comprising: a molded article obtained by forming a blister on the unstretched sheet or film according to claim 1; and a sealing material. 3. The molded article has a blister for accommodating an article to be packaged, and a flange formed on the periphery of the blister, wherein the flange is fixed to a sealing material and sealed. The PTP or blister pack package according to claim 2, wherein 4. The PTP or blister pack package according to claim 2, wherein the sealing material is made of aluminum foil or the unstretched sheet or film according to claim 1. 5. The sealing material is coated on an aluminum foil or backing paper, and ( b ) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.01 to 10 dl / g and the softening temperature (TMA) is 50
A laminate of a cyclic olefin-based random copolymer (a ), which is a copolymer of ethylene and a cyclic olefin represented by the following general formula [1], having a temperature of 200 to 200 ° C .: 3. The PTP or blister pack package according to 3. Embedded image (In the formula [1], 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 a hydrogen atom, a halogen atom and a carbon atom. indicates an atom or group selected from the group consisting of hydrogen radical. the R ¹⁵ to R ¹⁸ may form a monocyclic or polycyclic bonded to each other, also R ¹⁵ and R ¹⁶ or R ^17,
And R ¹⁸ may form an alkylidene group. R ¹⁵
The monocyclic or polycyclic formed by to R ¹⁸ may have a double bond. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. ) 6. A package comprising the unstretched sheet or film according to claim 1 and a blister for accommodating the package, and a molded blister having a flange formed around the blister. A method for forming a package, wherein the package is housed and the flange portion of the molded body and the sealing material are fixed by heat sealing or an adhesive.