JP2007021755A - Polyolefinic resin laminated sheet and ptp package using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefinic resin laminated sheet improved in molding processability and oil resistance and suitably used as a PTP package or the like excellent in the balance of hand cutting properties and transparency. <P>SOLUTION: The polyolefinic resin laminated sheet comprises an A-layer, which constitutes an intermediate layer and the B-layers laminated on both sides of the A-layer as outer layers. The A-layer and the B-layers mainly consist of a cycloolefinic resin (a) and a polyethylenic resin (b) and the mixing mass ratio of both resins is (a)/(b)=60-100/0-40 mass% in the A-layer and (a)/(b)=5-40/60-95 mass% in the B-layers. The component (a) is dispersed in the B-layers and the average dispersing particle size thereof is 0.2-1.0 μm. The thickness of the A-layer of the laminated sheet is 60-95% of the total thickness of the laminated sheet. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyolefin-based resin laminate sheet used for various thermoforming and the like, and a PTP package using the same, and more specifically, packaging of pharmaceuticals and foods or blisters mainly referred to as PTP (press-through packaging) packaging. The present invention relates to a polyolefin-based resin laminate sheet suitable for packages and the like.

  In the packaging field of pharmaceuticals and foods, PTP (press-through packaging) packaging is performed to package solid agents such as capsules and tablets, granular foods, and the like. In the field of packaging of foods and the like, blister packages that are very similar to PTP packaging are often used for packaging foods and the like.

  With PTP packaging, for example, a transparent sheet is formed by pressure forming, vacuum forming or the like to form a pocket portion for storing a solid agent such as a capsule, and after storing the capsule or the like in the pocket portion, for example, by hand like an aluminum foil. It refers to packaging in a form in which foils and films of materials that can be easily torn or easily opened are laminated and integrated. According to PTP packaging, the solid agent or food stored in the pocket of the transparent sheet can be confirmed directly with the naked eye before opening, and when opening, push the solid agent etc. in the pocket with your finger to break the foil etc. Thus, the contents can be taken out.

  A blister package is a heat-sealed coated paper after forming a recess (pocket part) according to the form of food by vacuum forming the sheet and storing contents such as food in the recess (pocket part). A package that is sealed with a film or film.

  Polyvinyl chloride (hereinafter sometimes abbreviated as "PVC") is used as a sheet for PTP packaging and blister packaging, but it has good thermoformability, rigidity at room temperature, impact resistance, moderate moisture resistance, and transparency. Since it has the property, it has been used conventionally.

  However, PVC has a concern that hydrogen chloride gas generated at the time of combustion deteriorates the combustion furnace, and the generated hydrogen chloride gas pollutes the environment, and a material that replaces PVC is required. In recent years, polypropylene-based resins have begun to be used as an alternative material. However, since polypropylene-based resins are slightly inferior in moldability compared to PVC, molding is performed using a PTP molding apparatus for polypropylene-based resins. . However, when a polypropylene resin sheet is used, there is a problem that a tearing operation is required because it is difficult to cut by hand even if it is repeatedly bent along the slit portion provided on the sheet.

  In addition, cyclic olefin resins, which are excellent in moisture resistance like polypropylene resins, and are close to PVC in terms of transparency and viscoelasticity of materials, have been variously studied as one of alternative materials for molding sheets including PTP packaging applications. I came. However, while the cyclic olefin resin has excellent properties such as transparency, moisture resistance, mechanical strength, and moldability, it has problems such as insufficient impact resistance and poor oil resistance. Therefore, a multilayered sheet is being studied.

In Patent Document 1, a cyclic olefin-based resin and high-density polyethylene (density: 0.94 to 0.98 g / cm ³ ) are used in the outer layer, the inner layer, and the intermediate layer, and the outer layer and the inner layer have a higher density than the intermediate layer. A laminated sheet of polymer alloy in which the blending ratio of polyethylene is increased is disclosed.

  However, since this sheet uses high-density polyethylene, external haze is likely to deteriorate, and there is a problem in the visibility of the drug in pharmaceutical packaging applications.

Patent Document 2 discloses a sheet in which a layer made of a cyclic olefin-based resin and a layer formed by blending a low-medium density polyethylene (density: 0.920 to 0.940 g / cm ³ ) with a cyclic olefin-based resin are laminated. Is disclosed.

  Patent Document 2 describes that the molding processability, oil resistance, transparency, and hand cutting property of the molded sheet are good, and that the cyclic olefin-based resin, which is the main component constituting both outer layers, is low in volume. Although the resin composition with the density polyethylene and the hand cutting property of the molded sheet are disclosed, the relationship between the dispersion state of the cyclic olefin resin and the hand cutting property and transparency of the molded sheet is not disclosed or suggested. .

JP-A-6-305101 JP 2003-127287 A

  The present invention has been made in order to solve the above-mentioned problems, and the purpose thereof is PTP packaging having good moldability and oil resistance, and excellent balance between hand cutting and transparency. An object of the present invention is to provide a polyolefin-based resin laminate sheet that is suitably used.

  As a result of intensive studies, the inventors of the present application have a laminated structure mainly composed of a cyclic olefin resin and a polyethylene resin, and the dispersion state of the cyclic olefin resin in the outer layer is within a specified range. The present inventors have found a cyclic olefin-based resin laminate sheet having an excellent balance between hand cutting properties and transparency, and have completed the present invention.

That is, the present invention
(1) A laminated sheet comprising an A layer constituting an intermediate layer and a B layer as an outer layer laminated on both sides thereof, wherein the A layer and the B layer are (a) a cyclic olefin resin, (b) A polyethylene-based resin is the main component, and the mixing mass ratio is (a) / (b) = 60 to 100/0 to 40% by mass in the A layer, and (a) / (b) = in the B layer. 5 to 40/60 to 95% by mass, and in the layer B, the component (a) is dispersed, and the average dispersed particle size is 0.2 to 1.0 μm. A polyolefin-based resin laminate sheet, wherein the thickness of the layer is 60 to 95% of the total thickness.
(2) The glass transition temperature (Tg) of the cyclic olefin resin as the component (a) is 50 to 120 ° C., and the crystal melting peak temperature (Tm) of the polyethylene resin as the component (b) is 110 to 110 ° C. It is 130 degreeC and a density is 0.920-0.940 g / cm < ³ >, The polyolefin-type resin laminated sheet as described in (1) characterized by the above-mentioned.
(3) The cyclic olefin-based resin of the component (a) is a random copolymer of ethylene and a cyclic olefin, a cyclic olefin ring-opening (co) polymer, a hydrogenated product of a cyclic olefin ring-opening (co) polymer, and these The polyolefin resin laminated sheet according to any one of (1) to (2), which is at least one cyclic olefin resin selected from the group consisting of graft-modified products of (co) polymers.
(4) The polyolefin resin laminated sheet according to any one of (1) to (2), wherein the polyethylene resin of the component (b) is a resin polymerized using a metallocene catalyst.
(5) Any of (1) to (2), wherein the cyclic olefin resin described in (3) is used as the component (a) and the polyethylene resin described in (4) is used as the component (b). The polyolefin-based resin laminate sheet described in 1.
(6) A PTP package formed from the polyolefin-based resin laminate sheet according to any one of (1) to (5).
Is to provide.

  Forming process by laminating a resin layer composed mainly of cyclic olefin resin and polyethylene resin, and mixing the appropriate amount of each, and keeping the dispersion state of the cyclic olefin resin dispersed in the outer layer within the specified range A cyclic olefin-based resin laminate sheet having good suitability and oil resistance and excellent balance between hand cutting and transparency is obtained, and is particularly suitable for PTP packaging.

  Hereinafter, embodiments embodying the present invention will be described. It should be noted that the upper and lower limits of the numerical range in the present invention are those of the present invention as long as they have the same operational effects as those in the numerical range even if they are slightly outside the numerical range specified by the present invention. It is included in the equivalent range.

  First, the polyolefin-based resin laminate sheet of the present invention includes an A layer constituting an intermediate layer and an outer layer B layer laminated on both sides thereof. The A layer and the B layer are (a) a cyclic olefin resin, ( b) It is characterized by comprising a polyethylene resin as a main component.

  Here, the bonding form of the cyclic olefin resin (polymer) which is the component (a) used in the polyolefin resin laminated sheet of the present invention is not particularly limited, and the cyclic olefin represented by the following general formula (1) And a random copolymer of olefin and ethylene, a cyclic olefin ring-opening (co) polymer, a hydrogenated product of a cyclic olefin ring-opening (co) polymer, and a graft modification of these (co) polymers.

In general formula (1), R _{1 to} R ₁₂ are hydrogen atoms or hydrocarbon groups, which may be the same or different. R ₅ and R ₁₀ , or R ₁₁ and R ₁₂ may be integrated to form a divalent hydrocarbon group. R ₃ or R ₁₀ and R ₁₁ or R ₁₂ may form a ring with each other. n is 0 or a positive integer, and when R _{5 to} R ₈ are repeated a plurality of times, these may be the same or different.

  Here, examples of the cyclic olefin represented by the general formula (1) include bicyclohept-2-ene (2-norbornene) of the following formula (2) and derivatives thereof such as norbornene, 6-methylnorbornene, 6- Examples thereof include ethyl norbornene, 6-n-butylnorbornene, 5-propylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,6-dimethylnorbornene, 5-phenylnorbornene, and 5-benzylnorbornene.

  Examples of tetracyclo-3-dodecene of the following formula (3) and derivatives thereof include 8-methyltetracyclo-3-dodecene, 8-ethyltetracyclo-3-dodecene, and 8-hexyltetracyclo-3-dodecene. Examples thereof include 10-dimethyltetracyclo-3-dodecene and 5,10-dimethyltetracyclo-3-dodecene.

  In the polyolefin-based resin laminate sheet of the present invention, a ring-opening (co) polymer of a cyclic olefin and a hydride of a random copolymer of ethylene and a cyclic olefin can be suitably used. The copolymer with ethylene which has about 30-50 mol% of cyclic olefin represented by 1) can be illustrated. Moreover, what contains (alpha) -olefins other than ethylene, and a butadiene, isoprene, etc. may be contained as a 3rd component. Some have various glass transition temperatures depending on the content of the cyclic olefin. Specifically, the product name “Apel” manufactured by Mitsui Chemicals, Inc., the product name “TOPAS” manufactured by Ticona, and the product name “Zeonor” manufactured by Nippon Zeon Co., Ltd. can be exemplified.

  Examples of the cyclic olefin polymer include, for example, JP-A-60-168708, JP-A-612012016, JP-A-61-115912, JP-A-61-115916, JP-A-6-115916. It can be produced according to known methods described in JP-A Nos. 61-271308, 61-272216, 62-252406, 62-252407 and the like.

  Furthermore, in the present invention, as the cyclic olefin-based resin, the cyclic olefin-based random copolymer, the cyclic olefin ring-opening (co) polymer, or the hydrogenated product of the cyclic olefin ring-opening (co) polymer (hydrogen) For example, a graft polymer obtained by modifying a compound) with a modifying agent such as an unsaturated carboxylic acid such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, (meth) acrylic acid, or an anhydride thereof may be used. it can. These modifiers can be used alone or in combination.

  The cyclic olefin resin, which is the component (a) used in the polyolefin resin laminate sheet of the present invention, preferably has a glass transition temperature (Tg) of 50 to 120 ° C. Here, if the glass transition temperature (Tg) is 50 ° C. or higher, the heat resistance of the sheet is maintained, and the concave portion (pocket portion) subjected to PTP molding is deformed when stored at a temperature higher than room temperature. This is preferable because it is difficult for defects to occur. On the other hand, a glass transition temperature (Tg) of 120 ° C. or lower is preferable because defects such as adhesion troubles between the front and back layers are unlikely to occur during PTP molding, and molding can be performed with good thickness accuracy. From these things, the glass transition temperature (Tg) of cyclic olefin resin becomes like this. More preferably, it is 60-110 degreeC, More preferably, it is 65-105 degreeC.

  In addition, the glass transition temperature (Tg) used in this invention is the value calculated | required as follows. That is, using a viscoelastic spectrometer DVA-200 (manufactured by IT Measurement Co., Ltd.), measurement was performed at a vibration frequency of 10 Hz, a strain of 0.1%, and a heating rate of 3 ° C./min. The peak value of E ″) was determined, and the temperature at that time was defined as the glass transition temperature (Tg).

Next, as the polyethylene resin as the component (b) used for the outer layer (B layer) laminated on both sides of the polyolefin resin laminated sheet of the present invention, the crystal melting peak temperature (Tm) is 110 to 130 ° C. And having a density of 0.920 to 0.940 g / cm ³ (hereinafter sometimes abbreviated as low to medium density polyethylene). Here, if the crystal melting peak temperature is 110 ° C. or higher, it is preferable because the sheet can be satisfactorily molded without sticking to the sheet heating portion at the time of PTP molding. This is preferable because stable PTP molding at a relatively low temperature, which has been performed with a sheet, is possible. Accordingly, the lower limit of the crystal melting peak temperature (Tm) of the polyethylene resin is more preferably 112 ° C. or higher, and the upper limit is more preferably 128 ° C. or lower. Further, if the density of the polyethylene-based resin is 0.920 g / cm ³ or more, it is preferable because the sheet can be molded without sticking to the heating portion at the time of PTP molding, while 0.940 g / cm ³ or less is preferable. For example, the external haze is hardly deteriorated during extrusion molding, and thus a sheet having a good appearance can be obtained. From these things, more preferably the lower limit of the density of the polyethylene resin is 0.921 g / cm ³ or more, more preferably 0.922 g / cm ³ or more. Further, more preferably the upper limit is 0.937 g / cm ³ or less, still more preferably 0.935 g / cm ³ or less. In order to improve the transparency of the sheet, it is preferable to use a polyethylene resin polymerized using a homogeneous catalyst (metallocene catalyst or the like) having a narrow molecular weight distribution and high transparency. In the A layer constituting the intermediate layer, high-density polyethylene may be used together with the low-medium-density polyethylene as the polyethylene-based resin as the component (b). Here, the high-density polyethylene has a crystal melting peak temperature (Tm) exceeding 130 ° C. and a density exceeding 0.940 g / cm ³ . When high-density polyethylene is used only for the A layer constituting the intermediate layer, the external haze is hardly deteriorated, and a decrease in moisture resistance is suppressed, which is preferable.

  Next, as for the A layer which comprises the intermediate | middle layer of the polyolefin-type resin lamination sheet of this invention, the mixing mass ratio of the said (a), (b) component is (a) / (b) = 60-100 / 0. It is important to be 40% by mass. Here, when the content of the component (a) is 60% by mass or more and 100% by mass or less, the elastic modulus at the time of PTP molding is sufficiently small, so that the moldability is good and the moisture resistance can be secured. Moreover, if content of (b) component is 40 mass% or less, since a moldability and impact resistance are favorable and a significant transparency fall does not arise, it is preferable. From these, it is more preferable that the mixing mass ratio of the components (a) to (b) is (a) / (b) = 65 to 95/5 to 35% by mass, and (a) / (b) = 70 to 90/10 to 30% by mass is more preferable.

  Moreover, as for B layer which comprises both the outer layers of the polyolefin-type resin laminated sheet of this invention, the mixing mass ratio of said (a), (b) component is (a) / (b) = 5-40 / 60-95. It is important to be mass%. Here, if content of (a) component is 5 mass% or more, it is preferable in the hand cutability evaluation of a PTP molded sheet, since the hand cut property of a slit part can be improved. On the other hand, if the content of the component (a) is 40% by mass or less, the oil resistance and transparency of the sheet are hardly reduced, which is preferable. From these, it is more preferable that the mixing mass ratio of the components (a) and (b) is (a) / (b) = 10 to 35/65 to 90% by mass, and (a) / (b) = 15-30 / 70-85 mass% is still more preferable. In addition, although the composition of B layer which comprises both outer layers may be the same or different by the surface layer and a back layer, it is preferable from points, such as dimensional stability (such as curl prevention).

  Moreover, as for B layer which comprises both the outer layers of the polyolefin-type resin laminated sheet of this invention, the mixing mass ratio of said (a), (b) component is (a) / (b) = 5-40 / 60-95. In addition to the mass%, it is important that the component (a) is further dispersed and the average dispersed particle diameter is 0.2 to 1.0 μm. Here, it is preferable that the average dispersed particle diameter is 0.2 μm or more and 1.0 μm or less because the balance between hand cutting and transparency is good. For these reasons, the lower limit of the average dispersed particle diameter is more preferably 0.3 μm or more, and further preferably 0.4 μm or more. Moreover, as an upper limit, it is more preferable that it is 0.9 micrometer or less, and it is still more preferable that it is 0.8 micrometer or less. Here, the average dispersed particle size means that a sample is cut out from a direction perpendicular to the longitudinal direction (flow direction) of the obtained laminated sheet, the sample is dyed with ruthenium tetroxide, and then a thin piece having a thickness of about 700 mm is collected. The cross section of the B layer constituting the outer layer was observed with a transmission electron microscope (JEM-1200EX, manufactured by JEOL Ltd.) at an acceleration voltage of 80 KV and 20,000 times. This is a value obtained by measuring the maximum dispersed particle diameter of each domain of the cyclic polyolefin resin in the actual size of 4 μm × 4 μm and calculating the average value.

  Factors affecting the average dispersed particle size of component (a) in layer B constituting both outer layers of the polyolefin-based resin laminate sheet of the present invention include melt viscosity at the molding temperature of each component used, screw design, extruder Type (single screw extruder, twin screw extruder, etc.) and shear energy (specific energy). In the present invention, for example, with respect to the melt viscosity, the melt viscosity ratio (ρa / ρb) between the melt viscosity (ρa) of the component (a) and the melt viscosity (ρb) of the component (b) in the B layer at the molding temperature. Is preferably in the range of 0.1 to 10, more preferably 0.2 to 5.0, and still more preferably 0.5 to 2.0. As the type of extruder, a production method in which a single-screw extruder is used for melt-kneading and forming a sheet is preferably used. In particular, the intermediate layer is a twin-screw extruder in the same direction, and the front and back layers are single. A production method in which a sheet is melt-kneaded using a shaft extruder and formed into a sheet by a co-extrusion method is preferably used.

  In the present invention, the tensile elongation at break of the sheet composed of the resin composition of the B layer constituting the outer layer (single layer sheet only of the B layer) is preferably 500% or less, more preferably 100 to 400%. Yes, more preferably 120 to 350%. This is because the tensile break elongation of the polyolefin resin laminated sheet of the present invention, particularly the tensile break elongation in the direction perpendicular to the slit forming direction of the B layer constituting the outer layer, is easy to break the sheet when the sheet is folded at the slit portion. It is presumed that it affects the hand cutting performance. Here, if the tensile elongation at break is 500% or less, it is preferable because the sheet is easily cut when folded along the slit portion and the hand cutting property is good. On the other hand, if the tensile elongation at break is too small, the hand tearability is good, but on the other hand, it tends to cause problems such as cracking from the slit when the sheet falls, so the lower limit is 100% or more. Is preferred. Further, the tensile breaking elongation of the B layer constituting the outer layer depends on the mixing mass ratio of the components (a) and (b) constituting the B layer, but the type (molecular weight) of the polyethylene resin as the component (b) , Molecular weight distribution, degree of branching distribution, polymerization catalyst species, etc.), so that it is preferable to select appropriately.

  Next, it is important that the thickness ratio of the intermediate layer (A layer) of the polyolefin-based resin laminate sheet of the present invention is 60 to 95% with respect to the total thickness of the sheet. Here, if the thickness ratio with respect to the total thickness of the sheet is 60% or more and 95% or less, it is preferable because the moldability, oil resistance, transparency, hand cutting property, and the like are good while ensuring moisture resistance. From these things, it is more preferable that the thickness ratio with respect to the total thickness of the sheet is 65 to 90%.

  Although the total thickness of the polyolefin-type resin laminated sheet of this invention does not have a restriction | limiting in particular, Usually, it is about 20-1000 micrometers. For example, when used for a PTP package, it is generally 200 to 350 μm. Similarly, the thickness of the outer layer (B layer) is not particularly limited, but is preferably 5 μm or more. Here, the thicknesses of both outer layers (B layer) may be the same or different.

  The polyolefin-based resin laminate sheet of the present invention is most preferably used in a three-layer configuration of an A layer constituting an intermediate layer and an B layer as an outer layer laminated on both front and back sides, but is limited to this configuration. Instead, the intermediate layer may include layers other than the A layer. For example, (B layer) / (A layer) / (B layer) / (A layer) / (B layer) 5 layer constitution, adhesive resin between intermediate layer (A layer) and outer layer (B layer) (B layer) / adhesive layer / (A layer) / adhesive layer / (B layer) 5 layer constitution or (B layer) / adhesive layer / (A layer) / adhesive layer / ( Examples include a 9-layer configuration of (B layer) / adhesive layer / (A layer) / adhesive layer / (B layer). In addition, the resin composition of each adhesive layer may be the same or different.

  Other components may be appropriately added to the polyolefin-based resin laminate sheet of the present invention as long as the gist of the present invention is not impaired. Here, other components may be added only to the A layer or the B layer, or may be added to both the A layer and the B layer. Examples of other components include various improvers and additives, such as impact resistance improvers such as polyolefin-based and polystyrene-based thermoplastic elastomers, and petroleum resins (petroleum resins, terpene resins, coumarone-indenes). Resins, rosin resins, or hydrogenated derivatives thereof), stabilizers, antioxidants, UV absorbers, light stabilizers, nucleating agents, antibacterial / antifungal agents, antistatic agents, slipping agents, etc. And recycled resin generated from trimming loss and the like (usually added to the A layer constituting the intermediate layer).

  The above-mentioned petroleum resins (hereinafter abbreviated as component (c)) are suitably used for the polyolefin-based resin laminate sheet of the present invention. It is considered that by mixing the petroleum resin as component (c), it can enter the molecular gap of the cyclic olefin resin, suppress the molecular motion of the cyclic olefin resin, and further improve the moisture resistance.

  Here, examples of the petroleum resin include an alicyclic petroleum resin obtained by polymerizing cyclopentadiene or a dimer thereof, and an aromatic petroleum resin obtained by polymerizing the C9 component. Examples of the terpene resin include a terpene-phenol resin obtained by polymerizing β-pinene. Examples of rosin resins include rosin resins such as gum rosin and wood rosin, and esterified rosin resins modified with glycerin, pentaerythritol, and the like.

  Petroleum resins as component (c) exhibit relatively good compatibility when mixed with cyclic olefin resin as component (a) and polyethylene resin as component (b). Further, since the color tone, thermal stability, compatibility and the like are particularly good, it is preferable to use a hydrogenated petroleum resin or terpene resin as the petroleum resin as the component (c). Specifically, Mitsui Chemicals' product names “Hilets” and “Petrogin”, Arakawa Chemical Industries' product name “Arcon”, Yashara Chemicals' product name “Clearon”, Idemitsu Petrochemical Co., Ltd. ) And trade name “Escolez” of Tonex Co., Ltd. can be used.

  The softening point of the petroleum resin component (c) is preferably 90 to 150 ° C, and more preferably 110 to 140 ° C. Here, if the softening point of petroleum resins is 90 ° C. or higher, moisture resistance can be improved efficiently. On the other hand, if it is 150 ° C. or lower, good compatibility is maintained and transparency is improved. It is preferable because it is difficult for the decrease to occur.

  Moreover, it is preferable that it is 50-120 degreeC, and, as for the glass transition temperature (Tg) calculated | required by the differential scanning calorimetry of petroleum resin which is (c) component, it is more preferable that it is 60-110 degreeC. Here, if the glass transition temperature (Tg) of petroleum resins is 50 ° C. or higher, moisture resistance can be improved efficiently. On the other hand, if it is 120 ° C. or lower, PTP moldability and transparency are improved. It is preferable because it is difficult for the decrease to occur. From these facts, the relationship between the glass transition temperature (Tg) of the petroleum resin as component (c) and the glass transition temperature (Tg) of the cyclic olefin resin as component (a) is as follows: It is particularly preferred that the glass transition temperature (Tg) of a certain petroleum resin is equal to or greater than the glass transition temperature (Tg) of the cyclic olefin resin that is the component (a).

  (C) Petroleum resins as components may cause problems such as volatilization of contained low molecular weight materials or bleeding on the surface of the sheet due to bleed on the surface of the sheet during extrusion molding. Therefore, it is more preferable to add the component (c) only to the A layer constituting the intermediate layer.

  Moreover, in the polyolefin-type resin laminated sheet of this invention, (c) component is 5-50 with respect to 100 mass parts of resin compositions which have (a) component and (b) component which comprise A layer as a main component. It is preferable to mix | blend a mass part, and it is further preferable that it is 10-40 mass parts. Here, if the compounding quantity of (c) component is 5 mass parts or more, since transparency and moisture-proof property can be improved, it is preferable. On the other hand, if it is 50 parts by mass or less, the melt viscosity is significantly reduced, extrusion molding becomes unstable, and problems such as a decrease in impact resistance of the entire laminated sheet are less likely to occur.

  Next, although the manufacturing method of the polyolefin-type resin lamination sheet of this invention is demonstrated, it can carry out by a conventionally well-known method and is not specifically limited. For example, the resin can be melted using a plurality of extruders, co-extruded from a T-die, and cooled with a cast roll to produce a sheet.

  The resin composition constituting each layer of the polyolefin-based resin laminate sheet of the present invention may be pre-compounded using a twin-screw extruder, a kneader, a Henschel mixer, etc., or each material is dry blended and directly extruded. It may be thrown into. However, when pre-compounding using a twin-screw extruder or the like, if the dispersibility of the component (a) in the B layer is excessively improved, the hand cutting property at the slit portion may be lowered. It is preferable to select appropriately and pay attention to the content and dispersion diameter of the component (a) in the B layer. The extrusion molding temperature is appropriately adjusted depending on the flow characteristics and film-forming property of the mixed resin composition, but is generally 260 ° C. or less, preferably in the range of 200 to 250 ° C. In addition, when petroleum resins are blended, low molecular weight components contained in petroleum resins volatilize during extrusion, or bleed on the surface of the sheet and dirt adheres to the cast roll. Since a problem may occur, a vent port may be provided in the cylinder portion of the extruder to remove low molecular weight components of petroleum resins. In addition, the cyclic olefin-based resin as component (a) depends on the primary structure, but it is easy to generate fish eyes and other defects due to shearing during extrusion. It is also preferable to use a method such as purging or extruding with a lubricant (PE wax, antioxidant or the like) attached thereto.

  Hereinafter, although an Example and a comparative example demonstrate in more detail, this invention is not limited to these.

In addition, the various measured values and evaluation about the sheet | seat etc. which are shown in this specification were calculated | required as follows. Here, the flow direction of the laminated sheet from the extruder is referred to as the longitudinal direction.
(1) Crystal melting peak temperature (Tm)
Using a differential scanning calorimeter “DSC-7” (manufactured by PerkinElmer), the temperature was determined from a thermograph when 10 mg of a sample was heated at a heating rate of 10 ° C./min according to JIS K7121.

(2) Melt viscosity A Koka-type flow tester “CFT-500C” (manufactured by Shimadzu Corporation) is attached with a nozzle (diameter 1 mm × length 10 mm), pre-heated at 240 ° C. for 5 minutes, and then melt viscosity sheared The speed dependency was measured, and the apparent viscosity (Pa · s) at a shear rate of 100 s ⁻¹ was determined.

(3) Average dispersed particle size
A sample is cut out from the direction perpendicular to the longitudinal direction (flow direction) of the obtained laminated sheet, and the sample is dyed with ruthenium tetroxide, and then a thin piece having a thickness of about 700 mm is collected to obtain a layer B constituting the outer layer. The cross section was observed with a transmission electron microscope (JEM-1200EX, manufactured by JEOL Ltd.) at an acceleration voltage of 80 KV and 20,000 times. The maximum dispersed particle size of each domain of the cyclic polyolefin resin in the actual size of 4 μm × 4 μm was measured, and the average value was defined as the average dispersed particle size. The unit is μm.

(4) Oil resistance The obtained laminated sheet was immersed in n-heptane and evaluated for appearance change, transparency, etc. after standing at 23 ° C. for 3 days. The thing to do was described as "x".

(5) Tensile elongation at break
A single-layer sheet made of the resin composition of the outer layer (B layer) is prepared, and the direction perpendicular to the longitudinal direction (flow direction) of the sheet is a temperature of 23 ° C. and a test speed of 200 mm / min in accordance with JIS K7127. The tensile breaking elongation was measured under the conditions.
Here, the single-layer sheet (thickness 50 μm) used for the sample was charged into the single-layer extruder (φ75 mm, L / D = 32, rotation speed: 80 rpm) with the resin composition of the outer layer being set at a set temperature of 240 ° C. After melt-kneading, it was extruded from a T-die, taken with a cast roll at 50 ° C., and cooled and solidified.

(6) Hand cutting property The product name “FBP-200U” (manufactured by CKD Co., Ltd.) is used as the molding apparatus for PTP, and the PTP sheet (the slit is in the longitudinal direction (flow direction)) of the laminated sheet. Formed) and then laminated with aluminum foil (17 μm), and then punched into the form of PTP packaging. Next, using a PTP molded sheet, it is bent by hand about 100 degrees so that the aluminum foil side becomes concave, and then bent by hand so that the aluminum foil side becomes convex. That is, one reciprocal bending operation is performed. A case where it was easily divided into two was indicated as “◯”, and a case where it was not easily torn was indicated as “x”.

The following raw materials were used as the component (a), the component (b), and the component (c) constituting the polyolefin-based resin laminated sheets of Examples and Comparative Examples.
Raw material a1; manufactured by Nippon Zeon Co., Ltd. (trade name: ZEONOR 750R) glass transition temperature (Tg): 78 ° C., melt viscosity: 740 Pa · s
Raw material a2; manufactured by Mitsui Chemicals, Inc. (trade name: Apel APL 6509) glass transition temperature (Tg): 85 ° C., melt viscosity: 500 Pa · s
Raw material b1: Low density polyethylene (trade name: Novatec UJ960) manufactured by Nippon Polyethylene Co., Ltd. Tm: 126 ° C., MFR: 5.0 g / 10 min (JIS K 7210), density: 0.935 g / cm ³ , melt viscosity: 570 Pa · s
Raw material b2: manufactured by Ube Industries, Ltd., polyethylene synthesized by a homogeneous catalyst (trade name: UMERIT 3540F) Tm: 125 ° C., MFR: 4.0 g / 10 min (JIS K 7210), density: 0.931 g / cm ^3. Melt viscosity: 700 Pa · s
Raw material c1: manufactured by Arakawa Chemical Industries, Ltd., hydrogenated petroleum resin (trade name: Alcon P125) Softening point: 125 ° C. (glass transition temperature determined by differential scanning calorimetry: 75 ° C.)

Example 1
As shown in Table 1, the raw material a1 is used as the cyclic olefin resin, the raw material b1 is used as the polyethylene resin, and the mixing mass ratio thereof is (a1) / (b1) = 90/10% by mass. The composition is an intermediate layer (A layer), the raw material a1 is used as the cyclic olefin resin, the raw material b1 is used as the polyethylene resin, and the mixing mass ratio thereof is (a1) / (b1) = 20/80 mass%. A certain resin composition is used as the outer layer (B layer), the intermediate layer (A layer) is a single screw extruder (φ75 mm, L / D = 32, rotation speed: 80 rpm, double flight screw), and the front and back layers (B layer) are single. It is put into a shaft extruder (φ65 mm, L / D = 35, rotation speed: 30 rpm, double flight screw), and after melt-kneading at a set temperature of 240 ° C., the thickness of each layer is the outer layer (B layer) / intermediate layer (A layer) ) / Outer layer (B Layer) = 50 μm / 250 μm / 50 μm were co-extruded from a three-layer die, taken up with a cast roll at 50 ° C., and cooled and solidified to produce a 350 μm thick laminated sheet.

  The obtained sheet was evaluated for various physical properties and processability. Moreover, comprehensive evaluation was also performed about the obtained result, and all evaluation was favorable, and the thing which is satisfactory in practical use was described as "(circle)", and the thing which is inferior in any one was described as "*". The results are shown in Table 1. Moreover, the photograph which observed the B layer which is an outer layer of the obtained lamination sheet with the transmission electron microscope is shown in FIG. The photograph (dimension: 8 cm × 8 cm) is a photograph magnified 20,000 times. In the actual size, a range of 4 μm × 4 μm is shown, and a length of 1 cm (scale in the figure) corresponds to 0.5 μm. The domain (circular portion) dispersed in the photograph is the cyclic olefin resin as the component (a), and the matrix is the polyethylene resin as the component (b).

(Example 2)
As shown in Table 1, the thickness of each layer was the same as in Example 1 except that the thickness was changed to be outer layer (B layer) / intermediate layer (A layer) / outer layer (B layer) = 30 μm / 290 μm / 30 μm. Thus, a laminated sheet was produced. The results of evaluating the obtained laminated sheet are shown in Table 1.

(Example 3)
As shown in Table 1, the raw material a1 is used as the cyclic olefin resin, the raw material b1 is used as the polyethylene resin, and the mixing mass ratio thereof is (a1) / (b1) = 60/40% by mass. The composition is an intermediate layer (A layer), the raw material a1 is used as the cyclic olefin resin, the raw material b1 is used as the polyethylene resin, and the mixing mass ratio thereof is (a1) / (b1) = 30/70% by mass. A laminated sheet was prepared in the same manner as in Example 1 except that a certain resin composition was used as the outer layer (B layer). The results of evaluating the obtained laminated sheet are shown in Table 1.

Example 4
As shown in Table 1, the raw material a2 is used as the cyclic olefin resin, the raw material b2 is used as the polyethylene resin, and the mixing mass ratio thereof is (a2) / (b2) = 90/10% by mass. The composition is an intermediate layer (A layer), the raw material a2 is used as the cyclic olefin resin, the raw material b2 is used as the polyethylene resin, and the mixing mass ratio thereof is (a2) / (b2) = 20/80 mass%. A laminated sheet was prepared in the same manner as in Example 1 except that a certain resin composition was used as the outer layer (B layer). The results of evaluating the obtained laminated sheet are shown in Table 1.

(Example 5)
As shown in Table 1, the raw material a1 is used as the cyclic olefin resin, the raw material b1 is used as the polyethylene resin, and the mixing mass ratio thereof is (a1) / (b1) = 90/10% by mass. A laminated sheet was produced in the same manner as in Example 1 except that the resin composition in which 25 parts by mass of the raw material c1 as a petroleum resin was mixed with 100 parts by mass of the product was an intermediate layer (A layer). The results of evaluating the obtained laminated sheet are shown in Table 1. Moreover, it was 0.26 g / m < ² > * day when the moisture permeability of the obtained lamination sheet was measured based on JISK7129 (A method). Moreover, as reference data, in the laminated sheet obtained from Example 1 in which petroleum resins were not blended, the moisture permeability was 0.37 g / m ² · day, and moisture resistance was improved by blending petroleum resins. It is confirmed that it can be further improved.

(Comparative Example 1)
As shown in Table 1, the raw material a1 is used as the cyclic olefin-based resin, the raw material b1 is used as the polyethylene-based resin, and the mixing mass ratio thereof is (a1) / (b1) = 20/80% by mass. Except that the product was used as the outer layer (B layer), and the resin composition was once melt-kneaded at a set temperature of 240 ° C. by a co-directional twin screw extruder (φ40 mm, L / D = 36, rotation speed: 100 rpm). Produced a laminated sheet in the same manner as in Example 1. The results of evaluating the obtained laminated sheet are shown in Table 1. Moreover, the photograph which observed the B layer which is the outer layer of the obtained lamination sheet with the transmission electron microscope is shown in FIG. The domain (circular portion) dispersed in the photograph is the cyclic olefin resin as the component (a), and the matrix is the polyethylene resin as the component (b). Compared with FIG. 1 of Example 1, it can confirm that the dispersed particle diameter (domain size) of cyclic olefin resin which is (a) component is small.

(Comparative Example 2)
As shown in Table 1, the raw material a1 is used as the cyclic olefin resin, the raw material b2 is used as the polyethylene resin, and the mixing mass ratio thereof is (a1) / (b2) = 90/10% by mass. A laminated sheet was produced in the same manner as in Example 1 except that the product was an intermediate layer (A layer), and the outer layer (B layer) was formed using 100% by mass of the raw material b2 as a polyethylene resin. The results of evaluating the obtained laminated sheet are shown in Table 1.

(Comparative Example 3)
As shown in Table 1, the raw material a2 is used as the cyclic olefin resin, the raw material b2 is used as the polyethylene resin, and the mixing mass ratio thereof is (a2) / (b2) = 90/10% by mass. The composition is an intermediate layer (A layer), the raw material a2 is used as the cyclic olefin resin, the raw material b2 is used as the polyethylene resin, and the mixing mass ratio thereof is (a2) / (b2) = 60/40% by mass. A laminated sheet was prepared in the same manner as in Example 1 except that a certain resin composition was used as the outer layer (B layer). The results of evaluating the obtained laminated sheet are shown in Table 1.

(Comparative Example 4)
As shown in Table 1, the thickness of each layer was the same as in Example 1 except that the thickness was changed to be outer layer (B layer) / intermediate layer (A layer) / outer layer (B layer) = 100 μm / 150 μm / 100 μm. Thus, a laminated sheet was produced. The results of evaluating the obtained laminated sheet are shown in Table 1.

  From Table 1, it can confirm that the polyolefin-type resin laminated sheet prescribed | regulated by this invention has favorable moldability, oil resistance, and the hand cutting property of the slit part of a molded sheet (Examples 1-5). In Example 5, it can be confirmed that the moisture resistance is further improved by blending petroleum resins. On the other hand, (Comparative Example 1) When the resin composition of the outer layer is once melt-kneaded with a twin-screw extruder, the dispersed particle size of the cyclic olefin-based resin as the component (a) becomes small, and is hand cut. The sex was insufficient. (Comparative Example 2) When no cyclic olefin-based resin was blended in the outer layer, the hand cutting ability of the slit portion of the molded sheet was insufficient. (Comparative Example 3) When the blended amount of the cyclic olefin resin blended in the outer layer exceeded the amount specified in the present invention, the oil resistance was insufficient. (Comparative example 4) When the thickness ratio with respect to the total thickness of the intermediate layer was less than the range defined in the present invention, the hand cutting property of the slit portion of the molded sheet was insufficient.

It is the photograph which observed the B layer which is the outer layer of the lamination sheet obtained in Example 1 with the transmission electron microscope. It is the photograph which observed B layer which is the outer layer of the lamination sheet obtained by the comparative example 1 with the transmission electron microscope.

Claims (6)

A laminated sheet comprising an A layer constituting an intermediate layer and a B layer as an outer layer laminated on both sides thereof, wherein the A layer and the B layer are (a) a cyclic olefin resin and (b) a polyethylene resin. The mixing mass ratio of the layer A is (a) / (b) = 60 to 100/0 to 40% by mass, and the layer B is (a) / (b) = 5 to 40. In the B layer, the component (a) is dispersed, the average dispersed particle diameter is 0.2 to 1.0 μm, and the thickness of the A layer of the laminated sheet Is a polyolefin-based resin laminate sheet characterized in that is 60 to 95% of the total thickness. The cyclic olefin resin as the component (a) has a glass transition temperature (Tg) of 50 to 120 ° C., and the crystal melting peak temperature (Tm) of the polyethylene resin as the component (b) is 110 to 130 ° C. The polyolefin-based resin laminated sheet according to claim 1, wherein the polyolefin-based resin laminated sheet has a density of 0.920 to 0.940 g / cm ³ . The cyclic olefin-based resin of the component (a) is a random copolymer of ethylene and a cyclic olefin, a cyclic olefin ring-opening (co) polymer, a hydrogenated product of a cyclic olefin ring-opening (co) polymer, and these (copolymers). 3) The polyolefin resin laminate sheet according to any one of claims 1 to 2, which is at least one cyclic olefin resin selected from the group consisting of graft modified products of polymers. The polyolefin resin laminated sheet according to any one of claims 1 to 2, wherein the polyethylene resin as the component (b) is a resin polymerized using a metallocene catalyst. The cyclic olefin resin according to claim 3 is used as the (a) component, and the polyethylene resin according to claim 4 is used as the (b) component, respectively. Polyolefin resin laminated sheet. The PTP package body shape | molded from the polyolefin resin laminated sheet as described in any one of Claims 1-5.