JPH11105217A - Laminated film for press through pack cover - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blister cover film having characteristics being equivalent to aluminum foil by a method wherein a heat-sealable resin layer A, a cyclic olefin based resin layer B, a heat-sealing heat-resistant resin layer C are laminated in the order of the layer A/the layer B/the layer C, and the piercing strength is specified. SOLUTION: A heat-sealable resin layer A, a cyclic olefin based resin layer B and a heat-sealing heat-resistant resin layer C are laminated in the order of the layer A/the layer B/the layer C, and a three layer structure of which the piercing strength is less than 5N is formed. The layer A is a layer to press- bond a laminated film for cover to a blister, and generally, the blister is formed of polypropylene or a semi-hardened poly(vinyl chloride), and the layer A is formed of a resin having a heat-press-bonding property to these materials, and the layer B becomes a core material layer for this laminated film for cover, and is a layer which develops an easy pierceabillity and moisture-proofness of the film. Also, the layer C is a layer which makes this film withstand the heating at the time of heat-sealing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a PTP (Press Through Pa) used mainly for packaging pharmaceuticals such as tablets and capsules.
ck) It relates to a laminated film having an easy press-through property and a moisture-proof property suitable for a cover film in packaging.

[0002]

BACKGROUND OF THE INVENTION For packaging of pharmaceuticals such as tablets and capsules, a packaging form called PTP is used.
This PTP package is composed of a blister having a concave portion for accommodating the packaged object, and an aluminum film serving as a blister cover for covering the concave portion from the back surface of the blister after a capsule or the like is accommodated in the concave portion. In this PTP packaging, the blister cover film must be easily press-through because the packaged object is taken out by piercing the blister cover film. At the same time, the blister cover film also needs to have an action of protecting the packaged object from moisture, oxygen, and the like. From such a point, conventionally, an aluminum foil having a heat-fusible layer has been used as a blister cover film. This aluminum foil is impermeable to moisture, is easily laminated with a resin such as a heat-fusible resin, and has excellent press-through properties.

[0003] However, while blisters are made of synthetic resin such as polyvinyl chloride or polypropylene, the blister cover film is made of aluminum foil. However, there is a problem that aluminum remains. Also, the production of aluminum requires a large amount of electrical energy, and aluminum is becoming disadvantageous in terms of cost. Further, in the current situation in which recycling of resources is proposed from depletion of resources, there is also a problem that PTP having an aluminum foil adhered to the back surface is difficult to reuse after use. Furthermore, there is also a theory that aluminum causes Alzheimer's disease in some cases. Under such circumstances, development of a blister cover film containing no aluminum is desired.

[0004] However, characteristics such as easy press-through property and moisture permeation resistance achieved by a blister cover film using an aluminum foil are extremely difficult to achieve with a resin film. For example, many resin films generally have higher toughness than aluminum foil, and even when a capsule or the like accommodated in a blister or the like is pushed up, the blister cover does not easily break through and the press-through property is poor. It is conceivable to use a thin film in order to exhibit this easy press-through property. However, as the film becomes thinner, the moisture resistance is significantly reduced. It is also conceivable to use coated paper or the like in order to ensure easy press-through properties, but in this case also, it is difficult to ensure sufficient moisture permeability.

Further, in order to ensure easy press-through properties, it has been proposed to blend a large amount of a filler into a resin such as polypropylene to reduce the toughness of the resin and use it as a blister cover film. , The moisture resistance decreases. In order to ensure this moisture permeation resistance, the blister cover film must be thickened, which is not practical.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel blister cover film having properties equivalent to those of an aluminum foil conventionally used as a blister cover film.

[0007]

The laminated film for a press-through pack cover of the present invention has a heat-sealing resin (A) layer, a cyclic olefin-based resin (B) layer, and a heat-sealing heat-resistant resin (C) layer, These layers are (A) layer / (B) layer /
(C) The film is laminated in the order of the layers and has a piercing strength of less than 5N.

[0008] The laminated film for a press-through pack cover of the present invention is generally such that the cyclic olefin-based resin is a relatively brittle resin and, when used as a blister cover film, has the same easy press-through characteristics as aluminum foil. Is used. The layer made of the cyclic olefin-based resin (B) is provided on one surface with a layer made of a heat-sealable resin (A) necessary for heat-press bonding with a blister, and the other surface is provided with a layer of the cyclic olefin-based resin. A layer made of a heat-sealing heat-resistant resin (C), which complements the characteristics of the resin such as solvent resistance and moisture permeability.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Next, the laminated film for a press-through pack cover of the present invention will be specifically described.

The laminated film for a press-through pack cover of the present invention has at least a three-layer structure of a heat-sealing resin (A) layer / a cyclic olefin-based resin (B) layer / a heat-sealing heat-resistant resin (C) layer.

The heat-sealable resin (A) layer is a layer for thermocompression bonding the laminated film for a press-through pack cover of the present invention to a blister. The cyclic olefin-based resin (B) layer serves as a core layer in the laminated film for a press-through pack cover of the present invention, and is a layer for allowing the film to exhibit easy breakthrough (press-through) and moisture-proof properties. .

The heat-sealing heat-resistant resin (C) layer is a layer for making the laminated film for a press-through pack cover of the present invention resistant to heating during heat sealing.

First, the cyclic olefin resin (B) serving as the core material layer will be described. The cyclic olefin resin forming the core material layer of the laminated film for a press-through pack cover of the present invention is composed of ethylene and the formula [I] Or a random copolymer with a cyclic olefin represented by [II] (cyclic olefin random copolymer), a ring-opened ring polymer or copolymer of a cyclic olefin represented by the formula [I] or [II] Is the above equation
Ring opening (co) of cyclic olefin represented by [I] or [II]
A hydride of a polymer or a graft-modified product of the above (co) polymer can also be used.

Among the cyclic olefin resins used in the present invention, the ethylene / cyclic olefin random copolymer is a copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II], preferably ethylene. / Cyclic olefin (molar ratio) is a copolymer obtained by copolymerization at a ratio of 20 to 95/80 to 5.

[0015]

Embedded image

In the above formula [I], n is 0 or 1,
m is 0 or a positive integer, q is 0 or 1,
R¹~ R¹⁸And R^aAnd R^bAre each independently water
Substituted with an element atom, halogen atom or halogen
Is a good hydrocarbon group; ^Fifteen~ R¹⁸Are connected to each other
May form a single ring or multiple rings, and
May have a double bond in the polycyclic ring;^FifteenAnd R¹⁶
With or R¹⁷And R ¹⁸Form an alkylidene group with
May be.

[0017]

Embedded image

In the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2,
R ^{1 to} R ¹⁹ each independently represent a hydrogen atom, a halogen atom,
A hydrocarbon group or an alkoxy group which may be substituted with halogen, wherein a carbon atom to which R ⁹ or R ¹⁰ is bonded and a carbon atom to which R ¹³ is bonded or a carbon atom to which R ¹¹ is bonded; May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or It may form a polycyclic aromatic ring.

Examples of the cyclic olefin forming the cyclic olefin resin used in the present invention include bicyclo [2.2.
1] Hept-2-ene derivative, tetracyclo [4.4.0.12,5.17,
10] -3-dodecene derivatives, hexacyclo [6.6.1.1 ^{3, 6} .1
^10,13 .2 ^2,7 .0 ^9,14] -3-heptadecene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8 .0 ^12,17 ] -5-docosene derivative. Such cyclic olefins can be used alone or in combination.

The cyclic olefin as described above is randomly copolymerized with ethylene to form a cyclic olefin-based random copolymer. Such a cyclic olefin-based random copolymer, in addition to cyclic olefin and ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1- octadecene and 1-eicosene carbon number such as 3-20 α-olefins; cyclopentene,
Cyclohexene 3a, 5,6,7a-tetrahydro-4,7-methano-1H
-Cycloolefins such as indene, 1,4-hexadiene, 4
Non-conjugated dienes such as -methyl-, 4-hexadiene and 5-vinyl-2-norbornene; norbornene such as norbornene-2 and 5-chloronorbornene may be copolymerized.

In the present invention, as the cyclic olefin-based resin, a ring-opened (co) polymer of the above-mentioned cyclic olefin can also be used. Further, as the cyclic olefin-based resin, a hydrogenated product of the above-mentioned cyclic olefin ring-opening (co) polymer can also be used. Further, in the present invention, as the cyclic olefin resin,
A cyclic olefin random copolymer, a cyclic olefin ring-opening (co) polymer or a hydrogenated product of a cyclic olefin ring-opening (co) polymer as described above is used, for example, with maleic anhydride, maleic acid, itaconic anhydride, itacone A graft product modified with a modifying agent such as an acid, an unsaturated carboxylic acid such as (meth) acrylic acid, or an anhydride thereof can also be used.
These modifiers can be used alone or in combination.

These cyclic olefin resins can be used alone or in combination of two or more. Incidentally, such a cyclic olefin-based resin is disclosed in JP-A-60-168.
No. 708, No. 61-120816, No. 61-115912, No. 61-115916
No. 61-271308, No. 61-272216, No. 62-252406, and No. 62-252407.

In preparing the graft-modified product, an unsaturated carboxylic acid, a derivative thereof, or the like is used as a modifying agent. Further, the cyclic olefin-based resin, within a range that does not impair the object of the present invention, an ultraviolet absorber, a heat stabilizer, a weather stabilizer, a light stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, Nucleating agents, lubricants, dyes and pigments that absorb only light of a specific wavelength, natural oils, synthetic oils,
Additives such as waxes or translucent fillers may be included.

The intrinsic viscosity [μ] of such a cyclic olefin resin measured in decalin at 135 ° C. is as follows:
Usually within the range of 0.01 to 20 dl / g, preferably 0.05.
It is in the range of 10 to 10 dl / g. The crystallinity of these cyclic olefin-based resins measured using X-rays is as follows:
It is usually less than 5%, often 0%.

The softening temperature (TMA) of the above-mentioned cyclic olefin resin as measured by a thermal mechanical analyzer is usually 60 ° C. or higher, preferably 7 ° C.
0 ° C. or higher, and the glass transition point (Tg) is usually 30
° C or higher, preferably 60 ° C or higher, more preferably 70 ° C or higher.
２３０230 ° C.

A melt flow rate (MFR: AS) of this cyclic olefin resin measured at 260 ° C.
TM D 1238) is usually 1 to 100 g / 10 minutes,
Preferably it is 5 to 50 g / 10 minutes.

The thickness of such a cyclic olefin resin (B) layer is set so that the moisture resistance of the entire laminated film for a press-through pack cover of the present invention is usually 5 g / m ² · 24 hr or less. .

To achieve such moisture resistance, a ring
Thickness of refining resin (B) layer (L _bμm) is the following formula
Can be set.

[0029]

(Equation 2)

However, in the above equation, t = 5,
L _a is (A) layer thickness (usually 1 to 20 [mu] m), L _b is (B)
Layer thickness, L _c is the (C) layer thickness (usually 1 to 20 [mu] m), T _a is (A) layer resin moisture permeation coefficient, the T _c is (C) layer resin permeance.

As is clear from the above equation, the thickness of the layer (B) differs depending on the layers (A) and (C).
μm, preferably 20 to 58 μm, particularly preferably 25 μm.
５８58 μm.

The above-mentioned cyclic olefin resin (B)
On one surface of the layer, a heat-sealable resin (A) layer is laminated. As the resin for forming the layer (A), a resin having thermocompression bonding property to the adhesive surface of the blister to which the laminated film for a press-through pack cover of the present invention is adhered is used. In general, the blister is formed of polypropylene or semi-cured polyvinyl chloride. Therefore, in the present invention, the layer (A) is formed of a resin having heat-pressing properties with respect to polypropylene and / or semi-cured polyvinyl chloride. Is preferred.

Generally, the temperature at which the cover film is thermocompressed to the blister is 100 to 200 ° C., the sealing pressure is 0.05 to 1 MPa, and the press time is 0.5 to 3.0 seconds. In the present invention, a resin that can be pressure-bonded to the blister under such conditions can be used. In order to heat-seal under such conditions, the Vicat softening point of the heat-sealable resin forming this layer (measured by ASTN D1525, the same applies hereinafter) is usually 15 ° C. higher than the heat-seal temperature.
Or more, preferably 20 ° C. or more, more preferably 25 ° C.
It is preferable to use a lower resin. Therefore, the Vicat softening point of this heat sealing resin is usually 30 to 1
00 ° C., preferably 40 to 70 ° C., particularly preferably 40 ° C.
８０80 ° C.

Further, considering the film forming property, the melt index (MFR) of the heat-sealable resin measured at 190 ° C. or 230 ° C. is usually 0.1 to 100 g / 1.
0 minutes, preferably 1 to 50 g / 10 minutes, particularly preferably 2 to
It is in the range of 20 g / 10 minutes.

The heat-sealable resin (A) layer is made of a resin having a heat-sealing strength of 3 N / 15 mm or more with respect to polypropylene and / or semi-rigid polyvinyl chloride, which is generally used as a blister-forming resin. It is preferred to use.

Examples of such a resin include a graft-modified ethylene α-olefin copolymer-based resin graft-modified with an unsaturated carboxylic acid or a derivative thereof, a polyolefin-based heat-sealable resin composition, and an ethylene-vinyl acetate copolymer. Systematic resins can be mentioned.

Examples of such a resin or resin composition include (A) 15 to 80% by weight of an ethylene-α, β-unsaturated carboxylic acid copolymer or a metal neutralized product thereof, (B) polyethylene, ethylene-α- 10 to 80% by weight of one or more resins selected from olefin copolymers, ethylene-vinyl ester copolymers and ethylene-α, β-unsaturated carboxylic acid ester copolymers, (C) tackifying resin 3 to 30% by weight and (D) an aliphatic polyamide, an aliphatic bisamide,
Resins containing 300 ppm to 10% by weight of one or more additives selected from polyethylene glycol, hydrogenated castor oil and silica (see Japanese Patent Publication No. 63-1982). Specific examples of such a resin or resin composition include a composition containing an ethylene- (meth) acrylic acid copolymer, an ethylene-vinyl acetate copolymer, a dipentene polymer, and an oleic acid amide; Acrylic acid copolymer, ethylene
Composition containing vinyl acetate copolymer, alicyclic hydrocarbon resin and oleamide, ethylene- (meth)
Acrylic acid copolymer, ethylene-vinyl acetate copolymer,
Composition containing alicyclic hydrocarbon resin, erucamide, stearamide and silica, partially neutralized ethylene- (meth) acrylic acid copolymer, ethylene-ethyl acrylate copolymer, β- Composition containing pinene copolymer, erucic acid amide and ethylene bisamide oleate, partially neutralized ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-butene-1 copolymer Copolymer, vinyl toluene-α-methylstyrene copolymer, oleic amide, methylene bisamide stearate and silica-containing composition, partially neutralized ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer A composition containing a polymer, a styrene-α-olefin copolymer, erucamide, stearamide and silica; it can.

In the present invention, as such a heat-sealable resin, for example, a resin commercially available under a trade name such as an ENA resin, a CMPS resin, or an admer resin can be used.

The thickness of the layer (A) made of such a heat-sealing resin is usually 1 to 20 μm, preferably 2 to 20 μm.
10 μm, particularly preferably 4 to 6 μm. If the thickness of the heat sealing resin (A) layer is less than 1 μm, sufficient heat sealing strength may not be exhibited. On the other hand, if it exceeds 20 μm, the press-through property may decrease.

In the laminated film for a press-through pack cover of the present invention, the heat-resistant heat-sealing resin is applied to the surface of the cyclic olefin-based resin (B), which is the core material layer, on which the heat-sealing resin (A) layer is not formed. (C) The layer is laminated.

The heat-sealing heat-resistant resin (C) layer protects the laminated film for the press-through pack cover of the present invention during heat sealing, and cooperates with the layer (A) to form the cyclic olefin resin (B) layer. Complements the characteristics of

In order for such a heat-sealing heat-resistant resin (C) layer to have heat resistance against heating during heat-sealing, the heat-sealing heat-resistant resin must have the Vicat softening property of the heat-sealing resin (A). Usually one more than a point
0 ° C. or higher, preferably 20 to 40 ° C., particularly preferably 3 ° C.
It is desirable to use a resin having a Vicat softening point higher by 0 to 40C. By using a resin having such a Vicat softening point, the laminated film for a press-through pack cover of the present invention can be protected from heating during heat sealing.

Further, considering the film forming property, the melt index (MFR) of the heat-sealing heat-resistant resin measured at 190 ° C. or 230 ° C. is usually 0.1 to 100 g.
/ 10 min, preferably 1 to 50 g / 10 min, particularly preferably 2 g
It is in the range of ２０20 g / 10 minutes.

Examples of the resin forming the heat-sealing heat-resistant resin (C) layer include polypropylene, polyethylene, linear low-density polyethylene, linear medium-density polyethylene, high-density polyethylene, and ethylene having 3 or more carbon atoms. Copolymers with α-olefins, homopolymers or copolymers of α-olefins having 3 or more carbon atoms can be mentioned. Specifically, for example, polypropylene, polyethylene, linear low-density polyethylene, ethylene 4-Methylpentene-1 copolymer can be used. Particularly, in the present invention, a polyolefin-based resin having a Vicat softening point higher by 10 ° C. or more than the Vicat softening point of the resin forming the heat sealable resin (A) layer is preferable.

The thickness of such a heat-sealing heat-resistant resin (C) layer is usually 1 to 20 μm, preferably 2 to 10 μm.
m, particularly preferably in the range of 4 to 6 μm. If the thickness of the heat-sealing heat-resistant resin (C) layer is less than 1 μm, sufficient heat-sealing strength may not be exhibited.
On the other hand, if it exceeds 20 μm, the press-through property may decrease.

In the present invention, when the thickness of the heat-sealing heat-resistant resin (C) layer is Lc and the thickness of the cyclic olefin-based resin (B) layer is Lb, the value of Lc / Lb is usually 0.05 to 0.40, preferably 0.10 to 0.35, particularly preferably 0.15 to 0.30. The laminated film for a press-through pack cover of the present invention focuses on the fact that the cyclic olefin resin has a relatively high moisture permeability and is a relatively brittle resin, and forms this core material layer with the cyclic olefin resin. The surface is covered with a heat-sealing heat-resistant resin (C) layer to suppress a change in film properties due to heating at the time of heat sealing, and to make the cyclic olefin-based resin (B) layer brittle. Is complemented by laminating a heat-sealing heat-resistant resin (C) layer having a thickness that does not impair the breath-through property, and furthermore, the heat-resistance of the heat-sealing heat-resistant resin ( By laminating the layers C), characteristics comparable to those obtained when aluminum foil is used are secured. As described above, since the film of the present invention has the same press-through property as the case where an aluminum foil is used, and the moisture-permeation resistance that does not substantially cause a problem without using the aluminum foil, Lc It is desirable that the value of / Lb be within the above range.

Further, the heat-sealing heat-resistant resin (C)
The layer is preferably made of a polyolefin-based resin as exemplified above, and such a polyolefin resin is
Since it has excellent solvent resistance, it is possible to prevent erosion of the film by a solvent when printing on the laminated film for a press-through pack cover of the present invention. In addition, additives such as a slip agent and an antistatic agent can be uniformly blended with the polyolefin resin that is preferably used. By providing such a layer, a heat sealing device can be used for heat sealing. Can be stably supplied.

The heat-sealing heat-resistant resin (C) layer forming the laminated film for the press-through pack cover of the present invention contains a slip agent and an antistatic agent, and if necessary, an antiblocking agent, an ultraviolet absorber, a heat stabilizer, and weather resistance. Contains additives such as stabilizers, light stabilizers, antifogging agents, nucleating agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes or translucent fillers that absorb only light of a specific wavelength Is preferred. Such an additive can be uniformly and stably compounded in a linear medium-low-density polyethylene resin. Such additives are usually incorporated in the linear low-medium density polyethylene resin in an amount of 10% by weight or less, preferably 7% by weight or less. It is difficult to mix the above additives into the cyclic olefin resin, but it is necessary to stably mix the above additives into the resin forming the heat-sealing heat-resistant resin (C) as described above. it can.

Examples of slip agents that can be used in the present invention include higher fatty acid amides such as erucamide and oleic acid amide, and higher fatty acid bisamides such as ethylenebisoleic amide and ethylenebiserucamide. be able to. Examples of the antistatic agent include glycerin higher fatty acid mono- or diester, diglycerin higher fatty acid mono- or diester, and the like.

Further, as an additive to such an ethylene (co) polymer, a slip agent, an antistatic agent, an antiblocking agent and the like are mixed and marketed. In the present invention, such a mixture is used alone or in combination. Can also be used. Examples of such a mixture include Masterbatch AZ-20M for Ultrazex (manufactured by Mitsui Petrochemical Industry Co., Ltd.) and antistatic agent masterbatch liquemaster MPE-6 (manufactured by Riken Vitamin Co., Ltd.). it can.

The laminated film for a press-through pack cover of the present invention can be produced by, for example, three-layer coextrusion by a co-extrusion T-die method, and can be produced by, for example, three-layer coextrusion by a coextrusion inflation method. And dry lamination ((A) layer film /
Adhesive / (B) layer film / adhesive / (C) layer film), sandwich extrusion ((A) layer film / (B) layer extrusion / (C) layer film), and the like. Among these methods, the co-extrusion T-die method and the co-extrusion inflation method are preferred.

The overall thickness of the laminated film for a press-through pack cover of the present invention having the above structure is usually 100 μm or less, and more preferably 20 to 100 μm.
80 μm, particularly preferably in the range of 30 to 60 μm.

The laminated film for a press-through cover of the present invention has a piercing strength of less than 5N, preferably 0.5.
To 4.0 N, particularly preferably 1.0 to 3.0 N, and the moisture resistance (moisture permeability) is usually 5 g / m ² · 24 hr or less, preferably 4 g.
/ m ² · 24 hr or less, particularly preferably 3 g / m ² · 24 hr or less, and the heat seal strength is usually 3 N / 15 mm or more, preferably 4 N / 15 mm or more, particularly preferably 5 N / 15 mm or more.

The laminated film for a press-through pack cover of the present invention basically has a three-layer structure as described above, but may further have another layer laminated as necessary.

The laminated film for a press-through pack cover of the present invention can be used by filling the recessed portion of the blister with a package, and then contacting the film of the present invention on the back surface of the blister, followed by thermocompression. The heat sealing conditions at this time are usually a temperature of 140 to 180 ° C., a pressure of 0.1 to 1 MPa, and a heat sealing time of 0.5 to 3.0 seconds.

[0056]

According to the laminated film for a press-through pack cover of the present invention, a cyclic olefin resin (B) layer is used as a core material layer, a heat-sealable resin (A) layer is provided on one side, and a heat-sealable layer is provided on the other side. The film of the present invention having the heat-resistant resin (C) layer laminated thereon and having such a configuration can be used in place of the aluminum foil conventionally used for press-through pack covers. That is,
The film of the present invention has the same press-through properties as aluminum foil, and also has excellent moisture-proof properties. Furthermore, since it does not contain metal, it has become possible to reuse the resin forming the press-through pack after use. In addition, even when incinerated, it can be completely incinerated. Further, a film can be supplied at lower cost than when aluminum foil is used.

Further, since this film is transparent or translucent, the packaged medicines and the like can be confirmed from the back.

[0058]

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

The processing methods of the films used in the examples and comparative examples of the present invention and the methods for measuring and evaluating the physical properties are as follows. The film processing method uses a multi-manifold three-layer three-layer T-die (die opening width 1450 mm) and an extruder (screw diameter 7).
(A) layer / (B) layer / (5 mm, 75 mm, 75 mm) using a T-die casting molding machine at a resin temperature of 230 ° C. in the T-die portion while each extruded resin is laminated.
(C) Extrude a three-layer film as a layer, and immediately
The film was wound around a cooling roll at 0 ° C., solidified by cooling, taken up at a take-up speed of 40 m / min, and wound up into a roll as a film for evaluation.

Film evaluation method and conditions (1) Press-through property The press-through property was evaluated based on the magnitude of the piercing strength of the film and the ease with which a hole was directly formed in the film with the thumb. The criteria are as follows.

Puncture strength Tensile strength measurement A metal needle having a tip diameter of 1 mm is attached to the strength sensing part of the noble (tensilon), and the measurement film is horizontally fixed to the other side. In this state, the tension was moved from the vertical direction of the film at a speed of 50 mm / min, and the maximum strength when the metal needle pierced the film and penetrated the needle was measured.

Perforation by Thumb (Press-Through Property) A hole was punched a plurality of times with the thumb in the produced film, and the resistance at that time was evaluated in three steps as follows.

It is easy to make a hole with a small resistance.... ○ There is a little resistance but it is easy to make a hole. ·· × × (2) Moistureproofness The water vapor permeability was measured by the cup method (JIS Z0208). (3) Heat sealability The heat seal strength of the heat-sealable resin (A) layer between the 200-μm-thick polypropylene and semi-curable polyvinyl chloride sheet and the evaluation film was measured by a single-sided heating bar sealer.

The heat sealing conditions are as follows. Sealing pressure: 0.196 MPa Sealing temperature: 140 ° C Sealing time: 1.0 second

[0065]

Example 1 Using a resin described below, a laminated film was processed and evaluated in accordance with the above-mentioned film processing method and film physical property evaluation method.

Table 1 shows the results. Resin used Heat sealable resin (A) layer (A-1) Ethylene-vinyl acetate copolymer resin (MFR (at 190 ° C.): 8 g / 1, which is a multipurpose seal resin)
0 min, density 0.922 g / cm ³ , Vicat softening point: 58
℃, Mitsui DuPont Polychemical Co., Ltd., trade name “C
MPS: V70 ") cyclic olefin resin (B) layer (B-1) ethylene-cyclic olefin random copolymer, MFR (at 260 ° C): 25 g / 10 minutes, glass transition temperature: 105 ° C, Mitsui Petrochemical Industries ( Co., Ltd., trade name "Apel: APL6011T") heat-sealing heat-resistant resin (C) layer (C-1) linear low-density polyethylene resin (MFR (at1
90 ° C.): 2.1 g / 10 min, density: 0.945 g / c
m ³ , Vicat softening point: 115 ° C, Mitsui Petrochemical Co., Ltd.
Made, trade name “Ultzex: Uz4020L”) Film composition Heat-sealable resin (A) layer Layer thickness: 5 μm Cyclic olefin-based resin (B) layer Layer thickness: 25 μm Heat-seal heat-resistant resin (C) layer Layer Thickness: 5 μm Total thickness of (A) + (B) + (C): 35 μm

[0067]

Example 2 A film was produced in the same manner as in Example 1 except that the cyclic olefin-based resin (B) layer was formed of the following resin, and the film obtained under the same conditions was evaluated.

Cyclic olefin resin (B) layer (B-2) Ethylene-cycloolefin random copolymer, MFR (at 260 ° C.): 40 g / 10 minutes, glass transition temperature: 80 ° C., Mitsui Petrochemical Industry Co., Ltd. The product name is "Apel: APL6509T". The evaluation results are shown in Table 1.

[0069]

Example 3 A film was produced in the same manner as in Example 1 except that the heat-sealing heat-resistant resin (C) layer was formed of the following resin, and the thickness of each layer was changed as described below. The obtained film was evaluated.

(C-2) Polypropylene resin, (MFR
(At 230 ° C): 7.0 g / 10 min, density: 0.910 g
/ Cm ³ , Vicat softening point: 155 ° C., manufactured by Grand Polymer Co., Ltd., trade name “Grand Polypro: F107D”
V ") Film configuration Heat-sealable resin (A) layer Layer thickness: 3 μm Cyclic olefin-based resin (B) layer Layer thickness: 25 μm Heat-seal heat-resistant resin (C) layer Layer thickness: 3 μm (A) + (B) + (C) total thickness 31 μm The evaluation results are shown in Table 1.

[0071]

Example 4 A film was produced in the same manner as in Example 1 except that the heat-sealable resin (A) layer was formed of the following resin, and the film obtained under the same conditions was evaluated.

Heat sealable resin (A) layer (A-2) Graft-modified ethylene-α-olefin random copolymer (MFR (at 230 ° C.): 5.7 g / 10
, Vicat softening point: 112 ° C., manufactured by Mitsui Petrochemical Industries, Ltd., trade name “Admer: QF551”) The evaluation results are shown in Table 1.

[0073]

Comparative Example 1 A film was produced in the same manner as in Example 1 except that the thickness of each layer was changed as described below, and the film obtained under the same conditions was evaluated.

Film composition Heat-sealable resin (A) layer Layer thickness: 5 μm Cyclic olefin-based resin (B) layer Layer thickness: 25 μm Heat-seal heat-resistant resin (C) layer Layer thickness: 30 μm (A) + (B) + (C) total thickness 60 μm The evaluation results are shown in Table 1.

[0075]

Comparative Example 2 A film was produced in the same manner as in Example 1 except that the heat-sealable resin (A) layer was formed of the following resin, and the film obtained under the same conditions was evaluated.

Heat sealable resin (A) layer (A-3) Linear low density polyethylene, (MFR (at19
0 ° C.): 2.1 g / 10 min, density: 0.940 g / cm ³ , Vicat softening point: 115 ° C., trade name “Ultzex: Uz4020L” manufactured by Mitsui Petrochemical Industries, Ltd.) Shown in

[0077]

Comparative Example 3 A film was produced in the same manner as in Example 1 except that the heat-sealable resin (C) layer was formed of the following resin, and the film obtained under the same conditions was evaluated.

Heat sealable resin (A) layer (A-4) random polypropylene resin, (MFR (at
230 ° C.): 6.0 g / 10 min, density: 0.910 g / cm ³ ,
Vicat softening point: 125 ° C., manufactured by Grand Polymer Co., Ltd., trade name “Grand Polypro: F327”) The evaluation results are shown in Table 1.

[0079]

Comparative Example 4 In Example 1, a single-layer film consisting of only the cyclic olefin-based resin (B) layer was used without providing the heat-sealing resin (A) layer and the heat-sealing heat-resistant resin (C) layer. Processing was performed according to the processing method described in Example 1, and the same evaluation as in Example 1 was performed.

Cyclic olefin resin (B) layer (B-2) Ethylene-cycloolefin random copolymer, MFR (at 260 ° C.): 40 g / 10 minutes, glass transition temperature: 80 ° C., Mitsui Petrochemical Industry Co., Ltd. Made, trade name "Apel: APL6509T") Film composition Heat sealable resin (A) layer Layer thickness ... 0 µm Cyclic olefin resin (B) layer Layer thickness ... 40 µm Heat seal heat resistant resin (C) layer Layer thickness ... 0 µm Total thickness of (A) + (B) + (C) ... 40 µm Table 1 shows the evaluation results.

[0081]

Reference Example 1 A film was produced in the same manner as in Example 1 except that the film structure was changed as described below, and the film obtained under the same conditions was evaluated.

Film configuration Heat sealable resin (A) layer Layer thickness: 5 μm Cyclic olefin resin (B) layer Layer thickness: 10 μm Heat seal heat resistant resin (C) layer Layer thickness: 5 μm (A) + (B) + (C) total thickness 20 μm The evaluation results are shown in Table 1.

[0083]

REFERENCE EXAMPLE 2 An evaluation was performed by the same method and under the same conditions as in Example 1 using an aluminum foil (thickness: 20 μm) coated with a heat seal layer which is currently commercially available.

Table 1 shows the evaluation results.

[0085]

[Table 1]

Claims (5)

[Claims] 1. A heat-sealing resin (A) layer, a cyclic olefin-based resin (B) layer, and a heat-sealing heat-resistant resin (C) layer, and these layers are (A) layer / (B) layer/
(C) A laminated film for a press-through pack cover which is laminated in the order of layers and has a piercing strength of less than 5N. 2. The heat-sealing resin (A) is made of a polyolefin resin having a heat-sealing strength of 3 N / 15 mm or more with respect to polypropylene and / or semi-rigid polyvinyl chloride. The laminated film for a press-through pack cover described in the above. 3. The method according to claim 1, wherein the cyclic olefin resin (B) layer is
It is composed of an ethylene / cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin, a hydrogenated product of a ring-opened (co) polymer of a cyclic olefin, and a graft-modified product of these (co) polymers. The laminated film for a press-through pack cover according to claim 1, wherein the laminated film is formed of at least one resin selected from the group. 4. The heat-sealing heat-resistant resin (C) layer,
The press according to claim 1, wherein the press is formed from a polyolefin resin having a Vicat softening point higher by at least 10 ° C. than a Vicat softening point (ASTN D1525) of the heat-sealing resin (A) layer forming resin. Laminated film for through pack cover. 5. The (A) layer thickness and the (C) layer thickness are both in the range of 1 to 20 μm, and the (B) layer thickness (L
_b μm) is within a range satisfying the following expression: The laminated film for a press-through pack cover according to any one of claims 1 to 4, wherein (Equation 1) (However, in the above formula is t = 5, L _a is (A) layer thickness, L _b is (B) layer thickness, L _c is the (C) layer thickness, T _a is (A) layer resin The moisture permeability coefficient, _Tc, is the resin moisture permeability coefficient of the (C) layer.)